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
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
• • 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
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/053—Sulfates
• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/057—Selenium or tellurium; Compounds thereof
  • B01J27/0573—Selenium; Compounds thereof
• • 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
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/14—Phosphorus; Compounds thereof
  • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
• • 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • C07C2521/08—Silica
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/24—Chromium, molybdenum or tungsten
  • C07C2523/28—Molybdenum
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/24—Chromium, molybdenum or tungsten
  • C07C2523/30—Tungsten
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
  • C07C2523/44—Palladium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/75—Cobalt
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/755—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/057—Selenium or tellurium; Compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/14—Phosphorus; Compounds thereof
  • C07C2527/16—Phosphorus; Compounds thereof containing oxygen
  • C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-

Definitions

• This patent pertains to improved solid superacid catalysts which utilize a high surface area support material and have high catalytic activity More particularly, it pertains to such supported solid superacid catalysts which are produced by anion-modification of tetravalent transition metal oxides and stabilized by small amounts of a base or noble metal additive, all precipitated onto a particulate substantially inert solid support material having high surface area.
• metal oxides having molybdate, sulfate, or tungstate anions deposited on metal oxides such as zirconia (Zr0 2 ) and titania ( TiO 2 ) > have been shown to possess superacidity characteristics.
• solid superacid catalyzed reactions reported in the literature have been isomerization of n-butane and alkylation of light paraffin/olefms (C 3 -C 5 ) which are normally carried out at low temperature and pressure conditions.
• hydrocracking of long-chain hydrocarbons using solid superacid catalysts require hydrogen pressure to stabilize the catalyst.
• the solid superacids reported so far as catalysts have been associated with some disadvantages such as high cost and rapid deactivation on-stream by coking due to their high intrinsic acidic character
• European Patent 0 653 398 Al to Angstadt et al disclosed a catalyst containing sulfated zirconia and heteropolyacids for alkylation of paraffins and olefins, and disclosed that the presence of heteropolyacid or 3 polyoxoanions in the solid superacid catalyst resulted in higher yields of desired high- octane components.
• the strong acidity of solid superacids is generated after they are calcined at high temperatures such as above 600°C.
• the known solid superacid catalysts have undesirably limited surface area and catalytic activity, and also have rapid deactivation rates
• the known active solid superacids based upon zirconia compounds have only mediocre and insufficient surface areas needed for providing high catalytic activity, and also require large amounts or concentrations of expensive additive metal compounds.
• some useful solid superacid catalysts have been developed, further improvements are desired to provide highly active solid superacid catalysts having increased surface areas and long active life, and which are useful for various commercially important catalytic reactions
• This invention provides improved supported solid superacid catalysts which have high surface area and high catalytic activity, and which advantageously utilize only small concentrations of active metal compounds.
• the supported solid superacid catalyst utilizes anion-modification of a tetravalent transition metal oxide of a Group IV metal such as hafnium (Hf), tin (Sn), titanium (Ti), zirconium (Zr), or mixtures thereof, modified by an anion compound such as molybdate (Mo0 4 ), phosphate (P0 4 ) , selenate (Se0 4 ), sulfate (S0 4 ) or tungstate (WOJ, and stabilized against deactivation by addition of a suitable active promotor metal, all precipitated uniformly onto a strong particulate support material having high surface area such as alumina (Al 2 0 3 ), silica (S ⁇ 0 2 ), or mixtures thereof having an initial surface area of 100-500 m 2 /gm .
• Suitable active promotor metals may include small concentrations of a base metal including cobalt (Co) , nickel (Ni) or palladium (Pd), or a noble metal including platinum (Pt), rhodium (Rh), ruthenium (Ru) or mixtures thereof.
• the resulting supported superacid catalyst should have a composition of 70-90 wt. % support material, 5-20 wt. % transition metal oxide, 2-8 wt % anion modification compound, and 0.05-5 wt. % active promotor metal, and should have final total surface area after calcination of 100-450 m 2 /g .
• Preferred supported solid superacid catalyst compositions include either N ⁇ /Zr0 2 /S0 4 or Pt/Zr 0 2 /S0 4 each precipitated onto an alumina (Al 2 0 3 ) support material having 140-45- m 2 /gm surface area, with the percentage of the support material being 75-85 wt. %, the active transition metal oxide being 6-1 8 wt. % and the active promotor metal being between 0. 1 and 4 wt. % of the total catalyst, which has a final total surface area after calcination of 1 30-400 m 2 /gm .
• supported solid superacid catalysts produced according to the invention advantageously utilize significantly lesser amounts of the active metal compounds, but provide high surface area and high catalytic activity along with low deactivation rates, and also have relatively low cost as compared to known liquid or solid superacid catalysts. Because the catalyst active sites are generally proportional to the surface area of the support material being used, the supported solid superacid catalyst of this invention provides substantially increased number of activity sites as compared to the known unsupported solid superacid catalysts. These new supported solid superacid catalysts are effective and useful for alkylation, hydrocracking and isomenzation reactions at milder reaction conditions than those required when using conventional corrosive mineral acid catalysts, such as hydrofluoric acid (HF) and sulfuric acid (H 2 S0 4 )
• the supported solid superacid catalysts according to this invention are prepared by precipitation of hydroxides of Group IV metals, such as hafnium, tin, titanium, or zirconium onto a particulate high surface area metal oxide support material such as alumina or silica in a thin uniform layer, followed by anion-treatment with molybdate (Mo0 4 ), phosphate (P0 4 ), selenate (Se0 4 ), sulfate (S0 4 ), or tungstate (W0 4 ) and also addition of small amounts of a hydrogenation function active promotor metal such as cobalt, nickel, palladium, platinum, rhodium or ruthenium, or mixtures thereof, followed by calcination of the catalyst composition at temperature of 500-650°C for at least 2 hours to produce the final catalyst product.
• a hydrogenation function active promotor metal such as cobalt, nickel, palladium, platinum, rhodium or ruthenium, or mixtures thereof
• the resulting catalyst having such metals precipitation onto the metal oxide support material can be accomplished from aqueous solutions or by vapor precipitation, which results in the total surface area and the number of active sites for the final catalyst being substantially increased It has been found that useful particulate supported solid superacid catalysts of this invention can be advantageously produced which contains a high concentration of 70-90 wt. support material such as alumina or silica, and contain only 5-20 wt. of the active transition metal oxide such as hafnia, stannic oxide, titania or zirconia; 2-8 wt.
• the anionic modification material such as molybdate, phosphate, sulfate or tungstate; and only about 0 05 5 wt of the stabilizing active base metal such as cobalt, nickel, or palladium, or a noble metal such as platinum, rhodium and ruthenium.
• These supported solid superacid catalysts should have an effective particle size of 20 100 mesh (U S. Sieve Series), equivalent to 0.84-0.1 5 mm (0.033-0 006 inch) , and have a final surface area after calcination of 100-450 m 2 /gm
• the preferred catalyst particle size is 30-60 mesh (0.60-0.25 mm) and has 1 30-400 m 2 /gm final surface area It has been found that these supported solid superacid catalysts provide high catalytic activity reactions with low catalyst deactivation rates, and have relatively low cost for various conversion reactions which are of significant industrial importance Reactions for which the catalysts of this invention are useful and desirable as compared to known liquid or solid superacids include alkylation of refinery gases for production of high- octane gasoline, cracking and isomerization of long chain paraffins to produce fuel products, conversion of waste plastics and low quality lube oils and waxes to produce value-added lubricating oils and chemicals
• This invention advantageously provides improved supported solid superacid type catalysts for which relatively small amounts of the active metal compounds are precipitated onto strong metal oxide support materials having high surface area
• the resulting high surface area catalyst provides unexpectedly high catalytic activity, and is useful in various process reactions under relatively mild temperature and pressure conditions.
• These supported catalysts are environmentally safe and Iower in cost than the corrosive liquid acids or unsupported low surface area solid superacids which they replace, and also are capable of periodic regeneration and continued reuse
• FIGURE 1 is a chart showing a correlation of the supported solid superacid catalyst surface area and its activity ration for alkylation for refinery gas feedstreams with a similar unsupported solid superacid catalyst
• FIGURE 2 shows a general comparison of long term performance and deactivation behavior for the supported solid superacid catalysts of this invention with deactivation of known unsupported type solid superacid catalyst.
• solid superacid catalysts can be at least maintained and usually appreciably improved by precipitating relatively small amounts of active superacid metal compounds uniformly onto a suitable high surface area metal oxide support material such as gamma alumina (y-A ⁇ 2 0 3 ) , silica (S ⁇ 0 2 ) or mixture thereof.
• a suitable high surface area metal oxide support material such as gamma alumina (y-A ⁇ 2 0 3 ) , silica (S ⁇ 0 2 ) or mixture thereof.
• a suitable high surface area metal oxide support material such as gamma alumina (y-A ⁇ 2 0 3 ) , silica (S ⁇ 0 2 ) or mixture thereof.
• the resulting supported solid superacid catalyst which contains only 5-20 wt. % of the active solid superacid materials and exhibit at least comparable and usually appreciably higher catalytic activity in conversion of hydrocarbons as compared to the known unsupported type solid superacid catalysts which contain considerably greater weight percent of the active metals
• noble metals Pt, Pd
• the supported catalyst particle strength is adequate to permit use of the catalyst in ebullated or fluidized bed type reactors.
• the enhanced catalytic activity and slow deactivation of the supported solid superacid catalyst according to the present invention makes possible alkylation of light refinery gases to produce the high quality alkylates as gasoline additives for enhancing octane rating of gasoline products, and cracking of high molecular weight hydrocarbons such as plastics, waxes, and low quality lube oils under low severity conditions.
• the present invention provides a series of supported solid superacid catalysts which exhibit high catalytic activity and are more cost effective and attractive for many commercial catalytic process applications than known liquid or solid superacid catalysts
• This supported solid superacid catalyst can be used in reactors containing either fixed or fluidized type catalyst beds.
• the known solid superacid catalysts usually have an undesirably short useful life such as only 4-6 hours. But the present supported solid superacid catalysts can advantageously maintain high catalytic activity for at least about 72 hours and usually longer before requiring regeneration of the used catalyst.
• the used supported solid superacid catalysts of this invention can be regenerated by contacting it with air at 500 650°C temperature for 2-4 hours, with the catalyst being retained either in-situ or in a separate container
• This invention also includes a method for preparation of the supported solid superacid catalysts having high surface areas.
• alumina or silica support material 100 gram of y-AI 2 0 3 having effective particle size of about 60 mesh (U.S. Sieve Series) with initial surface area above 200 m 2 /g is preheated at 1 80°C temperature for 24 hours to remove all physically adsorbed moisture.
• 30 grams of Zr(S0 4 ) 2 is slowly added to 300 ml distilled water, the resulting mixture being stirred for 60 mm. until the Zr(S0 4 ) 2 salt is completely dissolved .
• the y-AI 2 0 3 particles are then added to the solution with constant stirring, with the stirring speed being increased to maintain the solid y-A ⁇ 2 0 3 material in the suspension
• Hydrolysis of the prepared solution is carried out by adding 28 wt % of NH 4 0H at rate of 0.7-0.8 ml/min., the hydrolysis step being completed at final pH of 9.5.
• the particle solution is filtered to remove excess ammonium solution and the supported zirconium hydroxide is washed twice with distilled water, each washing step being followed by a filtration step
• the support particles containing zirconium hydroxide are oven dried at 1 10°C temperature for 24 hours.
• Sulfate anion is introduced by sulfating the solid particles with 1 .0 N H 2 S0 4 for one hour.
• the sulfated zirconium hydroxide on the alumina support is dried in an oven at 1 10°C temperature for 1 2 hours
• Impregnation of nickel onto the dried catalyst material is carried out by the incipient wetness method. Based on the amount of the sulfated particulate solid used, 0.5-2 wt% nickel is introduced onto the surface of the sulfated solid . Typically, 0.85 grams of N ⁇ (N0 3 ) 2 .
• 6H 2 0 is dissolved in 1 2 ml distilled water. Impregnation of the solids is completed in three steps; each time 4.0 ml solution containing nickel salt is added to 10.0 grams sulfated solid, followed by drying at 1 10°C temperature. After introducing all the metal, the resulting sulfated solid is calcined at 620°C temperature for three hours to produce a supported solid superacid catalyst (N ⁇ /ZrO 2 /S0 4 /AI 2 O 3 ) having high surface area according to the invention
• a supported solid superacid catalyst utilizing silica (Si0 2 ) support material is produced similarly as described above for the alumina support material.
• the procedure to precipitate solid superacids on Si0 2 support is similar to the preparation of Pt/Zr0 2 /S0 4 /AI0 3 .
• One hundred grams of S ⁇ 0 2 gel having surface area of 345 m z /g is added 800 ml 0 1 5 M sulfate zirconium solution Hydrolysis is carried out until final pH of 9.5 is reached.
• Noble metal platinum additive is introduced the same way as for nickel to provide a supported solid supported catalyst Pt/Zr0 2 /S0 4 /S ⁇ 0 2 .
• the supported solid superacid catalysts of this invention can be advantageously used in processes for alkylation of light refinery C 3 % C 4 Stream gases to produce gasoline alkylates useful for improving the octane rating of gasoline products
• Useful reaction conditions for such a refinery gas alkylation process are 70-250°C temperature, 0-500 psig. pressure, and space velocity of 100- 1 000 volume gas feed/hr/volume of catalyst bed (Vf/hr/Vc)
• Preferred process reaction conditions are 100-200°C temperature, 0-200 psig. pressure, and space velocity of 1 60-400 Vf/hr/Vc.
• These supported solid superacid catalysts can also be advantageously used for cracking high molecular weight polymeric feed materials such as high density polyethylene (HDPE) , polyethylene and polystyrene, in a single catalytic reactor to produce aromatic products.
• Useful reaction conditions for such cracking processes are 100-500°C temperature, and 0-100 psig . pressure.
• Preferred reaction conditions are 1 25-450°C, temperature and 10-80 psig. pressure.
• Catalyst A Catalyst B
• BET surface area of Al 2 0 3 support material is 1 86 m /g; particle size was 60 mesh (U.S. Sieve Series) or 0.250 mm.
• the supported catalyst B contains about 80 wt % support material while the total active material specified as N ⁇ /Zr0 2 /S0 4 is only about 20 wt%. Due to precipitation of the active metals onto the high surface area support material Al 2 0 3 , the surface area of supported catalyst B was increased by about 60% The catalytic activities of these two solid superacid catalysts A and B towards cracking of plastics and alkylation of aromatics were compared using the same reaction conditions A 20 ml microautoclave was successfully charged with 1 .0 gram of dry catalyst and 1 .0 gram of polypropylene having average molecular weight of 250, 000. Four grams of toluene were added as the aromatic solvent compound.
• Catalyst active material is defined as N ⁇ /Zr0 2 /S0 4 .
• Alkyl groups on alkylated aromatics are C, -C 4 paraffinic substituents.
• catalysts A and B described in Table 1 were each introduced successively into a 20 ml microautoclave reactor together with a feed mixture including 0.5 gram polypropylene, 0.5 gram high density polyethylene (HDPE) , and 4.0 gram toluene to provide a plastics : solvent weight ratio of 1 :4. It is known that HDPE is a major component of typical waste plastics stream and which is the most difficult to crack.
• the reaction conditions used and results achieved for each solid superacid catalyst are provided in Table 3 TABLE 3
• Catalyst activity g.product/g. active 2 0 25 matenal.hr 10.0
• Alkyl groups on alkylated aromatics are C T -C,, paraffinic substituents.
• Catalyst D had the same composition as supported catalyst B, but was regenerated by heating it in air at 550°C for 2 hours to remove carbon deposits
• Alkyl groups on alkylated aromatics are C,-C 4 paraffinic substituents.
• Feed F l Feed F-2:
• the gasoline formation rate calculated on the basis of weight of gasoline produced per gram of active material per hour is almost six times greater than that of unsupported catalyst E. Furthermore, the selectivity for undesired higher molecular weight products (C n -C 14 ) was reduced with the supported catalyst F, thereby indicating that further oligomerization reaction was suppressed when the supported solid superacid was used
• Another supported solid superacid catalyst G was prepared by precipitating Pt/Zr0 2 /S0 4 onto high surface area silica (S ⁇ 0 2 ) support, as described in the catalyst preparation method . As also shown in Table 5, the final BET surface area of silica supported solid superacid catalyst G is increased to 1 96 m 2 /g The activity of the supported solid superacid catalyst G was compared with supported solid superacid catalyst F for alkylation of refinery gases In the comparison experiments, a refinery gas feed composition F2 having composition which resembles that in commercial alkylation processes was used.
• gasoline formation rate of 0.4 g/g active material was achieved with the silica supported solid superacid catalyst G, which was even higher than with alumina supported solid superacid catalyst F It is believed that supported solid superacid catalyst G has greater active sites than supported solid superacid catalyst F because of its higher surface area.
• Curve A shows percent n-butane conversion vs. onstream time for the unsupported solid superacid Mn Fe/Zr0 2 /S0 4 for isomenzation of n-butane. Data obtained from "Coal Liquefaction and Gas Conversion", Proceedings of DOE Contractors Review Conference, Pittsburgh, 1 995, pp.295, Figure 4.
• Curve B shows alkylation of refinery gas feeds F1 and F2 with supported catalyst Pt/Zr0 2 /S0 4 /Al 2 0 3 conducted at 1 70°C temperature, ambient pressure, and at 240 gas hourly space velocity. It is seen that the supported solid superacid catalyst remained very active after 72 hours on stream operation

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=24235157

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (30)

Family Cites Families (8)

• 1996
  • 1996-11-18 AU AU77365/96A patent/AU7736596A/en not_active Abandoned
  • 1996-11-18 EP EP96940501A patent/EP0873191A1/de not_active Withdrawn
  • 1996-11-18 WO PCT/US1996/018436 patent/WO1997018892A1/en not_active Application Discontinuation
  • 1996-11-18 CA CA002238034A patent/CA2238034A1/en not_active Abandoned

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events