WO2017001445A1 - A hydrocarbon conversion catalyst for producing less saturated hydrocarbon product - Google Patents

A hydrocarbon conversion catalyst for producing less saturated hydrocarbon product Download PDF

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Publication number
WO2017001445A1
WO2017001445A1 PCT/EP2016/065084 EP2016065084W WO2017001445A1 WO 2017001445 A1 WO2017001445 A1 WO 2017001445A1 EP 2016065084 W EP2016065084 W EP 2016065084W WO 2017001445 A1 WO2017001445 A1 WO 2017001445A1
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Prior art keywords
mass fraction
catalyst
range
hydrocarbon
mixtures
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PCT/EP2016/065084
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French (fr)
Inventor
Kongkiat Suriye
Amnart Jantharasuk
Wuttithep Jareewatchara
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SMH Co., Ltd.
Scholz, Volker
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Application filed by SMH Co., Ltd., Scholz, Volker filed Critical SMH Co., Ltd.
Publication of WO2017001445A1 publication Critical patent/WO2017001445A1/en

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    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • 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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • 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
    • B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • 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
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • 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
    • C07C2523/16—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
    • C07C2523/42—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
    • C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/652—Chromium, molybdenum or tungsten
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a catalyst for hydrocarbon conversion. More specifically, the present invention is directed to a catalyst for converting a hydrocarbon feed to a less saturated hydrocarbon product.
  • Olefins especially light olefins including ethylene and propylene, are valuable hydrocarbon products. They are useful for preparing a wide variety of end products, including ethylene oxide, propylene oxide, ethylbenzene, acetone, phenol, polyethylene, polypropylene, other polymers, and other petrochemical products. Even though their prices have been fluctuated over time, their demands in the industry have still been continuously growing.
  • US 8,198,498 B2 disclosed a carbon nanotube catalyst coated with metal oxides for using in hydrocarbon cracking process.
  • the process is still highly energy intensive because it has to be carried out at quite high temperatures, and preferably with addition of steam to the feed stream, in order to achieve improved yield of the desirable olefins product.
  • it is the object to provide a catalyst for converting a hydrocarbon feed to a less saturated hydrocarbon product which may be operated under mild conditions, in particular at comparably low temperatures, but which allows to produce the less saturated hydrocarbon product with high selectivity to achieve the desired product.
  • the present invention provides a catalyst in oxidic form comprising metals Ml, M2, M3 and M4, wherein:
  • Ml is selected from Si, Al, Zr, and mixtures thereof;
  • M2 is selected from Pt, Cr, and mixtures thereof;
  • M3 is selected from W, Mo, Re, and mixtures thereof;
  • M4 is selected from Sn, K, Y, Yb and mixtures thereof; wherein mass fraction of Ml is in the range of 0.1 to 0.8; mass fraction of M2 is in the range of 0.001 to 0.2; mass fraction of M3 is in the range of 0.001 to 0.2; mass fraction of M4 is in the range of 0.0001 to 0.2; and mass fraction of oxygen is in the range of 0.1 to 0.8.
  • the inventive catalyst allows converting a hydrocarbon feed to olefins products with high selectivity and at relatively mild conditions.
  • the inventive catalyst is a hydrocarbon conversion catalyst, i.e. a catalyst for use in a hydrocarbon conversion process, being a multi-metal composition comprising:
  • Ml is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof, preferably Pt; M3 is selected from W, Mo, Re, and mixtures thereof, preferably W; M4 is selected from Sn, K, Y, Yb and mixtures thereof; and oxygen; wherein mass fraction of Ml is in the range of 0.1 to 0.8, preferably 0.2 to 0.6; mass fraction of M2 is in the range of 0.001 to 0.2, preferably 0.0015 to 0.15, more preferably 0.005 to 0.1; mass fraction of M3 is in the range of 0.001 to 0.2, preferably 0.005 to 0.15, more preferably 0.01 to 0.1; mass fraction of M4 is in the range ofO.0001 to 0.2, preferably 0.00015 to 0.03, more preferably 0.005 to 0.02; and mass fraction of oxygen is in the range of 0.1 to 0.8, preferably 0.2 to 0.5.
  • mass fraction is related to the total mass (weight) of the inventive catalyst.
  • the catalyst has preferably the formula M1M2M3M40.
  • the inventive catalyst further comprises M5 (i.e. is a catalyst having the formula M1M2M3M4M50), wherein M5 is selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, , and mixtures thereof, preferably Mg, Ca, and mixture thereof; and mass fraction of M5 is in the range of 0.005 to 0.1 , preferably 0.01 to 0.09.
  • M5 i.e. is a catalyst having the formula M1M2M3M4M50
  • M5 is selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, , and mixtures thereof, preferably Mg, Ca, and mixture thereof
  • mass fraction of M5 is in the range of 0.005 to 0.1 , preferably 0.01 to 0.09.
  • the inventive catalyst can be prepared by mixing all precursors of the element Ml to M5 together followed by a suitable heat treatment in order to obtain the desired multi-metal composition.
  • Element precursors are starting compounds containing the desired elements which can be converted to the desired form of elements, preferably oxides, in the final catalyst by a suitable heat treatment.
  • precursor to Ml to M5 may include oxides, halides, alkoxide, nitrates, carbonates, formate, oxalates, amine, or hydroxides of the elements.
  • element precursors can occur in dry form or wet form.
  • the element precursors may conveniently be provided in powder form. Powder of the element precursors can be easily mixed by physical mixing in a blender.
  • the element precursors' mixture is then subjected to a suitable heat treatment, preferably calcination, to obtain the final hydrocarbon conversion catalyst.
  • the element precursors may be provided in solution and/or suspension form.
  • a mixture of the element precursors' solutions and/or suspensions is then dried to remove the solvents. Subsequently, the dried mixture is subjected to a suitable heat treatment, preferably calcination, to obtain the final catalyst.
  • some of the element precursors are provided in dry form and some of the element precursors are provided in wet form.
  • the dry and wet element precursors can be combined by conventional methods including
  • the obtained mixture is then subjected to a suitable heat treatment, preferably calcination, to obtain the final catalyst.
  • a suitable heat treatment involves a selected atmosphere and a selected temperature capable of removing and/or converting at least a part of the element precursors to the desired form of the corresponding elements in the final catalyst. Particularly preferred is the elements are in oxides form in the final catalyst.
  • the selected atmosphere may include oxidizing atmosphere, reducing atmosphere, and inert atmosphere.
  • the prepared catalyst powder is subjected to calcination in air at a temperature in the range of 300°C to 800°C for 1 to 24 hours, even more preferably 400°C to 600°C for 2 to 10 hours
  • preparation of the catalyst according to the present invention may further involve forming the catalyst powder into a shape suitable for a commercial reactor.
  • Shapes suitable for a commercial reactor may include pellets, extrudates, spheres, and the like.
  • Sufficient binder materials may be further added to the catalyst composition to facilitate forming of the catalyst. Providing the catalyst in a specific shape allows more easy use thereof.
  • the inventive catalyst can be used in a hydrocarbon conversion process wherein a hydrocarbon feed stream is contacted with the inventive catalyst.
  • the hydrocarbon feed stream comprises a paraffmic hydrocarbon.
  • the hydrocarbon feed stream comprises a paraffin having 2 to 5 carbon atoms.
  • the hydrocarbon feed stream comprises a paraffin selected from ethane, propane, butane, pentane and mixtures thereof, preferably propane, butane, and a mixture thereof.
  • the hydrocarbon conversion process is carried out at a temperature in the range of 200°C to 700°C, preferably 300°C to 600°C, even more preferably 350°C to 550°C.
  • the inventive catalyst allows to drive the hydrocarbon conversion process at the before mentioned preferred temperatures which are comparably low with respect to the processes know in the art.
  • the process is carried out at a pressure in the range of 0.01 to 10 bar gauge, preferably 0.05 to 5 bar gauge.
  • the contact time needed to obtain a desirable yield of olefins product depends upon several factors such operating temperature, operating pressure, and catalyst activity. In an
  • the process is carried out at a weight hourly space velocity (WHS V) in the range of 0.01 to 20 hr "1 , preferably 0.05 to 5 hr 1 .
  • WHS V weight hourly space velocity
  • the process can be conducted in a batch manner or a continuous manner. For commercial scale, it is favorable that the process is continuously operated. Continuous operation can be performed with fixed bed, fluidized bed, or other techniques known in the art with fixed bed being typically preferred.
  • the catalyst Prior to contacting with the hydrocarbon feed stream, the catalyst may optionally be pretreated.
  • the pretreatment condition may include contacting the catalyst with an inert gas, an oxidizing gas, a reducing gas, a hydrocarbon, preferably a C2-C6 aliphatic hydrocarbon, and any mixture thereof .
  • the pretreatment may be divided into several steps wherein each step may employ different conditions and atmospheres. It is generally preferred that the pretreatment is performed at a heated temperature, preferably 200°C to 700°C, more preferably 300°C to 600°C, even more preferably 350°C to 550°C.
  • the hydrocarbon conversion process comprises a regeneration step wherein the regeneration step includes contacting the hydrocarbo conversion catalyst with an oxidizing agent at a high temperature. The regeneration step should be carefully controlled to avoid overheating and destroying structure of the catalyst.
  • the regeneration step includes contacting the hydrocarbo conversion catalyst with an oxidizing agent at a high temperature. The regeneration step should be carefully controlled to avoid overheating and destroying structure of the catalyst.
  • regeneration step is carried out at a temperature in the range of 200°C to 700° C, preferably 300°C to 600°C.
  • Other known regeneration techniques can be employed without limitation.
  • the inventive catalyst according to the present invention is capable of converting light paraffin feed with high selectivity to light olefins, including ethylene, propylene, and butenes. Significantly low amount of less valued by-products such as methane and heavier
  • hydrocarbons are produced.
  • a zeolite catalyst containing 0.95 mass fraction of Si and 0.05 mass fraction of Al was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h "1 . Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
  • Example 2 (comparative) A catalyst containing 0.5 mass fraction of Al, 0.45 mass fraction of O, and 0.05 mass fraction of Pt was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h "1 Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
  • a catalyst containing 0.306 mass fraction of Si, 0.012 mass fraction of Al, 0.031 mass fraction of Mg, 0.044 mass fraction of W, 0.387 mass fraction of O, 0.189 mass fraction of Zr, 0.02 mass fraction of Pt, and 0.011 mass fraction of Y was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h "1 . Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
  • a catalyst containing 0.248 mass fractio of Si, 0.213 mass fraction of Al, 0.031 mass fraction of Mg, 0.044 mass fraction of W, 0.433 mass fraction of 0, 0.02 mass fraction of Pt, and 0.01 1 mass fraction of K was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 fa "1 . Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
  • the selectivity of total olefins was calculated from selectivity of olefin products including ethylene, propylene, and butenes.

Abstract

The present invention relates to a catalyst in oxidic form comprising metals M1, M2, M3 and M4, wherein: M1 is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof; M3 is selected from W, Mo, Re, and mixtures thereof; and M4 is selected from Sn, K, Y, Yb and mixtures thereof; mass fraction of M1 is in the range of 0.1 to 0.8; mass fraction of M2 is in the range of 0.001 to 0.2; mass fraction of M3 is in the range of 0.001 to 0.2; mass fraction of M4 is in the range of 0.0001 to 0.2. The catalyst is useful for converting a hydrocarbon feed to a less saturated hydrocarbon product.

Description

TITLE
A HYDROCARBON CONVERSION CATALYST FOR PRODUCING LESS SATURATED HYDROCARBON PRODUCT
FIELD OF INVENTION
The present invention relates to a catalyst for hydrocarbon conversion. More specifically, the present invention is directed to a catalyst for converting a hydrocarbon feed to a less saturated hydrocarbon product.
BACKGROUND OF INVENTION
Olefins, especially light olefins including ethylene and propylene, are valuable hydrocarbon products. They are useful for preparing a wide variety of end products, including ethylene oxide, propylene oxide, ethylbenzene, acetone, phenol, polyethylene, polypropylene, other polymers, and other petrochemical products. Even though their prices have been fluctuated over time, their demands in the industry have still been continuously growing.
To serve the industrial needs, many methods have been used to produce olefins. However, it is typically more economically attractive to produce olefins from lower valued feedstock such as paraffin. A conventional method for converting paraffins to olefins is thermal cracking. This is a highly energy intensive method and product selectivity is difficult to be adjusted and controlled. Catalytic cracking is a later developed method. With appropriate catalytic materials, generally zeolite-based materials, hydrocarbon cracking can occur at less severe operating condition.
Several improvements on catalytic cracking have been studied and disclosed. For example, US 8,933,286 B2 disclosed a catalytic crackin process using a zeolite catalyst modified with nickel. The process can be operated at milder operating condition. However, significant amount of by-products including methane and C5+ hydrocarbons can be observed and there was no indication regarding stability of the catalyst.
US 8,198,498 B2 disclosed a carbon nanotube catalyst coated with metal oxides for using in hydrocarbon cracking process. The process is still highly energy intensive because it has to be carried out at quite high temperatures, and preferably with addition of steam to the feed stream, in order to achieve improved yield of the desirable olefins product.
It is the object of the present invention to provide catalysts for hydrocarbon conversion overcoming drawbacks of the prior art. In particular, it is the object to provide a catalyst for converting a hydrocarbon feed to a less saturated hydrocarbon product which may be operated under mild conditions, in particular at comparably low temperatures, but which allows to produce the less saturated hydrocarbon product with high selectivity to achieve the desired product.
SUMMARY OF INVENTION
The present invention provides a catalyst in oxidic form comprising metals Ml, M2, M3 and M4, wherein:
Ml is selected from Si, Al, Zr, and mixtures thereof;
M2 is selected from Pt, Cr, and mixtures thereof;
M3 is selected from W, Mo, Re, and mixtures thereof; and
M4 is selected from Sn, K, Y, Yb and mixtures thereof; wherein mass fraction of Ml is in the range of 0.1 to 0.8; mass fraction of M2 is in the range of 0.001 to 0.2; mass fraction of M3 is in the range of 0.001 to 0.2; mass fraction of M4 is in the range of 0.0001 to 0.2; and mass fraction of oxygen is in the range of 0.1 to 0.8.
The inventive catalyst allows converting a hydrocarbon feed to olefins products with high selectivity and at relatively mild conditions. DETAILED DESCRIPTION
In an embodiment, the inventive catalyst is a hydrocarbon conversion catalyst, i.e. a catalyst for use in a hydrocarbon conversion process, being a multi-metal composition comprising:
Ml is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof, preferably Pt; M3 is selected from W, Mo, Re, and mixtures thereof, preferably W; M4 is selected from Sn, K, Y, Yb and mixtures thereof; and oxygen; wherein mass fraction of Ml is in the range of 0.1 to 0.8, preferably 0.2 to 0.6; mass fraction of M2 is in the range of 0.001 to 0.2, preferably 0.0015 to 0.15, more preferably 0.005 to 0.1; mass fraction of M3 is in the range of 0.001 to 0.2, preferably 0.005 to 0.15, more preferably 0.01 to 0.1; mass fraction of M4 is in the range ofO.0001 to 0.2, preferably 0.00015 to 0.03, more preferably 0.005 to 0.02; and mass fraction of oxygen is in the range of 0.1 to 0.8, preferably 0.2 to 0.5.
In this regard, it may be provided that the term "mass fraction" is related to the total mass (weight) of the inventive catalyst.
In one embodiment, the catalyst has preferably the formula M1M2M3M40.
In another embodiment, the inventive catalyst further comprises M5 (i.e. is a catalyst having the formula M1M2M3M4M50), wherein M5 is selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, , and mixtures thereof, preferably Mg, Ca, and mixture thereof; and mass fraction of M5 is in the range of 0.005 to 0.1 , preferably 0.01 to 0.09.
Each of the above embodiments related to a preferred metal or referring to specific amounts of the respective ingredient being comprised in the catalyst allows achieving a better catalyst, i.e. a catalyst showing improved selectivity and being operable at lower
temperatures. Each of the above embodiments alone is suitable for improving the catalyst. However, combinations of one or more of the above preferred metals or preferred amounts thereof may synergistically improve the catalyst.
The inventive catalyst can be prepared by mixing all precursors of the element Ml to M5 together followed by a suitable heat treatment in order to obtain the desired multi-metal composition. Element precursors are starting compounds containing the desired elements which can be converted to the desired form of elements, preferably oxides, in the final catalyst by a suitable heat treatment. For example, precursor to Ml to M5 may include oxides, halides, alkoxide, nitrates, carbonates, formate, oxalates, amine, or hydroxides of the elements.
Mixing of element precursors can occur in dry form or wet form. When they are mixed in dry form, the element precursors may conveniently be provided in powder form. Powder of the element precursors can be easily mixed by physical mixing in a blender. The element precursors' mixture is then subjected to a suitable heat treatment, preferably calcination, to obtain the final hydrocarbon conversion catalyst. When they are mixed in wet form, the element precursors may be provided in solution and/or suspension form. A mixture of the element precursors' solutions and/or suspensions is then dried to remove the solvents. Subsequently, the dried mixture is subjected to a suitable heat treatment, preferably calcination, to obtain the final catalyst. Alternatively, some of the element precursors are provided in dry form and some of the element precursors are provided in wet form. The dry and wet element precursors can be combined by conventional methods including
impregnation, incipient wetness, ion-exchange, or other methods known in the art. The obtained mixture is then subjected to a suitable heat treatment, preferably calcination, to obtain the final catalyst. A suitable heat treatment involves a selected atmosphere and a selected temperature capable of removing and/or converting at least a part of the element precursors to the desired form of the corresponding elements in the final catalyst. Particularly preferred is the elements are in oxides form in the final catalyst. The selected atmosphere may include oxidizing atmosphere, reducing atmosphere, and inert atmosphere. In a preferred embodiment, the prepared catalyst powder is subjected to calcination in air at a temperature in the range of 300°C to 800°C for 1 to 24 hours, even more preferably 400°C to 600°C for 2 to 10 hours
In another embodiment, preparation of the catalyst according to the present invention may further involve forming the catalyst powder into a shape suitable for a commercial reactor. Shapes suitable for a commercial reactor may include pellets, extrudates, spheres, and the like. Sufficient binder materials may be further added to the catalyst composition to facilitate forming of the catalyst. Providing the catalyst in a specific shape allows more easy use thereof.
The inventive catalyst can be used in a hydrocarbon conversion process wherein a hydrocarbon feed stream is contacted with the inventive catalyst. In order to produce olefins product, it is favorable that the hydrocarbon feed stream comprises a paraffmic hydrocarbon. In a preferred embodiment, the hydrocarbon feed stream comprises a paraffin having 2 to 5 carbon atoms. In a more specific embodiment, the hydrocarbon feed stream comprises a paraffin selected from ethane, propane, butane, pentane and mixtures thereof, preferably propane, butane, and a mixture thereof.
Also for the purpose of olefins production, the hydrocarbon conversion process is carried out at a temperature in the range of 200°C to 700°C, preferably 300°C to 600°C, even more preferably 350°C to 550°C. The inventive catalyst allows to drive the hydrocarbon conversion process at the before mentioned preferred temperatures which are comparably low with respect to the processes know in the art. In another embodiment, the process is carried out at a pressure in the range of 0.01 to 10 bar gauge, preferably 0.05 to 5 bar gauge. The contact time needed to obtain a desirable yield of olefins product depends upon several factors such operating temperature, operating pressure, and catalyst activity. In an
embodiment, the process is carried out at a weight hourly space velocity (WHS V) in the range of 0.01 to 20 hr"1, preferably 0.05 to 5 hr 1. The process can be conducted in a batch manner or a continuous manner. For commercial scale, it is favorable that the process is continuously operated. Continuous operation can be performed with fixed bed, fluidized bed, or other techniques known in the art with fixed bed being typically preferred.
Prior to contacting with the hydrocarbon feed stream, the catalyst may optionally be pretreated. The pretreatment condition may include contacting the catalyst with an inert gas, an oxidizing gas, a reducing gas, a hydrocarbon, preferably a C2-C6 aliphatic hydrocarbon, and any mixture thereof . The pretreatment may be divided into several steps wherein each step may employ different conditions and atmospheres. It is generally preferred that the pretreatment is performed at a heated temperature, preferably 200°C to 700°C, more preferably 300°C to 600°C, even more preferably 350°C to 550°C.
After contacted with the hydrocarbon feed stream at the operating condition, some poisonous substances, heavy hydrocarbons, and coke may deposit on the surface of the catalyst. This normally affects activity of the catalyst to gradually drop over time. A suitable regeneration can be performed on the used catalyst to recover at least some of its activity. In an embodiment, the hydrocarbon conversion process comprises a regeneration step wherein the regeneration step includes contacting the hydrocarbo conversion catalyst with an oxidizing agent at a high temperature. The regeneration step should be carefully controlled to avoid overheating and destroying structure of the catalyst. In an embodiment, the
regeneration step is carried out at a temperature in the range of 200°C to 700° C, preferably 300°C to 600°C. Other known regeneration techniques can be employed without limitation.
The inventive catalyst according to the present invention is capable of converting light paraffin feed with high selectivity to light olefins, including ethylene, propylene, and butenes. Significantly low amount of less valued by-products such as methane and heavier
hydrocarbons are produced.
Embodiments and advantages of the present invention are further illustrated by the following examples.
EXAMPLES
Example 1 (comparative)
A zeolite catalyst containing 0.95 mass fraction of Si and 0.05 mass fraction of Al was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h"1. Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Example 2 (comparative) A catalyst containing 0.5 mass fraction of Al, 0.45 mass fraction of O, and 0.05 mass fraction of Pt was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h"1 Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Example 3 (comparative)
A catalyst containing 0.245 mass fraction of Si, 0.215 mass fraction of Al, 0.045 mass fraction of W, 0.475 mass fraction of O, and 0.02 mass fraction of Pt was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 If 1. Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Example 4 (inventive)
A catalyst containing 0.26 mass fraction of Si, 0.21 mass fraction of Al, 0.045 mass fraction of W, 0.455 mass fraction of O, 0.02 mass fraction of Pt, and 0.01 mass fraction of K was contacted with propane at 475 °C, 1 bar gauge, and WHSV of 0.12 h"1. Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Example 5 (inventive)
A catalyst containing 0.26 mass fraction of Si, 0.21 mass fraction of Al, 0.045 mass fraction of W, 0.455 mass fraction of O, 0.02 mass fraction of Pt, and 0.01 mass fraction of Sn was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h"1. Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Example 6 (inventive)
A catalyst containing 0.306 mass fraction of Si, 0.012 mass fraction of Al, 0.031 mass fraction of Mg, 0.044 mass fraction of W, 0.387 mass fraction of O, 0.189 mass fraction of Zr, 0.02 mass fraction of Pt, and 0.011 mass fraction of Y was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 h"1. Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Example 7 (inventive)
A catalyst containing 0.248 mass fractio of Si, 0.213 mass fraction of Al, 0.031 mass fraction of Mg, 0.044 mass fraction of W, 0.433 mass fraction of 0, 0.02 mass fraction of Pt, and 0.01 1 mass fraction of K was contacted with propane at 475°C, 1 bar gauge, and WHSV of 0.12 fa"1. Results of this reaction at time on stream 3 hours and 8 hours are displayed in Table 1.
Table 1
Figure imgf000009_0001
The selectivity of total olefins was calculated from selectivity of olefin products including ethylene, propylene, and butenes.
It can be s en that using of the inventive catalysts for conversion of a paraffinic hydrocarbon feed results in higher selectivity of total olefin products and lower production of methane and heavier hydrocarbons.
The features disclosed in the foregoing description and in the claims may, both separately and in any combination, be material for realizing the invention in diverse forms thereof.

Claims

1. A catalyst in oxidic form comprising metals Ml, M2, M3 and M4} wherein:
Ml is selected from Si, Al, Zr, and mixtures thereof; M2 is selected from Pt, Cr, and mixtures thereof; M3 is selected from W, Mo, Re, and mixtures thereof; and M4 is selected from Sn, K, Y, Yb and mixtures thereof; wherein mass fraction of Ml is in the range of 0.1 to 0.8; mass fraction of M2 is in the range of 0.001 to 0.2; mass fraction of M3 is in the range of 0.001 to 0.2; mass fraction of M4 is in the range of 0.0001 to 0.2; and mass fraction of oxygen is in the range of 0.1 to 0.8.
2. The catalyst according to claim 1 wherein M2 is Pt.
3. The catalyst according to claim 1 wherein M3 is W.
4. The catalyst according to claim 1 wherein the mass fraction of Ml is in the range of 0.2 to 0.6.
5. The catalyst according to claim 1 wherein the mass fraction of M2 is in the range of O.0015 to O.15.
6. The catalyst according to claim 1 wherein the mass fraction of M3 is in the range of O.005 to O.15.
7. The catalyst according to claim 1 wherein the mass fraction of M4 is in the range of 0.00015 to 0.03
8. The catalyst according to claim 1 wherein the mass fraction of oxygen is in the range of 0.2 to 0.5.
9. The catalyst according to any of the preceding claims further comprising M5 selected from Mg, Ca, Mn, Fe, Co, Ni, Cu, and mixtures thereof, wherein mass fraction of M5 is in the range of 0.005 to 0.1. 2017/001445
10. The catalyst according to claim 9 wherein the mass fraction of M5 is in the range of 0.01 to 0.09.
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