WO1992002456A1 - Alumine utilisable dans des applications ayant recours a la catalyse - Google Patents

Alumine utilisable dans des applications ayant recours a la catalyse Download PDF

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Publication number
WO1992002456A1
WO1992002456A1 PCT/US1990/004248 US9004248W WO9202456A1 WO 1992002456 A1 WO1992002456 A1 WO 1992002456A1 US 9004248 W US9004248 W US 9004248W WO 9202456 A1 WO9202456 A1 WO 9202456A1
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WO
WIPO (PCT)
Prior art keywords
alumina
substrate
rehydration
bondable
hdn
Prior art date
Application number
PCT/US1990/004248
Other languages
English (en)
Inventor
Lee A. Pedersen
Emmanuel K. Saforo
Alan Pearson
David G. Gatty
Original Assignee
Aluminum Company Of America
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/712,872 external-priority patent/US5032379A/en
Application filed by Aluminum Company Of America filed Critical Aluminum Company Of America
Priority to PCT/US1990/004248 priority Critical patent/WO1992002456A1/fr
Publication of WO1992002456A1 publication Critical patent/WO1992002456A1/fr

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Classifications

    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst

Definitions

  • This invention relates to alumina products suitable for catalytic applications and to methods for producing such alumina products.
  • alumina having greater than 0.4 cc/g pore volume in the range 30 to 200 Angstroms pore diameter (2) a catalyst containing gamma alumina but essentially no eta
  • Figures 1 and 3-6 provide pore size distribution information.
  • Figure 2 is a plot of k versus substrate composition.
  • Figure 7 is a tabular presentation of carbon and hydrogen content for catalysts HDN-3 and -7.
  • Figure 8 is a tabular presentation of k versus activation temperature.
  • Figure 9 is a schematic presentation of a batch reactor system.
  • Ni and Mo were incorporated onto the heat treated aluminas by successive impregnation, drying and
  • Nitrogen ppms versus time of reaction was plotted to get pseudo-first order rate constants, or k values. These k's have been a very useful tool for comparing catalysts.
  • catalysts By altering the morphology of the alumina, catalysts have been produced with HDN activity 10-40% better than the activity of a well-regarded commercial sample tested under the same conditions.
  • Characteristic of the substrates disclosed herein is a high pore volume, e . g. greater than 0.4, preferably greater than 0.9 cc/ 3 , coupled with high surface area, e.g. greater than 300 m 2 /g. With the high catalytically active metal oxide loading, the surface of the finished catalyst is still around 200 m 2 /g.
  • CP rehydration bondable aluminas which means that upon hydration or hydrothermal treatment the particles will bond or coalesce.
  • the nominal median particle sizes are as follows: CP-1 1 micron; CP-05 0.3 microns. Further information on these materials is to be found in the following adapted from U.S. Patent Application Serial Nos. 553,101 and 582,934 of Alan Pearson.
  • hydrated alumina i.e. Al(OH) 3
  • This step is, per se, well known in the art, and discussed in e.g. U.S. Patent Nos. 2,915,365 and 3,222,129.
  • activation is described in U.S. Patent No. 4,051,072, column 3, line 46 to column 4, line 7, which portion is incorporated herein by reference.
  • Preferred activation conditions are inlet air temperature of 700 to 870°C, outlet temperature of 350 to 500°C and a powder
  • This "partially calcined" or “activated” powder typically has a
  • a significant property of the powder for this invention is that it must rehydrate to bond the individual powder particles together in a reasonable time during a forming step as set forth, for example, in Steps (5) and (6) of the Alumina Preparation Procedure in this Example below.
  • Suitable activated powder is e.g. Alcoa
  • Activated Alumina Powders CP-1 of Aluminum Company of America The CP Powders are rehydratable and form a hydroxyl bond upon contact with water. The rehydration reaction is exothermic. Typical physical properties for CP powders appear in Table I. The median particle sizes are the "50% ⁇ " entries.
  • the CP-1 particles have a different pore size distribution, i.e. different particle porosity, from that of the particles of CP-05. Mixing various ratios of CP-1 particles with CP-05 particles consequently permits tailoring of pore size distribution. To repeat, the pore size distribution of the mixture is a function of the relative proportions of CP-1 and CP-05 material in the mixture. Combining two or more
  • particle types of different individual-particle pore diameter size distributions leads to the ability to tailor-make new grades of rehydration bondable alumina exhibiting pore diameter size distributions different from those of the starting materials.
  • Table II gives the percentage of pore volume in the different Angstrom size ranges for three
  • Alumina having two very distinct major pore size range modes such as that demonstrated by CP-5 alumina above is termed a support with bimodal pore distribution or a bimodal support.
  • the CP-1 material contained phosphate dispersant residue.
  • a disadvantageous aspect of CP-5 alumina is the high quantity of pore volume at the small pore diameter (or micropore) region of the distribution. Thus, there is 46% in the 40-20 range, compared with, respectively 8.4 and 15% for CP-05 and CP-1 material. These small pores may tend to plug faster with e.g. carbon deposits.
  • the above-prepared alumina substrate which is a 50:50 weight mixture of CP-1 and CP-05 powders, has a He density (g/cc) of 3.02, surface area 352 m 2 /g and the following pore size distribution:
  • Figure 1 presents the pore volume information graphically. The area under the curve gives the pore volume. Note that two peaks are present in the curve.
  • FIG. 1 it is a plot of the derivative of the pore volume (V in cc/g) versus In (pore diameter in Angstroms).
  • the derivative values have been In normalized (i.e., dV is divided by In d 2 - In d 1 , instead of d 2 - d 1 ). This correction allows one to calculate the pore volume associated with a
  • Figure 1 for HDN-8 shows a bimodal distribution with peaks around 100 and around 1000 Angstroms, and the pore volumes are approximately 0.41 cc/g (30% of total pore volume) and 0.82 cc/g (59% of total pore volume), respectively.
  • This nickel nitrate solution was added to the alumina substrate, the solution being kept slightly more than enough to cover the powder
  • Step 6 The dried product of Step 6 was calcined at 400°C for 4 hours with a gentle flow of air in the calcination oven.
  • Step 7 The calcined product of Step 7 constituted the catalyst HDN-8 containing about 6 wt% NiO and 18 wt% MoO 3 . Its pore size distribution was as presented in Figure 1.
  • the catalyst was further treated by presulfiding prior to testing. This sulfiding
  • the boat was removed from the tube and the catalyst was immediately slurried in hexadecane.
  • Figure 9 shows the batch reactor system which was used to test the catalyst for HDN
  • autoclave vessel 300 cc, Autoclave Engineering
  • hexadecane being used to wash the catalyst out of the container and into the autoclave.
  • the reactor vessel also contained 1.5 g of CS 2 to keep the catalyst in the sulfided form.
  • the reactor system contained 1.0018 g of catalyst HDN-8, 4.5 g of synthetic crude and 150.6 g of hexadecane.
  • the autoclave vessel was closed and the loader was also connected to the system.
  • the vessel was stirred with an impeller at 1500 rpm to keep the catalyst well dispersed in the liquid medium.
  • the loader was pressurized to 1300 psig with H 2 and checked for leaks. The H 2 was released and a very small amount of H 2 was allowed in the reactor.
  • the reactor vessel was heated to 400°C over a 1 hour period and a sample was drawn to check for the absence of any synthetic crude in the reactor.
  • the required 400°C temperature was recovered and thereafter kept constant.
  • the samples are withdrawn and cooled to room temperature.
  • the pressure is kept constant at about 1000 psig.
  • the k values are determined by a "least squares" evaluation of the data.
  • the correlation number is greater than 94% in all cases.
  • Step 3 above there can be used instead of the Ni stipulated, Co, Fe, Cu, Zn, Cd and the lanthanide elements, and/or mixtures thereof, to produce the corresponding oxides.
  • Step 5 above there can be used instead of the Mo salt, salts of W, Nb, Ta, Te, V heteropoly acids generally, and/or mixtures thereof, to produce the corresponding oxides.
  • Step 1 there can be used promoter quantities of oxide of Zr, Ti, Cr, Si, alkali earths, lanthanides and/or their mixtures or solid state reaction products, preferably in a quanitity of up to 10%.
  • catalysts are HDN-3, 7, 9, and 2. They were prepared and tested in the same way as done for catalyst HDN-8 in Example I, the only differences being in alumina substrate preparation.
  • Figure 2 shows k value as a function of substrate composition.
  • Alcoa A is the above referenced CP-1 alumina;
  • Alcoa B is CP-05 alumina.
  • Water used for rehydration of the various substrate compositions is derivable from the "% solids" information in Table VII below.
  • Increased packing can be achieved additionally by experimentally varying the amount of water used for rehydration and then measuring density, in order to determine the amount of water required for maximum density for a given mix of rehydration bondable
  • Figure 7 gives the analytical results for C and H content of used catalyst. This shows that a carbonaceous material is deposited in the catalyst pores and that the coke content and composition seems to be related to the activity of the catalyst.
  • Crush strength was 8, 17, 15, and 9 lbs., respectively.
  • HDN-4 were, respectively, in the Tables. Experimental procedure was for Example I, except as otherwise indicated. HDN-4 was more active, i.e. had a greater k value, than HDN-1.
  • Extrusion formation provides an alternate to the "slurry-cast, crush, size" procedure given in the above section Alumina Preparation Procedure.
  • the formulation includes a plasticizer, such as an organic plasticizer, e.g. Avicel, a product of FMC,
  • plasticizer is a slowing of the rehydration, to provide greater working time, so that the extruded mixture is plastic during extrusion and is solidified by
  • powder ingredients are first dry mixed in a Simpson Mix Muller mixer to achieve blending.
  • the desired amount of water is then added and mixing continued for 15 minutes, followed by extrusion in bench-scale extruders, such as Type L of LUWA, Charlotte, NC, or the "B-B Gun"
  • Pore volume distribution as a function of pore size is about the same for each of Samples 18 to 20. This is shown in Table X. Table VI
  • the Interparticle Correction is the amount of pore volume contributed by the interstices between particles.
  • substrate of the invention is preferably characterized by a pore size distribution having 0.4 to 0.7 cc/g in the range 30 to 200 ⁇ and 0.3 to 0.8 cc/g in the range 500 to 5000 ⁇ . More preferably, the
  • volume/gram range is 0.5 to 0.7 cc/g in the range 30 to 200A.
  • % Solids was determined by dividing the weight of the alumina powder by the total weight of the alumina powder plus the water used.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

L'invention se rapporte: à une alumine, qui se caractérise par des pores ayant un volume supérieur à 0,4 cc/g pour des diamètres compris entre 30 et 200 Angstroms; à un catalyseur contenant de l'alumine gamma mais ne contenant en substance pas d'alumine êta; à un procédé d'adaptation spécifique de la répartition porométrique, qui consiste à agglomérer entre eux des mélanges de particules d'alumine agglomérable par réhydratation de porosité particulaire différente et/ou de granulométrie médiane différente; ainsi qu'à une technique d'extrusion de mélanges composés d'alumine agglomérable par réhydratation et d'eau.
PCT/US1990/004248 1985-03-18 1990-07-30 Alumine utilisable dans des applications ayant recours a la catalyse WO1992002456A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1990/004248 WO1992002456A1 (fr) 1985-03-18 1990-07-30 Alumine utilisable dans des applications ayant recours a la catalyse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/712,872 US5032379A (en) 1984-11-13 1985-03-18 Alumina suitable for catalytic applications
PCT/US1990/004248 WO1992002456A1 (fr) 1985-03-18 1990-07-30 Alumine utilisable dans des applications ayant recours a la catalyse

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WO1992002456A1 true WO1992002456A1 (fr) 1992-02-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5925592A (en) * 1995-10-04 1999-07-20 Katoh; Akira Process for preparing alumina carrier

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1245654A (en) * 1967-10-04 1971-09-08 Konink Zwavelzuurfabrieken V H Process for reducing the loss due to abrasion of alumina extrudates and of extruded catalysts based on alumina
US3850849A (en) * 1972-05-24 1974-11-26 Norton Co Formed alumina bodies for catalytic uses
US3856708A (en) * 1972-04-10 1974-12-24 Reynolds Metals Co Alumina catalyst support
US3898322A (en) * 1972-12-15 1975-08-05 Continental Oil Co Alumina having a binodal pore volume distribution
US4301033A (en) * 1978-11-06 1981-11-17 Nikki-Universal Co., Ltd. High apparent bulk density gamma alumina carrier and method of manufacture of same
US4315839A (en) * 1979-02-26 1982-02-16 Rhone-Poulenc Industries Spheroidal alumina particulates having bifold porosity and process for their preparation
US4356113A (en) * 1980-11-17 1982-10-26 Filtrol Corporation Substrates with calibrated pore size and catalysts employing the same
US4411771A (en) * 1980-12-24 1983-10-25 American Cyanamid Company Process for hydrotreating heavy hydrocarbons and catalyst used in said process
US4444899A (en) * 1980-04-21 1984-04-24 Sumitomo Aluminum Smelting Company, Limited Process for the production of low density activated alumina formed product
US4579839A (en) * 1983-11-18 1986-04-01 Aluminum Company Of America Rehydration bondable alumina
EP0176476A1 (fr) * 1984-09-14 1986-04-02 Schweizerische Aluminium Ag Procédé de préparation d'oxyde d'aluminium léger très actif dispersé et produits façonnés en oxyde d'aluminium léger et procédé de préparation des produits façonnés
US4795735A (en) * 1986-09-25 1989-01-03 Aluminum Company Of America Activated carbon/alumina composite
US4923843A (en) * 1986-09-25 1990-05-08 Aluminum Company Of America Peptized activated carbon/alumina composite
US4945079A (en) * 1984-11-13 1990-07-31 Aluminum Company Of America Catalyst of nickel and molybdenum supported on alumina

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1245654A (en) * 1967-10-04 1971-09-08 Konink Zwavelzuurfabrieken V H Process for reducing the loss due to abrasion of alumina extrudates and of extruded catalysts based on alumina
US3856708A (en) * 1972-04-10 1974-12-24 Reynolds Metals Co Alumina catalyst support
US3850849A (en) * 1972-05-24 1974-11-26 Norton Co Formed alumina bodies for catalytic uses
US3898322A (en) * 1972-12-15 1975-08-05 Continental Oil Co Alumina having a binodal pore volume distribution
US4301033A (en) * 1978-11-06 1981-11-17 Nikki-Universal Co., Ltd. High apparent bulk density gamma alumina carrier and method of manufacture of same
US4315839A (en) * 1979-02-26 1982-02-16 Rhone-Poulenc Industries Spheroidal alumina particulates having bifold porosity and process for their preparation
US4444899A (en) * 1980-04-21 1984-04-24 Sumitomo Aluminum Smelting Company, Limited Process for the production of low density activated alumina formed product
US4356113A (en) * 1980-11-17 1982-10-26 Filtrol Corporation Substrates with calibrated pore size and catalysts employing the same
US4411771A (en) * 1980-12-24 1983-10-25 American Cyanamid Company Process for hydrotreating heavy hydrocarbons and catalyst used in said process
US4579839A (en) * 1983-11-18 1986-04-01 Aluminum Company Of America Rehydration bondable alumina
EP0176476A1 (fr) * 1984-09-14 1986-04-02 Schweizerische Aluminium Ag Procédé de préparation d'oxyde d'aluminium léger très actif dispersé et produits façonnés en oxyde d'aluminium léger et procédé de préparation des produits façonnés
US4945079A (en) * 1984-11-13 1990-07-31 Aluminum Company Of America Catalyst of nickel and molybdenum supported on alumina
US4795735A (en) * 1986-09-25 1989-01-03 Aluminum Company Of America Activated carbon/alumina composite
US4923843A (en) * 1986-09-25 1990-05-08 Aluminum Company Of America Peptized activated carbon/alumina composite

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5925592A (en) * 1995-10-04 1999-07-20 Katoh; Akira Process for preparing alumina carrier

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