AU2020362824B2 - Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof - Google Patents

Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof Download PDF

Info

Publication number
AU2020362824B2
AU2020362824B2 AU2020362824A AU2020362824A AU2020362824B2 AU 2020362824 B2 AU2020362824 B2 AU 2020362824B2 AU 2020362824 A AU2020362824 A AU 2020362824A AU 2020362824 A AU2020362824 A AU 2020362824A AU 2020362824 B2 AU2020362824 B2 AU 2020362824B2
Authority
AU
Australia
Prior art keywords
catalyst
sulfur
group viii
dehydrogenation
loading
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.)
Active
Application number
AU2020362824A
Other versions
AU2020362824A1 (en
Inventor
Kennin SO
Ushio TAKA
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.)
Highchem Co Ltd
Original Assignee
Highchem Co Ltd
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 Highchem Co Ltd filed Critical Highchem Co Ltd
Publication of AU2020362824A1 publication Critical patent/AU2020362824A1/en
Application granted granted Critical
Publication of AU2020362824B2 publication Critical patent/AU2020362824B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • 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
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/06—Toluene
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A catalyst for dehydrogenation of cycloalkanes, comprising an alumina support, a VIII-group element, Sn element, sulfur element, and at least one doped metal selected from alkali metals, wherein VIII-group element and Sn element exist in the form of VIII

Description

CATALYST FOR DEHYDROGENATION OF CYCLOALKANES, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF FIELD OF THE INVENTION
The present application relates to a catalyst for dehydrogenation of cycloalkanes, its preparation
process and its use in dehydrogenation of cycloalkanes.
BACKGROUND OF THE INVENTION
As a clean and efficient environmentally friendly energy source, hydrogen energy is regarded as
the most potential energy source in the 21st century. Its development and utilization have become
a global research hotspot. At present, hydrogen storage technologies mainly include physical
hydrogen storage, adsorption hydrogen storage and chemical hydrogen storage. Physical
hydrogen storage technology has strict requirements and harsh operating conditions for hydrogen
storage equipment, which makes the use cost of this technology high. Adsorption hydrogen
storage and chemical hydrogen storage are the focus of current research. The technology of
liquid organic hydride hydrogen storage in chemical hydrogen storage realizes the storage and
release of hydrogenbyusingthereversiblehydrogenation-dehydrogenation reaction cycle
between unsaturated liquid aromatic hydrocarbons and the corresponding cycloalkanes. The
hydrogen storage capacity of liquid organic hydride is much higher than that of high-pressure
compression hydrogen storage and metal hydride hydrogen storage. In liquid organic hydrides,
cycloalkanes are in liquid state at normal temperature and pressure, so that the existing
transportation methods of petroleum chemicals can be used in this technology to realize
long-distance hydrogen transportation. However, because the dehydrogenation reaction in this
process is reversible, the hydrogen production rate is low, and the purity of hydrogen produced is
not high due to the occurrence of side reaction, which increases the separation cost. Therefore,
the development of a dehydrogenation catalyst with high stability, high conversion and high
selectivity has become the key to the application of organic liquid hydride hydrogen storage
technology.
The commonly used catalyst for dehydrogenation of cycloalkane is the supported metal catalyst,
and the active components thereof are Pt, Pd, Rh, Ni, Co, etc. As the most commonly used carrier of noble metal dehydrogenation catalyst, alumina has the characteristics of easy availability and high reaction activity. However, as it has many acidic active centers on the surface, it is easy to coke and inactivate the catalyst. Reference document 1 (JournalofFuel
Chemistry and Technology, 1998, 26(6), 543-547) reports adding an appropriate amount of K20
to a Pt supported dehydrogenation catalyst can change the strong acidic site on the catalyst
surface, which is conducive to preventing carbon deposition and improving the stability of the
catalyst. However, the effect of this method on improving the selectivity of catalyst is not
significant, and it cannot solve the problem of producing methane due to side reaction. In
addition, by adding a second metal component such as Ni, Mo, W, Re, Ir, Sn, etc., the
dehydrogenation activity of the catalyst can also be further improved and the performance
thereof can be improved. CN107376907A discloses a Pt-Sn supported hydrotalcite
dehydrogenation catalyst and a preparation process thereof. In the catalyst, Pt is in a reduced
state, Sn is in coexistence of a reduced state and an oxidized state. In the dehydrogenation
reaction of cycloalkanes, it has the advantages of mild reaction conditions, high selectivity, high
hydrogen release rate, etc. However, the conversion of the catalyst under the conditions of low
loading still needs to be further improved.
SUMMARY OF THE INVENTION
In view of the above situation of the prior art, the inventor has conducted extensive and in-depth
research on the field of catalyst for dehydrogenation of cycloalkane in hope of discovering a
catalyst for dehydrogenation of cycloalkane having the properties of improved cycloalkane
conversion, improved aromatic hydrocarbon selectivity and stability. The inventor found a
dehydrogenation catalyst comprising an alumina carrier, a group VIII element, Sn element, sulfur
element and at least one doping metal selected from alkali metals, wherein the alkali metal in the
catalyst is present in the form of oxide, and the group VIII element and Sn element are present in
the form of VIII3Sn intermetallic compound. When the catalyst is used in the dehydrogenation
reaction of cycloalkanes, it can maintain high conversion, selectivity and good stability under the
conditions of low loading of group VIII element. The present invention is realized based on the
above discovery.
The present invention attempts to provide a catalyst for dehydrogenation reaction when hydrogen is released from cycloalkanes. When the catalyst is used for dehydrogenation of cycloalkane, it can obtain improved cycloalkane conversion and improved aromatic hydrocarbon selectivity, and also has improved stability.
The present invention also attempts to provide a process for preparing a catalyst for dehydrogenation of cycloalkane. This process can not only easily prepare a catalyst for dehydrogenation of cycloalkane, but also obtain improved cycloalkane conversion and aromatic hydrocarbon selectivity as well as improved stability when the catalyst prepared by this process is used for dehydrogenation of cycloalkane.
The present invention also attempts to provide the use of the catalyst of the present invention or the catalyst prepared by the process of the present invention as a catalyst in dehydrogenation of cycloalkane. In this application, improved cycloalkane conversion, aromatic hydrocarbon selectivity and stability can be obtained.
The technical solution for realizing the above attempts of the present invention can be summarized as follows:
1. A catalyst for dehydrogenation of cycloalkanes, comprising an alumina carrier, a group VIII element, Sn element, sulfur element and at least one doping metal selected from alkali metals, wherein the group VIII element and Sn element are present in the formof VIII3Sn intermetallic compound, the alumina carrier has a specific surface area of above 150m 2/g, a pore volume of above 0.5cm3/g, an average pore diameter of 70 to 200A.
2. The catalyst according to Item 1, wherein the alumina carrier has a specific surface area of above 210m2/g, a pore volume of above 0.55cm 3/g, and an average pore diameter of 80 to 150A.
3. The catalyst according to Item 1 or 2, wherein the group VIII element is selected from one or more of Pt, Pd and Ir, preferably Pt, and the content of the group VIII element is 0.2 to 5.wt%, preferably 0.3 to 2.Owt%, based on the weight of the catalyst.
4. The catalyst according to any one of Items I to 3, wherein the content of Sn element is 0.04 to 1.Owt%, preferably 0.06 to 0.4wt%, based on the weight of the catalyst.
5. The catalyst according to any one of Items 1 to 4, wherein the content of sulfur element is 0.1 to 3wt%, preferably 0.3 to lwt%, based on the weight of the catalyst.
6. The catalyst according to any one of Items 1 to 5, wherein the content of the alkali metal
element is 0.1 to lwt%, preferably 0.2 to 0.5wt%, based on the weight of the catalyst.
7. A process for preparing the catalyst according to any one of Items 1 to 6, comprising the steps
of:
a. mixing an aluminum source and an adhesive uniformly, kneading and extruding to obtain an
alumina carrier;
b. drying and calcining, followed by loading a group VIII element and Sn element;
c. drying and calcining, followed by adding an alkali metal compound;
d. calcining and performing a reduction treatment to make the alkali metal present in the form of
oxide and the supported metal present in the formof VIII 3 Sn intermetallic compound,
wherein sulfur or a sulfur compound are present in the aluminum source, or sulfur or a sulfur
compound are added to the alumina carrier during or after the preparation of the alumina carrier.
8. The process according to Item 7, wherein the aluminum source is selected from one or more of
pseudo boehmite, boehmite and aluminum hydroxide, preferably pseudo boehmite.
9. The process according to Item 7 or 8, wherein the sulfur or sulfur compound is selected from
one or more of sulfur powder, sulfuric acid and sulfate.
10. The process according to any one of Items 7 to 9, wherein a metal acid, metal acid salt,
chloride, ammonia complex, carbonyl complex or their mixture of group VIII element are used
as raw materials, and the loading of group VIII element is realized by means of ion exchange,
impregnation or precipitation.
11. The process according to any one of Items 7 to 10, wherein a metal acid, metal acid salt,
chloride, ammonia complex, carbonyl complex or their mixture of Sn element are used as raw
materials, and the loading of Sn element is realized by means of successive impregnation or
co-impregnation.
12. The process according to any one of Items 7 to 11, wherein in step b, the molar ratio nvml: nsn of group VIII element and Sn element is 2 to 4, preferably 2.5 to 3.5.
13. The process according to any one of Items 7 to 12, wherein the metal acid, metal acid salt,
chloride, ammonia complex, carbonyl complex or their mixture of alkali metal element are used
as raw materials, and the loading of alkali metal element is realized by means of ion exchange,
impregnation or precipitation.
14. The process according to any one of Items 7 to 13, wherein drying is carried out after loading
the group VIII element and Sn element, and after standing, calcining is carried out at a
temperature of 300 to 750°C for a period of I to 12h.
15. The process according to any one of Items 7 to 14, wherein the catalyst is reduced with a
reducing agent, such as hydrogen, at a temperature of 350-800°C for a period of 0.5 to 24h.
16. Use of the catalyst according to any one of Items I to 6 in dehydrogenation of cycloalkanes.
These and other attempts, features and advantages of the present invention will be easily
understood by ordinary skilled artisans after consideration based on the following.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates the atomic structure of PtSn and Pt3Sn intermetallic compounds.
Figure 2 illustrates the XRD diffraction patterns of Pt, PtSn and Pt3Sn intermetallic compounds
in Comparative Example 1, Comparative Example 3 and Example 1.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect, the present invention provides a catalyst for dehydrogenation of cycloalkanes,
comprising an alumina carrier, a group VIII element, Sn element, sulfur element and at least one
doping metal selected from alkali metals, wherein the group VIII element and Sn element are
present in the form of VIII3Sn intermetallic compound.
In a catalyst containing two or more metals, the metal particles may form an intermetallic
compound with different ratios in addition to being present in the state of single element or alloy.
Intermetallic compound refers to a stoichiometric compound formed between two or more
metals.
In one embodiment, for the alumina carrier, the specific surface area of a porous carrier is above 150m 2 /g, the pore volume is above 0.5cm3/g, the average pore diameter is 70 to 200k, preferably the specific surface area is above 210m 2 /g, the pore volume is above 0.55cm 3/g, and the average pore diameter is 80 to 150A.
Preferably, the group VIII element in the catalyst is selected from one or more of Pt, Pd and Ir, preferably Pt, with a content of 0.2 to 5.wt%, preferably 0.3 to 2.Owt%, based on the weight of the catalyst.
Preferably, the content of Sn element in the catalyst is 0.04 to1.wt%, preferably 0.06 to 0.4wt%, based on the weight of the catalyst.
Preferably, the content of sulfur element in the catalyst is 0.1 to 3wt%, preferably 0.3 to lwt%, based on the weight of the catalyst.
Preferably, the alkali metal in the catalyst is selected from one or more of Li, Na, K and Rb, preferably K, with a content of 0.1 to lwt%, preferably 0.2 to 0.5wt%, based on the weight of the catalyst.
In the second aspect, the present invention provides a process for preparing the catalyst of the present invention, comprising the steps of:
a. mixing an aluminum source and an adhesive uniformly, kneading and extruding to obtain an alumina carrier;
b. drying and calcining, followed by loading a group VIII element and Sn element;
c. drying and calcining, followed by adding an alkali metal compound;
d. calcining and performing a reduction treatment to make the alkali metal present in the form of oxide and the supported metal present in the formof VIII 3 Sn intermetallic compound,
wherein sulfur or a sulfur compound are present in the aluminum source, or sulfur or a sulfur compound are added to the alumina carrier during or after the preparation of the alumina carrier.
In one embodiment, after mixing the aluminum source and adhesive uniformly, the formed alumina carrier is obtained after kneading, extruding, drying and calcining. There are no special restrictions on the steps of kneading, extruding, drying and calcining, and any method known in the art can be used.
Preferably, the aluminum source is selected from one or more of pseudo boehmite, boehmite and
aluminum hydroxide, preferably pseudo boehmite.
Preferably, the adhesive is selected from one or more of nitric acid, sesbania powder,
polyacrylamide, methylcellulose, polyvinyl alcohol and sodium carboxymethylcellulose,
preferably nitric acid, sesbania powder and methylcellulose.
In a preferred embodiment, the sulfur or sulfur compound may be pre-existing in the aluminum
source used to prepare the catalyst carrier, or dispersed in the catalyst carrier during or after the
preparation of the catalyst carrier. For example, sulfur powder and a sulfur compound can be
mentioned, such as sulfuric acid, sulfate, etc., including aluminum sulfate, ammonium sulfate,
etc. From the point of view that sulfur may be dispersed on the carrier, a sulfur compound with
solubility in water or organic solvents is preferred, and sulfuric acid, aluminum sulfate,
ammonium sulfate and the like can be mentioned as such sulfur compound.
Preferably, a metal acid, metal acid salt, chloride, ammonia complex, carbonyl complex or their
mixture of group VIII element are used as raw materials, and the loading of group VIII element
is realized by means of ion exchange, impregnation or precipitation.
Preferably, a metal acid, metal acid salt, chloride, ammonia complex, carbonyl complex or their
mixture of Sn element are used as raw materials, and the loading of Sn element is realized by
means of successive impregnation or co-impregnation.
Preferably, in step b, the molar ratio nv : nsn of group VIII element and Sn element is 2 to 4,
preferably 2.5 to 3.5.
After loading the group VIII element and Sn element, the acidity of the catalyst surface is
adjusted by adding an alkali metal. Preferably, a metal acid, metal acid salt, chloride, ammonia
complex, carbonyl complex or their mixture of alkali metal element are used as raw materials,
and the loading of alkali metal element is realized by means of ion exchange, impregnation or
precipitation.
In a preferred embodiment, the catalyst of the present invention is optionally kept aside for 24h
after the group VIII element and Sn element are loaded, then is slowly stirred and dried the surface water vapor at about 30°C, dried, optionally kept aside at room temperature for one night, and then calcined at 300 to 750°C for 1 to 12h. The group VIII element and Sn element are present in the form of intermetallic compound of VIII 3Sn. After an alkali metal element is added, the catalyst is calcined again at a temperature of 300 to 500°C for a period of I to 12h.
In a preferred embodiment, the catalyst of the present invention is subjected to a reduction treatment before use, and a known catalyst reduction method can be adopted, that is, a method of reducing a catalyst by contacting a reducing agent such as hydrogen with the catalyst may be used to realize off-site pre-reduction or on-line reduction. Preferably, the reduction temperature is 350 to 800°C and the reduction time is 0.5 to 24h.
In the last aspect, the present invention provides the use of the catalyst of the present invention or the catalyst prepared by the process of the present invention as a catalyst in dehydrogenation of cycloalkanes.
In a preferred embodiment, the cycloalkane is selected from one or more of methylcyclohexane, cyclohexane and decahydronaphthalene, preferably methylcyclohexane or cyclohexane.
In a preferred embodiment, the dehydrogenation reaction is carried out in a fixed bed reactor using methylcyclohexane as raw material. The catalyst loading capacity varies depending on the reactor volume. Before feeding, the catalyst is subjected to a reduction treatment to make the supported metal present in the form of single element. The reduction conditions are: hydrogen pressure: 0.1 to 1OMPa, temperature: 300 to 800°C, time: 0.5 to 24h, preferably hydrogen pressure: 0.2 to 5MPa, temperature: 300 to 550°C, time: 3 to 8h. The reaction conditions are: hydrogen pressure: 0.1 to 1OMPa, temperature: 250 to 500°C, mass space velocity: 0.5 to 20h- 1 ,
hydrogen oil molar ratio: 0 to 15, preferably hydrogen pressure: 0.2 to 2MPa, temperature: 300 to 450°C, mass space velocity: 1 to 10h- 1, hydrogen oil molar ratio: 1 to 10.
EXAMPLES
The following examples further disclose the present invention, but the present invention is not limited to the following examples.
Comparative Example 1
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an impregnation method, with a sulfur loading of 0.5wt%. The obtained S containing aluminum powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for 12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2PtCl 2 solution (containing 0.00748g Pt per mL) by an impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at 60°C for 3h, 120°C for 12h and calcined at 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt% Pt/A 2 0 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The temperature is raised to 400°C at 10°C/min for 1h, and then it is cooled to the reaction temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to perform the reaction and the product is analyzed by gas chromatography. Reaction conditions: the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Comparative Example 2
lOg pseudo boehmite, 0.2g sesbania powder and 0.2g carboxymethyl cellulose are mixed uniformly. 12.5g nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for 12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2PtCl 2 solution (containing 0.00748g Pt per mL) by an impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at 60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated with SnCl 2 solution by an impregnation method of filling holes, with the molar ratio of ne: nsn=3.
After standing for 24h, it is stirred and the surface water thereof is evaporated while stirring at
30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation method of
filling holes is again used to impregnate it with KNO 3 solution, with a K loading of 0.3wt%.
After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt%
Pt-Sn-K2 0/A 2 0 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The
temperature is raised to 400°C at 10C/min for 1h, and then it is cooled to the reaction
temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to
perform the reaction and the product is analyzed by gas chromatography. Reaction conditions:
the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of
methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of
dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of
dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Comparative Example 3 (PtSn Structure)
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an
impregnation method, with a sulfur loading of 0.5wt%. The obtained S containing aluminum
powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g
nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded
for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a
diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for
12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2 PtCl 2 solution (containing 0.00748g Pt per mL) by an
impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at
60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated
with SnCl2 solution by an impregnation method of filling holes, with the molar ratio of ne:
nsn=0.6. After standing for 24h, it is stirred and the surface water thereof is evaporated while
stirring at 30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation method of filling holes is again used to impregnate it with KNO 3 solution, with a K loading of
0.3wt%. After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt%
Pt-Sn-K2 0/S-A1 20 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The
temperature is raised to 400°C at 10C/min for h, and then it is cooled to the reaction
temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to
perform the reaction and the product is analyzed by gas chromatography. Reaction conditions:
the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of
methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of
dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of
dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Example 1 (Pt3 Sn Structure)
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an
impregnation method, with a sulfur loading of 0.5wt%. The obtained S containing aluminum
powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g
nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded
for about lh. After the powder is completely kneaded, it is extruded by a strip extruder (with a
diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for
12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2 PtCl 2 solution (containing 0.00748g Pt per mL) by an
impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at
60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated
with SnCl 2 solution by an impregnation method of filling holes, with the molar ratio of nt: nsn= 3 .
After standing for 24h, it is stirred and the surface water thereof is evaporated while stirring at
30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation method of
filling holes is again used to impregnate it with KNO 3 solution, with a K loading of 0.3wt%.
After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt%
Pt-Sn-K2 0/S-A1 20 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The
temperature is raised to 400°C at 10C/min for 1h, and then it is cooled to the reaction
temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to
perform the reaction and the product is analyzed by gas chromatography. Reaction conditions:
the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of
methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of
dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of
dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Example 2 (Pt3 Sn Structure)
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an
impregnation method, with a sulfur loading of 0.5wt%. The obtained S containing aluminum
powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g
nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded
for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a
diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for
12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2 PtCl 2 solution (containing 0.00748g Pt per mL) by an
impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at
60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated
with SnCl2 solution by an impregnation method of filling holes, with the molar ratio of n:
nsn=3.4. After standing for 24h, it is stirred and the surface water thereof is evaporated while
stirring at 30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation
method of filling holes is again used to impregnate it with KNO 3 solution, with a K loading of
0.3wt%. After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt%
Pt-Sn-K2 0/S-A1 20 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The
temperature is raised to 400°C at 10C/min for 1h, and then it is cooled to the reaction temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to perform the reaction and the product is analyzed by gas chromatography. Reaction conditions: the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Example 3 (Pt3 Sn Structure)
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an impregnation method, with a sulfur loading of 0.8wt%. The obtained S containing aluminum powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for 12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2PtCl 2 solution (containing 0.00748g Pt per mL) by an impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at 60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated with SnCl 2 solution by an impregnation method of filling holes, with the molar ratio of n: nsn=3. After standing for 24h, it is stirred and the surface water thereof is evaporated while stirring at 30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation method of filling holes is again used to impregnate it with KNO 3 solution, with a K loading of 0.3wt%. After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt% Pt-Sn-K2 0/S-A1 20 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The temperature is raised to 400°C at 10C/min for 1h, and then it is cooled to the reaction temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to perform the reaction and the product is analyzed by gas chromatography. Reaction conditions: the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Example 4 (Pt3 Sn Structure)
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an
impregnation method, with a sulfur loading of 0.3wt%. The obtained S containing aluminum
powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g
nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded
for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a
diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for
12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2 PtCl 2 solution (containing 0.00748g Pt per mL) by an
impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at
60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated
with SnCl 2 solution by an impregnation method of filling holes, with the molar ratio of n: nsn=3.
After standing for 24h, it is stirred and the surface water thereof is evaporated while stirring at
30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation method of
filling holes is again used to impregnate it with KNO 3 solution, with a K loading of 0.3wt%.
After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt%
Pt-Sn-K2 0/S-A1 20 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The
temperature is raised to 400°C at 10C/min for 1h, and then it is cooled to the reaction
temperature in the hydrogen gas stream. The raw material oil methylcyclohexane is introduced to
perform the reaction and the product is analyzed by gas chromatography. Reaction conditions:
the temperature is 320°C and the reaction pressure is 0.4MPa. The liquid space velocity of
methylcyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 2. The results of
dehydrogenation of methylcyclohexane for 5h are shown in Table 1. The results of
dehydrogenation of methylcyclohexane for 24h are shown in Table 2.
Example 5 (Pt3 Sn Structure)
1g pseudo boehmite is taken and impregnated with aluminum sulfate solution by an
impregnation method, with a sulfur loading of 0.5wt%. The obtained S containing aluminum
powder is mixed uniformly with 0.2g sesbania powder and 0.2g carboxymethyl cellulose. 12.5g
nitric acid of 3.6wt% is added while stirring. The mixture is transferred to a kneader and kneaded
for about 1h. After the powder is completely kneaded, it is extruded by a strip extruder (with a
diameter of 1 to 2mm and length of about 5mm). The extruded strip carrier is dried at 120°C for
12h and calcined at 700°C for 3h to obtain a formed carrier.
It is then impregnated with H2 PtCl 2 solution (containing 0.00748g Pt per mL) by an
impregnation method of filling holes and kept aside for 24h, then dried under reduced pressure at
60°C for 3h, 120°C for 12h and calcined at 400°C for 3h to obtain a single platinum catalyst.
The prepared single platinum catalyst is reduced with pure hydrogen and then is impregnated
with SnCl 2 solution by an impregnation method of filling holes, with the molar ratio of n: nsn=3.
After standing for 24h, it is stirred and the surface water thereof is evaporated while stirring at
30°C, and then dried at 120°C for 12h and calcined at 400°C for 3h. The impregnation method of
filling holes is again used to impregnate it with KNO 3 solution, with a K loading of 0.3wt%.
After standing for 24h, it is dried at 120°C for 12h and calcined 400°C for 3h.
2mL of the prepared catalyst is reduced online with pure hydrogen to obtain 0.5wt%
Pt-Sn-K2 0/S-A1 20 3 catalyst. Reduction conditions: hydrogen flow rate 50mL/min. The
temperature is raised to 400°C at 10°C/min for 1h, and then it is raised to the reaction temperature
in the hydrogen gas stream. The raw material oil cyclohexane is introduced to perform the
reaction and the product is analyzed by gas chromatography. Reaction conditions: the
temperature is 480°C and the reaction pressure is 0.4MPa. The liquid space velocity of
cyclohexane is 2h-1 and the hydrogen oil ratio (mol/mol) is 4. The results of dehydrogenation of
cyclohexane for 5h and 24h are shown in Table 3.
Table 1. Results of dehydrogenation of methylcyclohexane for 5h
Comparative Comparative Comparative Example Example Example Example
Example 1 Example 2 Example 3 1 2 3 4
Reaction
temperature 320 320 320 320 320 320 320
(°C)
Conversion 96.2 95.2 31.4 99.3 99.4 99.2 98.8 (0%)
Toluene selectivity 99.2 98.8 96.8 99.6 99.5 99.4 99.1
(0%)
Methane
concentration 73 117 86 24 26 27 32
(ppm)
Table 2. Results of dehydrogenation of methylcyclohexane for 24h
Comparative Comparative Comparative Example Example Example Example
Example 1 Example 2 Example 3 1 2 3 4
Reaction
temperature 320 320 320 320 320 320 320
(°C)
Conversion 94.1 90.4 27.9 99.3 99.2 99.0 98.6 (0%)
Toluene selectivity 99.0 98.7 96.5 99.6 99.6 99.5 99.0 (0%)
Methane
concentration 78 98 79 24 23 21 31
(ppm)
Table 3. Results of dehydrogenation of cyclohexane for 5h and 24h
Example 5 Reaction for 5h Reaction for 24h
Reaction temperature (°C) 480 480
Conversion (%) 89.1 88.6
Benzene selectivity (%) 91.2 90.8
It can be seen from the above Examples and Comparative Examples that the catalyst provided by
the present invention has higher cycloalkane conversion and aromatic hydrocarbon selectivity
and better stability when used in dehydrogenation reactions of methylcyclohexane and
cyclohexane.
The above is only an embodiment of the present invention. It should be pointed out that
improvements and modifications made by those skilled in the art within the scope of the
principle of the present invention should also be regarded as the protection scope of the present
invention.
The reference to any prior art in this specification is not, and should not be taken as, an
acknowledgement or any form of suggestion that such prior art forms part of the common
general knowledge.
It will be understood that the terms "comprise" and "include" and any of their derivatives (e.g.
comprises, comprising, includes, including) as used in this specification, and the claims that
follow, is to be taken to be inclusive of features to which the term refers, and is not meant to
exclude the presence of any additional features unless otherwise stated or implied.
In some cases, a single embodiment may, for succinctness and/or to assist in understanding the
scope of the disclosure, combine multiple features. It is to be understood that in such a case,
these multiple features may be provided separately (in separate embodiments), or in any other
suitable combination. Alternatively, where separate features are described in separate
embodiments, these separate features may be combined into a single embodiment unless
otherwise stated or implied. This also applies to the claims which can be recombined in any
combination. That is a claim may be amended to include a feature defined in any other claim.
Further a phrase referring to "at least one of' a list of items refers to any combination of those items, including single members. As an example, "at least one of: a, b, or c" is intended to cover: a, b, c, a-b, a-c, b-c, and a-b-c.

Claims (20)

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:
1. A catalyst for dehydrogenation of cycloalkanes, comprising an alumina carrier, a group VIII element, Sn element, sulfur element and at least one doping metal selected from alkali metals, wherein the group VIII element and Sn element are present in the formof VIII3Sn intermetallic compound, the alumina carrier has a specific surface area of above 150m 2 /g, a pore volume of above 0.5cm 3/g, an average pore diameter of 70 to 200A.
2. The catalyst according to claim 1, wherein the alumina carrier has a specific surface area of above 210m 2 /g, a pore volume of above 0.55cm3/g, and an average pore diameter of 80 to 150A.
3. The catalyst according to claim 1 or 2, wherein the group VIII element is selected from one or more of Pt, Pd and Ir, and the content of the group VIII element is 0.2 to 5.wt%, based on the weight of the catalyst.
4. The catalyst according to claim 3, wherein the content of the group VIII element is 0.3 to 2.Owt%, based on the weight of the catalyst.
5. The catalyst according to any one of claims 1 to 4, wherein the content of Sn element is 0.04 to 1.Owt%, based on the weight of the catalyst.
6. The catalyst according to claim 5, wherein the content of Sn element is 0.06 to 0.4wt%, based on the weight of the catalyst.
7. The catalyst according to any one of claims 1 to 6, wherein the content of sulfur element is 0.1 to 3wt%, based on the weight of the catalyst.
8. The catalyst according to claim 7, wherein the content of sulfur element is 0.3 to lwt%, based on the weight of the catalyst.
9. The catalyst according to any one of claims 1 to 8, wherein the content of the alkali metal element is 0.1 to lwt%, based on the weight of the catalyst.
10. The catalyst according to claim 9, wherein the content of the alkali metal element is 0.2 to 0.5wt%, based on the weight of the catalyst.
11. A process for preparing the catalyst according to any one of claims 1 to 10, comprising the steps of: a. mixing an aluminum source and an adhesive uniformly, kneading and extruding to obtain an alumina carrier; b. drying and calcining, followed by loading a group VIII element and Sn element; c. drying and calcining, followed by adding an alkali metal compound; d. calcining and performing a reduction treatment to make the alkali metal present in the form of oxide and the supported metal present in the formof VIII3Sn intermetallic compound, wherein sulfur or a sulfur compound are present in the aluminum source, or sulfur or a sulfur compound are added to the alumina carrier during or after the preparation of the alumina carrier.
12. The process according to claim 11, wherein the aluminum source is selected from one or
more of pseudo boehmite, boehmite and aluminum hydroxide, preferably pseudo boehmite.
13. The process according to claim 11 or 12, wherein the sulfur or sulfur compound is selected
from one or more of sulfur powder, sulfuric acid and sulfate.
14. The process according to any one of claims 11 to 13, wherein a metal acid, metal acid salt,
chloride, ammonia complex, carbonyl complex or their mixture of group VIII element are used
as raw materials, and the loading of group VIII element is realized by means of ion exchange,
impregnation or precipitation.
15. The process according to any one of claims 11 to 14, wherein a metal acid, metal acid salt,
chloride, ammonia complex, carbonyl complex or their mixture of Sn element are used as raw
materials, and the loading of Sn element is realized by means of successive impregnation or
co-impregnation.
16. The process according to any one of claims 11 to 15, wherein in step b, the molar ratio nvm:
nsn of group VIII element and Sn element is 2 to 4, preferably 2.5 to 3.5.
17. The process according to any one of claims 11 to 16, wherein the metal acid, metal acid salt,
chloride, ammonia complex, carbonyl complex or their mixture of alkali metal element are used
as raw materials, and the loading of alkali metal element is realized by means of ion exchange,
impregnation or precipitation.
18. The process according to any one of claims 11 to 17, wherein drying is carried out after loading the group VIII element and Sn element, and after standing, calcining is carried out at a temperature of 300 to 750°C for a period of I to 12h.
19. The process according to any one of claims 11 to 18, wherein the catalyst is reduced with a
reducing agent, such as hydrogen, at a temperature of 350-800°C for a period of 0.5 to 24h.
20. Use of the catalyst according to any one of claims 1 to 10 in dehydrogenation of
cycloalkanes.
AU2020362824A 2019-10-11 2020-10-10 Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof Active AU2020362824B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201910962010.6 2019-10-11
CN201910962010.6A CN112642444A (en) 2019-10-11 2019-10-11 Catalyst for dehydrogenation of naphthenic hydrocarbon and preparation and application thereof
PCT/CN2020/120172 WO2021068934A1 (en) 2019-10-11 2020-10-10 Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof

Publications (2)

Publication Number Publication Date
AU2020362824A1 AU2020362824A1 (en) 2022-05-26
AU2020362824B2 true AU2020362824B2 (en) 2023-11-23

Family

ID=75343763

Family Applications (1)

Application Number Title Priority Date Filing Date
AU2020362824A Active AU2020362824B2 (en) 2019-10-11 2020-10-10 Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof

Country Status (4)

Country Link
JP (1) JP7411078B2 (en)
CN (1) CN112642444A (en)
AU (1) AU2020362824B2 (en)
WO (1) WO2021068934A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115703065B (en) * 2021-08-17 2024-05-07 中国石油天然气股份有限公司 Low temperature dehydrogenation method for hydrogenation aromatic compound
CN113866044B (en) * 2021-11-23 2024-04-19 云南电网有限责任公司电力科学研究院 Method for testing liquid organic hydrogen storage material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106693993A (en) * 2016-12-21 2017-05-24 北京赛诺时飞石化科技有限公司 Sulfur-containing light alkane dehydrogenation catalyst and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1013361B (en) * 1987-03-13 1991-07-31 中国科学院大连化学物理研究所 Catalyst containing pt, sn, li, s for dehydrogenation of saturated hydrocarbon
CN102531912B (en) 2011-12-31 2013-09-11 浙江工业大学 Preparation method of N-alkyl arylamine
CN107376907B (en) * 2017-07-28 2019-09-17 湘潭大学 A kind of platinum tin carried hydrotalcite dehydrogenation and its preparation method and application
CN107649125B (en) 2017-10-09 2020-04-14 中国石油大学(华东) Propane dehydrogenation Ptx-Sny binary alloy nano catalyst and preparation method thereof
CN110180537A (en) * 2019-06-12 2019-08-30 福州大学 One kind is for dehydrogenating low-carbon alkane metal alloy catalyst and its preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106693993A (en) * 2016-12-21 2017-05-24 北京赛诺时飞石化科技有限公司 Sulfur-containing light alkane dehydrogenation catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUNG. J. et al., "Effect of Direct Reduction Treatment on Pt–Sn/Al2O3 Catalyst for Propane Dehydrogenation", CATALYSTS, vol. 9, pages 446, Published 14 May 2019 *

Also Published As

Publication number Publication date
JP2022552169A (en) 2022-12-15
WO2021068934A1 (en) 2021-04-15
AU2020362824A1 (en) 2022-05-26
CN112642444A (en) 2021-04-13
JP7411078B2 (en) 2024-01-10

Similar Documents

Publication Publication Date Title
Wang et al. Investigation on modification of Ru/CNTs catalyst for the generation of COx-free hydrogen from ammonia
CN102049267B (en) Catalyst for preparing propylene by dehydrogenating propane as well as preparation method and applications thereof
JP5820817B2 (en) Ammonia synthesis catalyst and ammonia synthesis method
JP4907210B2 (en) Hydrogen storage and transport system
AU2020362824B2 (en) Catalyst for dehydrogenation of cycloalkanes, preparation method therefor and application thereof
CA2883503A1 (en) Catalyst for producing hydrogen and method for producing hydrogen
CA2730846A1 (en) Palladium-based catalyst for selective hydrogenation of acetylene
CN114700084B (en) Catalyst for hydrogenation and dehydrogenation of organic hydrogen storage liquid, preparation method thereof and hydrogenation and dehydrogenation method of organic hydrogen storage liquid
ITMI980857A1 (en) CATALYST CONTAINING AN AMORPHOUS ALLOY CONTAINING BORON ITS PREPARATION AND USE
Li et al. Effect of the morphology on the vapor phase benzene catalytic hydrogenation over Pd/CeO2 catalyst
CN114917929B (en) Catalyst for hydrogenation and dehydrogenation of organic liquid hydrogen storage material and preparation method and application thereof
JP4597024B2 (en) Cycloolefin production catalyst and cycloolefin production method
WO2023134779A1 (en) Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol
Shen et al. Water-induced gaseous formaldehyde decomposition using ruthenium organic crystalline particles
GB2269116A (en) A process for the production of aromatic alcohol by selective hydrogenation of aromatic ketone
JP2016059852A (en) Catalyst and ammonia synthesis method
Furusawa et al. Effect of alkali metal addition to a Ru/CeO2 catalyst prepared by NaBH4 reduction on the catalytic performance for H2 production via NH3 decomposition
JPH08253433A (en) Production of cycloolefin
JP2016209786A (en) Dehydrogenation catalyst, production system of hydrogen and method for producing hydrogen
CN107973682B (en) Method for preparing propylene by propane dehydrogenation
KR100510321B1 (en) Catalysts for refining reformed gas and process for selectively removing carbon monoxide in reformed gas using the same
JP4033976B2 (en) Method for producing cycloolefin
WO2022244797A1 (en) Method for producing isopropyl alcohol
CN111036204A (en) Glycerol hydrogenolysis method
CN111054410A (en) Liquid phase dehydrogenation catalyst, preparation and use

Legal Events

Date Code Title Description
FGA Letters patent sealed or granted (standard patent)