US20030181778A1 - Catalytic system for the production of olefins - Google Patents

Catalytic system for the production of olefins Download PDF

Info

Publication number
US20030181778A1
US20030181778A1 US10/359,191 US35919103A US2003181778A1 US 20030181778 A1 US20030181778 A1 US 20030181778A1 US 35919103 A US35919103 A US 35919103A US 2003181778 A1 US2003181778 A1 US 2003181778A1
Authority
US
United States
Prior art keywords
nitrides
deposited
oxy
catalytic
catalytic bed
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US10/359,191
Other languages
English (en)
Inventor
Luca Basini
Domenico Sanfilippo
Alessandra Guarinoni
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SnamProgetti SpA
Original Assignee
SnamProgetti SpA
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
Application filed by SnamProgetti SpA filed Critical SnamProgetti SpA
Assigned to SNAMPROGETTI S.P.A. reassignment SNAMPROGETTI S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASINI, LUCA, GUARINONI, ALESSANDRA, SANFILIPPO, DOMINICO
Publication of US20030181778A1 publication Critical patent/US20030181778A1/en
Assigned to SNAMPROGETTI S.P.A. reassignment SNAMPROGETTI S.P.A. RECORD TO CORRECT ASSIGNOR #2'S NAME ON AN ASSIGNMENT PREVIOUSLY RECORDED ON REEL/FRAME 014127/0105. (ASSIGNMENT OF ASSIGNOR'S INTEREST) Assignors: BASINI, LUCA, GUARINONI, ALESSANDRA, SANFILIPPO, DOMENICO
Priority to US11/561,092 priority Critical patent/US20070123744A1/en
Priority to US12/033,572 priority patent/US7829753B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • 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
    • C07C2523/42—Platinum
    • 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
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/644—Arsenic, antimony or bismuth
    • 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
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/652—Chromium, molybdenum or 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • 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
    • C07C2527/24—Nitrogen compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalytic system for the production of olefins by means of a partial oxidation process of saturated hydrocarbons such as ethane, propane, isobutane and naphtha.
  • saturated hydrocarbons such as ethane, propane, isobutane and naphtha.
  • the catalytic system and the reactor solutions described provide the possibility of effecting the partial oxidation reactions of saturated hydrocarbons to olefins also with a low contact time, at a high temperature and high pressure.
  • Olefins have various uses in the production field of polymers (for example, polyethylene, polypropylene), copolymers (for example, synthetic rubbers), plastic materials (for example, vinyl plastics), basic chemical products (for example, ethylene oxide, propylene oxide, cumene and acrolein) and high-octane products (for example, methyl tertbutyl ether).
  • polymers for example, polyethylene, polypropylene
  • copolymers for example, synthetic rubbers
  • plastic materials for example, vinyl plastics
  • basic chemical products for example, ethylene oxide, propylene oxide, cumene and acrolein
  • high-octane products for example, methyl tertbutyl ether
  • Olefins are industrially produced by means of non-catalytic steam cracking processes and fluid bed or mobile bed or fixed bed catalytic dehydrogenation processes.
  • Steam cracking is the most widely-used process for producing low molecular weight olefins such as ethylene and propylene and can treat mixed charges of hydrocarbons such as naphtha. Steam cracking processes can be divided into three zones where the following operations take place:
  • the chemical reactions in the steam cracking processes are pyrolysis reactions which are effected at high temperatures by passing a stream of saturated hydrocarbons and steam inside coiled tubes inserted in an oven.
  • the residence times of the gaseous stream of the reagents inside the tubes typically vary from 0.1 to 0.15 sec. but there are also technologies which use residence times of a few milliseconds.
  • the inlet temperatures of the tubes range from 500-700° C., whereas those at the outlet are within the range of 775-950° C.
  • the reaction zone of the plants is modular.
  • the modules have a capacity of about 100,000 tons/year; as a whole world-scale plants have a capacity which is even higher than 750,000 tons/year.
  • the yields vary from 50 to 60% on a molar basis depending on the charges used. Starting from ethane, the yields can range from 57-60% on a molar basis, with conversion values of ethane which can reach 67% and selectivity values to ethylene which can reach 83%.
  • Catalytic dehydrogenation processes are mainly used for the production of propylene, butenes and pentenes from pure charges of propane, isobutane, butane and isopentane (F. Buonomo, D. Sanfilippo, F. Trifiro, Dehydrogenation Reactions in: “Handbook of Heterogeneous Catalysis”, Vol. 5, pages 2140-2151, G. Ertl, H. Knozinger, J. Weitkamp Eds. VCH Verlagsgesellschaft mbH, Weinheim).
  • Industrial catalytic dehydrogenation processes are mainly based on three groups of materials consisting of:
  • mixed oxides such as molybdenum and vanadium oxides.
  • the reactor solutions used in catalytic dehydrogenation technologies comprise a reaction step in which the dehydrogenation of the hydrocarbon takes place, and a regeneration step of the catalyst consisting of a combustion process of the carbonaceous residues accumulated in the reaction step.
  • reaction solutions used comprise:
  • fluid bed reactors in which the catalyst circulates continuously between a regeneration and reaction reactor conveying the heat necessary for the dehydrogenation (FBD technology of Snamprogetti-Yarsintez, D. Sanfilippo, F. Buonomo, G. Fusco, M. Lupieri, I. Miracca Che.Eng.Sci. 1992, 47, 2313).
  • the reactions are carried out with a low contact time ( ⁇ 10 ms) and produce olefins from mixtures of the corresponding saturated alkanes and oxygen/air.
  • WO-00/14035 of Dow Chemical Company claims a catalytic partial oxidation process for the production of olefins effected by putting paraffins, oxygen and hydrogen in contact with each other.
  • the patent also claims the possibility of carrying out the reactions in a fluid bed reactor.
  • WO-00/14180 of Dow Chemical Company claims a partial oxidation process of hydrocarbons with an autothermal process in the presence of a catalyst comprising at least one metallic promoter supported on a fibrous monolithic carrier in which the presence of hydrogen together with oxygen and hydrocarbon is recommended.
  • the patent also claims a method for regenerating the catalyst during the reaction conditions
  • WO-00/37399 of BP Chemical Ltd. claims a production and separation process of olefins by means of the partial oxidation of hydrocarbons comprising a partial oxidation passage of hydrocarbons and a separation step by means of an interaction with a solution of a metallic salt capable of selectively absorbing the olefins.
  • WO-00/14036 of BP Chemical Ltd. claims a catalytic process for the production of olefins by means of the partial oxidation of hydrocarbons carried out in various steps.
  • combustion reactions are effected which do not completely use up the oxygen; in a second step with a second catalyst, the combustion products and the non-reacted oxygen are interacted with the other saturated hydrocarbon causing the total consumption of the oxygen and olefins.
  • WO-00/15587 of BP Chemical Ltd. claims a catalytic process for the production of olefins and synthesis gas by means of the partial oxidation of hydrocarbons.
  • premixed streams of hydrocarbons, oxygen and hydrogen creates problems relating to safety particularly when the premixed streams are within flammability and explosivity curves (as in the case of the mixtures described in the documents of literature mentioned above).
  • the catalytic beds must be filled and have such dimensions as to allow low pressure drops, with the consequent use, in most of the experiments described in literature, of fluid beds or catalytic beds consisting of monoliths.
  • the great increase in temperature and the increase in the number of reaction moles [2] may be a further cause of a pressure drop inside the catalytic bed.
  • the pressure drop can be limited by an increase in the total pressure, but this increase favours radicalic reactions in gaseous phase which form by-products with a high C/H ratio and in particular carbonaceous residues which deactivate the catalysts.
  • a catalytic system has now been found, which has an exceptional thermal, chemical and mechanical stability and provides the possibility of carrying out partial oxidation reactions of saturated hydrocarbons to olefins also with a low contact time, at a high temperature and high pressure.
  • the catalytic system, object of the present invention, for catalytic partial oxidation reactions of hydrocarbons is characterized in that it contains:
  • one or more metals belonging to the 1 st , 2 nd and 3 rd transition series preferably selected from Pt, Cr, V, Mo, W, Cu, Ru, Zn, Ag, Au, Rh, Mn, Fe, Co and Ni;
  • one or more elements of group IIIA, IVA or VA preferably selected from Sn, Ga, Pb, Sb, Bi, Si,
  • At least one of said metals or said elements is in the form of a nitride.
  • the metal (or metals) belonging to the 1 st , 2 nd or 3 rd transition series can be in the catalytic system in the form of a nitride (as counter-ion of the nitride or oxy-nitride) and/or deposited, in a quantity preferably ranging from 0.05 to 15% by weight, with respect to the nitride or oxy-nitride, whereas the element (or elements) of group IIIA, IVA or VA can be in the catalytic system in the form of a nitride (as counter-ion of the nitride or oxy-nitride) and/or deposited, in a quantity preferably ranging from 0.05 to 15% by weight, with respect to the nitride or oxy-nitride.
  • nitrides of transition metals have intrinsic catalytic properties, others can be used as carriers of metallic species with catalytic properties such as, for example, bimetallic or trimetallic systems (i.e. where there are two or three metals deposited on the nitride or on the oxy-nitride) preferably selected from the combinations Pt—Sn, Pt—Ga and Pt—Cu and the combinations Pt—Sn—Cr, Pt—Sn—Ga, Pt—Sn—Bi and Pt—Sn—Sb, respectively.
  • bimetallic or trimetallic systems i.e. where there are two or three metals deposited on the nitride or on the oxy-nitride
  • nitrides can be metioned, consisting of:
  • Si—N—B systems or Si—B—N—C systems such as Si 3 B 3 N 7 and SiBN 3 C (H. P. Baldus and M. Jansen, Angew. Chem. Int. Ed. Engl. 1997, 36, 328)
  • [0065] systems consisting of layers of aluminum nitrides deposited on oxide carriers by means of atomic layer epitaxy or chemical vapour deposition (M. E. Bartram, T. A. Michalske, J. W. Rogers, T. M. Mayer Chem. Mater. 1991, 3, 353; M. E. Bartram, T. A. Michalscke, J. W. Rogers, R. T. Paine, Chem. Mater., 1993, 5, 1424; C. Soto, V. Boiadjiev, W. T. Tysoe, Chem. Mater. 1996, 8, 2359)
  • nitrides AlN, Co 3 N, Cr 2 N, Fe 4 N, Mn 4 N, MoN, Si 3 N 4 , TiN, WN, VN can be prepared for example by means of the reactions [4-7] (as described in The Chemistry of Transition Metal Carbides and Nitrides, S. T. Oyama Ed., Blackie Academic Professional, Glasgow, 1996).
  • M Al, Cr, Ti, V, Mo, Mn, Co, Fe, W
  • Bimetallic nitrides containing transition metals of groups VIB and VIII can be prepared according to reaction [8] as described in EP 1036592; C. J. H. Jacobsen, Chem. Comm. 2000, 1057
  • Si—N—B systems or Si—B—N—C systems such as Si 3 B 3 N 7 and SiBN 3 C are prepared as described in P. Baldus, M. Jansen, D. Sporn, Science 1999, 285, 699 according to the reactions:
  • Systems consisting of layers of aluminum nitrides deposited on oxide carriers can, on the other hand, be obtained by means of consecutive adsorptions of aluminum alkyls (for example Al(CH 3 ) 3 ) and ammonia on oxide surfaces so as to obtain the reaction [13] with a method described for example in: A. Dabrowski “Adsorption and its application in industry and environmental protection, Studies in Surf. Sci. and Catalysis 1999, 120A, 715; C. Soto, V. Bojadjiev, W. T. Tysoe Chem. Mater. 1996, 8, 2359.
  • a further object of the present invention relates to a process for the production of olefins from gaseous paraffinic hydrocarbons, having from two to six carbon atoms, comprising a partial oxidation of said hydrocarbons with a gas containing molecular oxygen in the presence of the catalytic system specified above.
  • the partial oxidation is preferably effected at a temperature ranging from 450 to 1000° C., at a pressure ranging from 1 to 15 Atm and a space velocity ranging from 5000 to 800000 h ⁇ 1 .
  • the gas inlet zone and catalytic zone can either have a tubular shape, a sand-glass shape or a truncated-conical shape: the geometry is defined so as to maintain the surface rate values above the flame speed and contact times lower than the ignition delay in the zone prior to the catalytic bed and allow expansion of the product mixture, thus avoiding pressure drops, after the reactions have been activated.
  • a further object of the present invention relates to a process carried out using reactors in which the inlet zone and catalytic zone have a tubular shape or a sand-glass shape or a truncated-conical shape, with the particular characteristic of sending into the gas inlet zone a stream of oxygen, air or enriched air and a fuel, not having the function of directly producing olefins, preferably selected from natural gas, synthesis gas, hydrogen or a mixture of hydrogen and CO, and in the catalytic zone a gaseous stream of paraffinic hydrocarbons.
  • the gas increases in volume due to the increase in temperature and stoichiometry of the reactions and is overheated by temperature values ranging from 80 to 600° C., preferably 100-400° C., in the distribution zone and ranging from 600 to 1300° C., preferably from 700 to 950° C. in the reaction zone.
  • the differential filling of the catalytic bed with particles having an increasing diameter along the gas distribution direction can also be used to reduce pressure drops.
  • One of the solutions adopted therefore consists of a filling of catalyst particles with an increasing diameter along the gas distribution direction.
  • a further innovative aspect relates to the possibility of using not only various geometries but also different catalysts in different reaction zones.
  • the catalyst fillings are differentiated so as to preferably have two or three catalytic beds in series.
  • catalytic systems consisting of:
  • catalytic systems consisting of:
  • the ⁇ values range from 0° ⁇ 89°.
  • the value of the angle ⁇ and distance L are selected so as to:
  • FIG. 1B schematizes a reactor with a varying diameter in the direction of the gas distribution and a tubular reactor.
  • FIG. 1C a reactor with a varying diameter in the direction of the gas distribution and a tubular reactor are schematized.
  • the combustion of this mixture is effected in a first reaction zone (R1) and has the function of producing the heat and reagents which favour dehydrogenation reactions, in a second reaction zone (R2), of a second hydrocarbon reagent (F2) which can consist of ethane, propane, butane or a liquid hydrocarbon such as naphtha or any other reagent which must be transformed into an olefinic compound.
  • a first reaction zone R1
  • R2 second hydrocarbon reagent
  • F2 can consist of ethane, propane, butane or a liquid hydrocarbon such as naphtha or any other reagent which must be transformed into an olefinic compound.
  • the reactor was positioned in an oven, with the double objective of preheating the reagents and reducing the loss in heat of the system.
  • thermocouples at the beginning and at the end of the catalytic bed, co-axially positioned with respect to the distribution direction of the reagents/products, allowed the temperature of the gases at the inlet and outlet of the catalytic bed to be monitored.
  • the reactor was charged with a catalyst (indicated with the abbreviation PS7AL2 in Table 1) in which the carrier consisted of ⁇ -alumina pellets (more or less spherically shaped, with a particle diameter—d p —equal to 1.2 mm).
  • a catalyst indicated with the abbreviation PS7AL2 in Table 1
  • the carrier consisted of ⁇ -alumina pellets (more or less spherically shaped, with a particle diameter—d p —equal to 1.2 mm).
  • a commercial hydrochloric solution of Pt salts (H 2 PtCl 6 ) and Sn salts (SnCl 2 .4H 2 O) was dripped onto the carrier, so as to give a weight percentage of Pt equal to 2 and an atomic ratio Sn:Pt equal to 7:1.
  • PS7SN1, PS7SN3 and PS7SN4 refer to the same catalyst, obtained in different batches.
  • the catalytic materials already described in Example 2 were alternatively tested in a quartz reactor consisting of a distribution zone and a catalytic zone, both conical (sand-glass configuration).
  • the distribution zone has an inlet diameter of 15 mm and a height of 10 mm.
  • the catalytic zone has an inlet diameter of 4 mm, a height of 18 mm and an outlet diameter of 20 mm.
  • the catalytic pellets were positioned between two zones filled with ceramic material acting as a thermal shield.
  • thermocouples positioned longitudinally at the inlet and outlet of the catalytic bed, monitored the temperature of the gases at the inlet and outlet.
  • the reactor was positioned in an oven, with the double objective of preheating the reagents and reducing the loss of heat of the system.
  • Example 3A The gases fed in Examples 3A and 3B were ethane, nitrogen (percentage equal to 15% v/v approx.), oxygen and hydrogen.
  • Example 3C carried out at a very low space velocity and with a greater volume of catalyst), a mixture of hydrogen and carbon monoxide was fed, in addition to ethane and oxygen.
  • Example 1A Example 1B
  • Example 1C Example 1D Catalyst PS7AL2 PS7AL2 PS7AL2 PS7AL2 Reactor geometry tubular tubular tubular tubular Operating conditions T out (° C.) 828 787 771 768 p (bar) 1.319 1.22 1.21 1.23 GHSV (NL/kg/h) 603.600 389.300 380.600 402.400 C 2 H 6 /O 2 2.08 2.27 2.38 2.48 H 2 /O 2 2.185 2.000 2.000 2.000 Performance Conversion C 2 H 6 68.7% 64.0% 61.3% 59.0% Conversion O 2 100% 100% 100% 100% 100% 100% Selectivity C 2 H 4 79.9% 80.5% 81.3% 81.9% Selectivity CO 7.0% 6.8% 6.3% 6.0% Selectivity CO 2 1.8% 2.6% 2.2% 2.2% Selectivity CH 4 5.5% 5.3% 4.8% 4.7% Selectivity C 2 H 2 1.5% 1.6% 1.3% 1.2% Selectivity C 3 1.6% 1.4% 1.5% 1.4% Selectivity C 4> 2.7% 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
US10/359,191 2002-02-06 2003-02-06 Catalytic system for the production of olefins Abandoned US20030181778A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/561,092 US20070123744A1 (en) 2002-02-06 2006-11-17 Catalytic system for the production of olefins
US12/033,572 US7829753B2 (en) 2002-02-06 2008-02-19 Catalytic system for the production of olefins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2002A000214 2002-02-06
IT2002MI000214A ITMI20020214A1 (it) 2002-02-06 2002-02-06 Sistema catalitico per la produzione di olefine

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/561,092 Continuation US20070123744A1 (en) 2002-02-06 2006-11-17 Catalytic system for the production of olefins

Publications (1)

Publication Number Publication Date
US20030181778A1 true US20030181778A1 (en) 2003-09-25

Family

ID=11449116

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/359,191 Abandoned US20030181778A1 (en) 2002-02-06 2003-02-06 Catalytic system for the production of olefins
US11/561,092 Abandoned US20070123744A1 (en) 2002-02-06 2006-11-17 Catalytic system for the production of olefins
US12/033,572 Expired - Lifetime US7829753B2 (en) 2002-02-06 2008-02-19 Catalytic system for the production of olefins

Family Applications After (2)

Application Number Title Priority Date Filing Date
US11/561,092 Abandoned US20070123744A1 (en) 2002-02-06 2006-11-17 Catalytic system for the production of olefins
US12/033,572 Expired - Lifetime US7829753B2 (en) 2002-02-06 2008-02-19 Catalytic system for the production of olefins

Country Status (12)

Country Link
US (3) US20030181778A1 (de)
EP (1) EP1334958B1 (de)
AR (1) AR038351A1 (de)
AT (1) ATE439337T1 (de)
BR (1) BR0300283B1 (de)
DE (1) DE60328737D1 (de)
DK (1) DK1334958T3 (de)
EG (1) EG23310A (de)
ES (1) ES2331608T3 (de)
IT (1) ITMI20020214A1 (de)
PT (1) PT1334958E (de)
SA (1) SA03240044B1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090127512A1 (en) * 2007-11-21 2009-05-21 Eni S.P.A. Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses
CN113019412A (zh) * 2021-03-08 2021-06-25 大连理工大学 一种轻质烷烃脱氢制烯烃催化剂、其制备方法及应用
CN116120973A (zh) * 2021-11-12 2023-05-16 中国科学院大连化学物理研究所 一种合成气低温烷基化制取天然气的方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10309209A1 (de) * 2003-02-28 2004-09-09 Degussa Ag Verfahren zur Herstellung von Cyanwasserstoff nach dem BMA-Verfahren und Katalysator zu seiner Durchführung
WO2014167473A1 (en) 2013-04-08 2014-10-16 Saudi Basic Industries Corporation Reactor and process for paraffin dehydrogenation to olefins
WO2017044711A1 (en) * 2015-09-09 2017-03-16 Wisconsin Alumni Research Foundation Heterogeneous catalysts for the oxidative dehydrogenation of alkanes or oxidative coupling of methane
CN109126855B (zh) * 2018-09-25 2020-12-18 陕西师范大学 一种负载型GaN催化剂及其在催化CO2氧化丙烷脱氢反应中的应用
US20250066274A1 (en) 2023-08-22 2025-02-27 Chevron Phillips Chemical Company Lp Integrated processes utilizing water electrolysis and oxidative dehydrogenation of ethane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940684A (en) * 1987-09-28 1990-07-10 President Of Agency Of Industrial Science And Technology Method for preparing a catalyst supported on silicon carbide or silicon nitride
US5444173A (en) * 1993-11-19 1995-08-22 Akzo Nobel N.V. Catalytic bimetallic oxynitrides and nitrides
US6479027B1 (en) * 1999-10-29 2002-11-12 Haldor Topsoe A/S Process for the preparation of ammonia and ammonia synthesis gas
US20030013605A1 (en) * 2000-01-20 2003-01-16 Thomas Klassen Catalysis of the hydrogen sorption kinetics of hydrides by nitrides and carbides

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0266875B1 (de) 1986-09-10 1992-04-29 Hitachi, Ltd. Methode der katalytischen Verbrennung mit wärmebeständigem Katalysator
US4940884A (en) * 1987-12-28 1990-07-10 Ppg Industries, Inc. Dual bus bar arrangement for an electrically heatable transparency
JPH04118052A (ja) 1990-09-06 1992-04-20 Babcock Hitachi Kk 耐熱性燃焼触媒およびその製造方法
DE19600741A1 (de) * 1995-01-18 1996-07-25 Basf Ag Katalysator und dessen Verwendung bei der heterogenkatalytischen instationären oxidativen Dehydrierung von Alkylaromaten und Paraffinen
JP3826161B2 (ja) * 1995-06-08 2006-09-27 株式会社 日本触媒 バナジウム含有触媒およびその製造方法、並びに、その使用方法
DE19533484A1 (de) * 1995-09-12 1997-03-13 Basf Ag Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren
IT1283585B1 (it) 1996-04-11 1998-04-22 Snam Progetti Apparecchiatura per effettuare reazioni di ossidazione parziale

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940684A (en) * 1987-09-28 1990-07-10 President Of Agency Of Industrial Science And Technology Method for preparing a catalyst supported on silicon carbide or silicon nitride
US5444173A (en) * 1993-11-19 1995-08-22 Akzo Nobel N.V. Catalytic bimetallic oxynitrides and nitrides
US6479027B1 (en) * 1999-10-29 2002-11-12 Haldor Topsoe A/S Process for the preparation of ammonia and ammonia synthesis gas
US20030013605A1 (en) * 2000-01-20 2003-01-16 Thomas Klassen Catalysis of the hydrogen sorption kinetics of hydrides by nitrides and carbides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090127512A1 (en) * 2007-11-21 2009-05-21 Eni S.P.A. Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses
CN113019412A (zh) * 2021-03-08 2021-06-25 大连理工大学 一种轻质烷烃脱氢制烯烃催化剂、其制备方法及应用
CN116120973A (zh) * 2021-11-12 2023-05-16 中国科学院大连化学物理研究所 一种合成气低温烷基化制取天然气的方法

Also Published As

Publication number Publication date
EP1334958A1 (de) 2003-08-13
ATE439337T1 (de) 2009-08-15
US20080139862A1 (en) 2008-06-12
DK1334958T3 (da) 2009-12-07
DE60328737D1 (de) 2009-09-24
US20070123744A1 (en) 2007-05-31
AR038351A1 (es) 2005-01-12
EP1334958B1 (de) 2009-08-12
BR0300283B1 (pt) 2014-08-19
ITMI20020214A0 (it) 2002-02-06
US7829753B2 (en) 2010-11-09
ITMI20020214A1 (it) 2003-08-06
PT1334958E (pt) 2009-11-18
ES2331608T3 (es) 2010-01-11
SA03240044B1 (ar) 2009-08-11
BR0300283A (pt) 2004-02-10
EG23310A (en) 2004-11-30

Similar Documents

Publication Publication Date Title
US7829753B2 (en) Catalytic system for the production of olefins
US6365543B1 (en) Process for the production of an oxidation catalyst on-line
Huff et al. Production of olefins by oxidative dehydrogenation of propane and butane over monoliths at short contact times
AU751440B2 (en) On-line synthesis and regeneration of a catalyst used in autothermal oxidation
EP2691358B1 (de) Verfahren zur herstellung von olefinen
NZ227922A (en) Production of mono-olefins from paraffinic hydrocarbons
AU754209B2 (en) Process for the production of olefins
KR101489768B1 (ko) 알칸 스트림을 탈수소화하는 촉매 탈수소화 방법 및 장치
US20090318741A1 (en) Method of improving a dehydrogenation process
KR100900016B1 (ko) Ｃ2-ｃ30-알칸의 탈수소화 방법
US5220093A (en) Process for production of olefins from mixtures of light paraffins
AU2003234467A1 (en) Particulate supports for oxidative dehydrogenation
JP2006502218A (ja) 酸化的脱水素化触媒としての希土類金属
WO2004105937A1 (en) Multilayer catalyst, process for the preparation and use thereof in the partial oxidation of hydrocarbons in gaseous phase
US20040158112A1 (en) Silicon carbide-supported catalysts for oxidative dehydrogenation of hydrocarbons
AU2004244793A1 (en) Catalyst and process for the production of olefins
AU2004245273A1 (en) A catalyst comprising a metalic support and a process for the production of olefins

Legal Events

Date Code Title Description
AS Assignment

Owner name: SNAMPROGETTI S.P.A., ITALY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BASINI, LUCA;SANFILIPPO, DOMINICO;GUARINONI, ALESSANDRA;REEL/FRAME:014127/0105

Effective date: 20030514

AS Assignment

Owner name: SNAMPROGETTI S.P.A., ITALY

Free format text: RECORD TO CORRECT ASSIGNOR #2'S NAME ON AN ASSIGNMENT PREVIOUSLY RECORDED ON REEL/FRAME 014127/0105. (ASSIGNMENT OF ASSIGNOR'S INTEREST);ASSIGNORS:BASINI, LUCA;SANFILIPPO, DOMENICO;GUARINONI, ALESSANDRA;REEL/FRAME:014732/0743

Effective date: 20030514

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION