CN113908880A - Dehydrogenation catalyst and preparation method and application thereof - Google Patents

Dehydrogenation catalyst and preparation method and application thereof Download PDF

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CN113908880A
CN113908880A CN202111287614.9A CN202111287614A CN113908880A CN 113908880 A CN113908880 A CN 113908880A CN 202111287614 A CN202111287614 A CN 202111287614A CN 113908880 A CN113908880 A CN 113908880A
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catalyst
dehydrogenation catalyst
dodecane
dehydrogenation
molecular sieve
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朱善辉
樊卫斌
何月
董梅
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46—Iron group metals or copper

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Abstract

The invention provides a dehydrogenation catalyst and a preparation method and application thereof, belonging to the technical field of alkane dehydrogenation. The dehydrogenation catalyst of the present invention comprises a carrier and an active component supported on the carrier; the carrier is Na-type ZSM-5 molecular sieve; the active component is noble metal Pt; the mass content of active components in the dehydrogenation catalyst is 0.05-0.3%. The catalyst of the invention reduces the content of active noble metal Pt, saves the preparation cost of the catalyst, has ultra-long service life in the reaction of preparing the dodecamonoolefin by dehydrogenating n-dodecane, and can also improve the selectivity of the dodecamonoolefin.

Description

Dehydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of alkane dehydrogenation, in particular to a dehydrogenation catalyst and a preparation method and application thereof.
Background
The long-chain alkane generally refers to a linear alkane compound having a carbon number greater than 10. The preparation of long chain mono-olefin by dehydrogenation of long chain n-alkane is an important operation unit in petrochemical industry chain. Wherein, the long-chain n-dodecyl alkane is one of typical representatives of the long-chain alkane, and the dehydrogenation product of the long-chain n-dodecyl monoolefin (hereinafter, referred to as dodecyl monoolefin) is a key intermediate product for preparing dodecyl benzene sulfonate, and is mainly used for synthesizing surfactants, detergents and emulsifiers. The synthesis of dodecylbenzene sulfonate from dodecamonoene has the advantages of high atom utilization rate, less discharge of three wastes, meeting the requirements of green chemical industry and the like, so that the preparation of high-purity dodecane from n-dodecane by dehydrogenation has important application value.
At present, the widely used process for preparing dodecamonoolein by dehydrogenating n-dodecane is the Pacol process developed by UOP corporation in the United states, which adopts Pt-Sn-K/gamma-Al2O3A catalyst. However, industrial Pt-Sn-K/γ -Al2O3In the using process of the catalyst, n-dodecane can be subjected to hydrogenolysis, isomerization and coking at an acid site of the catalyst to generate serious carbon deposition, so that the catalyst is gradually deactivated, and Pt-Sn-K/gamma-Al is seriously influenced2O3The service life of the catalyst. To improve Pt-Sn-K/gamma-Al2O3The catalyst is easy to coke, and the catalyst is easy to coke (macroporous gamma-Al)2O3Preparation and n-dodecane dehydrogenation performance research, contemporary chemical industry, 2012,10,1030-2O3The catalyst can relieve the carbon deposit rate, but the n-dodecane conversion rate of the catalyst is reduced from 24.2% to 20.7% after the catalyst is operated for 24 hours. Akia et Al (Synthesis of high surface area gamma-Al)2O3as an effective catalyst support for hydrolysis of n-dopant, Journal of porous Materials 2010,17,85-90) by hydrothermal method2O3Specific surface area up to 384m2The supported Pt catalyst can stably run for 16h without deactivation.
The method takes high-content Pt as active metal, the catalyst is expensive, and most of catalyst carriers are gamma-Al2O3Is a carrier and has stronger acidity, so that the carbon deposit of the catalyst is serious and the catalyst is quickly inactivated.
Disclosure of Invention
The invention aims to provide a dehydrogenation catalyst, a preparation method and application thereof, the catalyst reduces the content of active noble metal Pt, saves the preparation cost of the catalyst, has ultra-long service life in the reaction of preparing dodecamonoolefin by dehydrogenating n-dodecane, and can improve the selectivity of the dodecamonoolefin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a dehydrogenation catalyst, which comprises a carrier and an active component loaded on the carrier; the carrier is Na-type ZSM-5 molecular sieve; the active component is noble metal Pt; the mass content of active components in the dehydrogenation catalyst is 0.05-0.3%.
Preferably, the catalyst also comprises an auxiliary agent loaded on the carrier, wherein the auxiliary agent comprises a metal oxide.
Preferably, the metal oxide comprises ZnO, Ga2O3、CeO2、Fe2O3And SnO2One or more of (a).
Preferably, the molar ratio of the noble metal Pt to the metal elements in the auxiliary agent is 1 (1-5).
Preferably, the specific surface area of the Na-type ZSM-5 molecular sieve is 300-400 m2/g。
The invention provides a preparation method of the dehydrogenation catalyst, which comprises the following steps:
dipping a Na-type ZSM-5 molecular sieve into a solution containing a Pt precursor, drying, and roasting to obtain a dehydrogenation catalyst;
the mass of Pt in the solution corresponds to the content of noble metal Pt in the dehydrogenation catalyst.
Preferably, when the dehydrogenation catalyst further comprises an auxiliary agent, the solution containing the Pt precursor further contains an auxiliary agent precursor;
the content of the auxiliary metal element in the auxiliary precursor corresponds to the content of the metal element in the auxiliary in the dehydrogenation catalyst.
Preferably, the roasting temperature is 500-550 ℃, and the heat preservation time is 2-5 h.
The invention provides an application of the dehydrogenation catalyst in the scheme or the dehydrogenation catalyst prepared by the preparation method in the scheme in the preparation of n-dodecamonoolefin through dehydrogenation reaction of n-dodecane.
Preferably, the temperature of the dehydrogenation reaction is 400-500 ℃, and the mass space velocity is 0.8-2 h-1。
The invention provides a dehydrogenation catalyst, which comprises a carrier and an active component loaded on the carrier; the carrier is Na-type ZSM-5 molecular sieve; the active component is noble metal Pt; the mass content of active components in the dehydrogenation catalyst is 0.05-0.3%.
The dehydrogenation catalyst provided by the invention has low content of active noble metal Pt, and the mass content is only 0.05-0.3%, so that the catalyst cost can be greatly saved. In addition, the Na-type ZSM-5 molecular sieve has high specific surface area and can form strong interaction with Pt, so that the catalyst is favorable for improving the dispersion degree of the Pt, and has high activity even under the condition of low content of the Pt; moreover, the low content of Pt can inhibit the cracking of n-dodecane, and is beneficial to improving the selectivity of the dodecamonooleine product. Besides, the Na-type ZSM-5 molecular sieve also has regular pore channels, can inhibit side reactions and improve the selectivity of target products, namely the dodecamonoolefin.
The results of the examples show that the catalyst provided by the invention has an ultra-long service life (>300h) in the reaction of preparing dodecamonoolefin by dehydrogenating n-dodecane, and can improve the selectivity (> 85%) of the dodecamonoolefin.
The catalyst of the present invention is used in catalyzing dehydrogenation of n-dodecane to prepare dodecamonoene and has the advantage of mild reaction condition.
Furthermore, the dehydrogenation catalyst provided by the invention also comprises an auxiliary agent, wherein the auxiliary agent can stabilize the active species Pt and improve the stability of the catalyst.
Drawings
FIG. 1 is a transmission electron micrograph of a Pt-Zn/Na-ZSM-5 catalyst prepared in example 1.
Detailed Description
The invention provides a dehydrogenation catalyst, which comprises a carrier and an active component loaded on the carrier; the carrier is Na-type ZSM-5 molecular sieve; the active component is noble metal Pt; the mass content of active components in the dehydrogenation catalyst is 0.05-0.3%.
The catalyst provided by the invention comprises a carrier, wherein the carrier is a Na-type ZSM-5 molecular sieve. In the invention, the specific surface area of the Na-type ZSM-5 molecular sieve is preferably 300-400 m2(ii) in terms of/g. The Na-type ZSM-5 molecular sieve has no special requirement on the silica-alumina ratio, and the Na-type ZSM-5 molecular sieve with the silica-alumina ratio can be well known in the field. In embodiments of the invention, the Na-type ZSM-5 molecular sieve has a silica to alumina ratio of 100, 200 or 500. In addition, the Na-type ZSM-5 molecular sieve has high specific surface area, can form strong interaction with Pt to form a Pt-O-Si bond, is beneficial to improving the dispersion degree of the Pt, and has high activity even under the condition of low content of the Pt. In addition, the Na-type ZSM-5 molecular sieve also has regular pore channels, Pt nano particles can be confined in the pore channels, the sintering of the Pt nano particles is inhibited, the stability of the catalyst is improved, in addition, the smaller micro-pore channels can inhibit the side reactions of cyclization, isomerization and the like of the dodecamonoolefin, and the selectivity of the target product dodecamonoolefin is improved.
The dehydrogenation catalyst provided by the invention comprises an active component loaded on the carrier, wherein the active component is a noble metal Pt; the mass content of the active component in the dehydrogenation catalyst is 0.05-0.3%, preferably 0.10-0.25%, and more preferably 0.15-0.20%. The dehydrogenation catalyst provided by the invention has low content of active noble metal Pt, and the mass content is only 0.05-0.3%, so that the catalyst cost can be greatly saved. Moreover, the low content of Pt inhibits the cracking of n-dodecane, and is instead beneficial to improving the selectivity of the dodecamonooleine product. In the present invention, the particle size of the noble metal Pt is preferably 1 to 10nm, and more preferably 2 to 5 nm.
The dehydrogenation catalyst provided by the present invention preferably further comprises a promoter supported on the carrier, the promoter comprising a metal oxide. In the present invention, the metal oxide preferably includes ZnO, Ga2O3、CeO2、Fe2O3And SnO2One or more of (a). When the auxiliary agents comprise a plurality of the substances, the proportion of each auxiliary agent is not specially required, and the auxiliary agents can be mixed at any proportion.
In the invention, the molar ratio of the noble metal Pt to the metal element in the promoter is preferably 1 (1-5), more preferably 1 (1.5-4.5), more preferably 1: (2-4). In the invention, the auxiliary agent can stabilize the active species Pt and improve the stability of the catalyst.
The invention provides a preparation method of the dehydrogenation catalyst, which comprises the following steps:
dipping a Na-type ZSM-5 molecular sieve into a solution containing a Pt precursor, drying, and roasting to obtain a dehydrogenation catalyst;
the mass of Pt in the solution corresponds to the content of noble metal Pt in the dehydrogenation catalyst.
In the invention, the Na-type ZSM-5 molecular sieve is preferably prepared by self, and the preparation method of the Na-type ZSM-5 molecular sieve has no special requirement and can be prepared by adopting a preparation method of the Na-type ZSM-5 molecular sieve well known in the field. In the embodiment of the present invention, the preparation method of the Na-type ZSM-5 molecular sieve preferably includes: adding sodium hydroxide, aluminum nitrate, tetrapropylammonium hydroxide, ethyl orthosilicate and water into a crystallization kettle, mixing, carrying out crystallization reaction, carrying out solid-liquid separation on a product system obtained by the crystallization reaction, drying the obtained solid, and roasting to obtain the Na-type ZSM-5 molecular sieve. The invention has no special requirements on the sodium hydroxide, the aluminum nitrate, the tetrapropylammonium hydroxide, the ethyl orthosilicate and the water, and the proper dosage is selected according to the silicon-aluminum ratio, which is common knowledge in the field and is not described again. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring time is preferably 20 min. The present invention does not require any particular speed of agitation, and can employ agitation speeds well known in the art. In the present invention, the temperature of the crystallization reaction is preferably 170 ℃ and the time is preferably 2 days. The drying conditions of the present invention are not particularly limited, and those well known in the art may be used. In the examples of the present invention, drying was carried out at 80 ℃ overnight. In the invention, the roasting temperature is preferably 550-600 ℃, and the roasting time is preferably 10-15 h. The invention utilizes roasting to remove the template agent tetrapropylammonium hydroxide.
In the present invention, the Pt precursor preferably includes one or more of chloroplatinic acid, sodium chloroplatinate, tetraammineplatinum dichloride and tetraammineplatinum nitrate, and when the Pt precursor includes a plurality of the above-mentioned substances, there is no particular requirement for the proportion of each Pt precursor in the present invention as long as the mass of Pt in the solution corresponding to the content of noble metal Pt in the dehydrogenation catalyst can be satisfied.
In the present invention, when the dehydrogenation catalyst further includes an auxiliary, the Pt precursor-containing solution further contains an auxiliary precursor; the content of the auxiliary metal element in the auxiliary precursor corresponds to the content of the metal element in the auxiliary in the dehydrogenation catalyst. In the invention, when the auxiliary agent is ZnO, the auxiliary agent precursor is preferably zinc chloride; when the auxiliary agent is Ga2O3When the precursor is gallium nitrate, the precursor of the auxiliary agent is preferably gallium nitrate; when the auxiliary agent is CeO2When the precursor is cerium nitrate, the precursor of the auxiliary agent is preferably cerium nitrate; when the auxiliary agent is Fe2O3In the case, the auxiliary agent precursor is preferably ferric nitrate; when the auxiliary agent is SnO2In this case, the assistant precursor is preferably tin chloride.
In the present invention, the impregnation is preferably an equal volume impregnation, i.e., the volume of the solution is equal to the water absorption of the Na-type ZSM-5 molecular sieve. In the present invention, the solvent of the solution containing the Pt precursor is preferably water. In the present invention, the time for the impregnation is preferably 24 hours.
The drying conditions of the present invention are not particularly limited, and those well known in the art may be used. In the examples of the present invention, in particular, the drying was carried out overnight at 80 ℃. In the invention, the roasting temperature is preferably 500-550 ℃, more preferably 510-540 ℃, and further preferably 520-530 ℃; the heat preservation time is preferably 2-5 h, and more preferably 3-4 h. In the present invention, the calcination is preferably performed in an air atmosphere. In the roasting process, the Pt precursor is decomposed to form Pt, and the auxiliary agent precursor forms corresponding metal oxide.
The invention provides an application of the dehydrogenation catalyst in the scheme or the dehydrogenation catalyst prepared by the preparation method in the scheme in the preparation of n-dodecamonoolefin through dehydrogenation reaction of n-dodecane.
In the invention, the temperature of the dehydrogenation reaction is preferably 400-500 ℃, more preferably 420-480 ℃, and further preferably 440-460 ℃; the mass space velocity is preferably 0.8-2 h-1More preferably 1.0 to 1.8 hours-1More preferably 1.2 to 1.6 hours-1. In the present invention, the dehydrogenation reaction preferably employs N2-H2The mixed gas is carrier gas, and N is2-H2N in the mixed gas2And H2The volume ratio of (1-10): 1, more preferably (2-8): 1, more preferably (4-6): 1. the flow rate of the carrier gas is not particularly required in the present invention, and may be a carrier gas flow rate well known in the art. In an embodiment of the invention, the carrier gas flow rate is 50 mL/min. In the present invention, the dehydrogenation reaction is preferably carried out under normal pressure conditions, i.e., 0.1 MPa. The dehydrogenation reaction is preferably carried out in a fixed bed reactor according to the present invention.
The dehydrogenation catalyst provided by the present invention, its preparation method and application are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The preparation method of the Na-type ZSM-5 molecular sieve used in the examples 1-3 comprises the following steps:
1.54g of sodium hydroxide, 0.24g of aluminum nitrate, 23.42g of tetrapropylammonium hydroxide, 40g of tetraethoxysilane and 86.2gh2O additionAnd (3) putting the mixture into a crystallization kettle, stirring the mixture for 20min at room temperature, crystallizing the mixture for 2 days in a homogeneous reactor at the temperature of 170 ℃, filtering the mixture, drying the mixture overnight at the temperature of 80 ℃, and roasting the dried mixture in a muffle furnace at the temperature of 580 ℃ for 12h to synthesize the Na-type ZSM-5 molecular sieve with the Si/Al ratio of 200.
The preparation method of the Na-type ZSM-5 molecular sieve used in the embodiments 4 to 6 comprises the following steps:
adding 1.54g of sodium hydroxide, 0.48g of aluminum nitrate, 23.42g of tetrapropylammonium hydroxide, 40g of tetraethoxysilane and 86.2g of water into a crystallization kettle, stirring at room temperature for 20min, crystallizing in a homogeneous phase reactor at 170 ℃ for 2 days, filtering, drying at 80 ℃ overnight, and roasting in a muffle furnace at 570 ℃ for 14h to synthesize the Na-type ZSM-5 molecular sieve with the Si/Al ratio of 100.
The preparation method of the Na-type ZSM-5 molecular sieve used in the examples 7 to 14 comprises the following steps:
adding 1.54g of sodium hydroxide, 0.096g of aluminum nitrate, 23.42g of tetrapropylammonium hydroxide, 40g of tetraethoxysilane and 86.2g of water into a crystallization kettle, stirring at room temperature for 20min, crystallizing in a homogeneous phase reactor at 170 ℃ for 2 days, filtering, drying at 80 ℃ overnight, and roasting in a muffle furnace at 570 ℃ for 14h to synthesize the Na-type ZSM-5 molecular sieve with the Si/Al ratio of 500.
Example 1
Weighing 20g of Na type ZSM-5 molecular sieve, adding chloroplatinic acid aqueous solution (0.053g +25mL of water) and 0.031g ZnCl2Soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting in a muffle furnace at 520 ℃ for 4h to obtain the catalyst Pt-Zn/Na-ZSM-5 (the mass content of Pt is 0.1%, and the molar ratio of Pt to Zn is 1: 1). The transmission electron microscope test result of the catalyst is shown in fig. 1, and as can be seen from fig. 1, the Pt nanoparticles are dispersed very uniformly, and the average particle size is only 2.3 nm.
Application example 1
The Pt-Zn/Na-ZSM-5 catalyst synthesized in example 1 was charged in a fixed bed reactor, N-dodecane was used as a raw material, and N2-H2(volume ratio is 4:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 435 ℃, the pressure is 0.1MPa, and the mass space velocity of the n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, n-twelveThe conversion of alkane was 13.7% and the selectivity to dodecamonoene was 89.1%. After the catalyst is operated for 300 hours, the conversion rate of n-dodecane is 10.7%, and the selectivity of the dodecamonoene is 91.1%, which shows that the catalyst has long service life.
Comparative example 1
20g of commercial gamma-Al was weighed2O3Adding chloroplatinic acid aqueous solution (0.053g +25mL water), soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting in a muffle furnace at 520 ℃ for 4h to obtain the catalyst Pt/gamma-Al2O3(Pt content: 0.1% by mass).
The catalyst of comparative example 1 was subjected to a performance test under the reaction conditions of application example 1, and the results showed that Pt/γ -Al2O3There was little activity, n-dodecane conversion was only 1.1%, dodecaolefin selectivity was 32.5%, and the catalyst was completely deactivated over 72 h.
Example 2
Weighing 20g of Na-type ZSM-5 molecular sieve, adding chloroplatinic acid aqueous solution (0.106g of water and 25mL of water) and 0.124g of zinc chloride, soaking for 24h in the same volume, drying overnight at 80 ℃, and roasting for 4h in a muffle furnace at 530 ℃ to obtain the catalyst Pt-Zn/Na-ZSM-5 (the mass content of Pt is 0.2%, and the molar ratio of Pt to Zn is 1: 2).
Application example 2
The Pt-Zn/Na-ZSM-5 catalyst synthesized in example 2 was charged in a fixed bed reactor, N-dodecane was used as a raw material, and N2-H2(volume ratio is 4:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 455 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.5h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 21.4% and the selectivity to dodecamonoolefin was 85.3%. The catalyst can stably operate for 500 hours, the conversion rate of n-dodecane is 18.2% after the catalyst operates for 500 hours, and the selectivity of the dodecamonoene is 89.6%.
Example 3
Weighing 20g of Na-type ZSM-5 molecular sieve, adding chloroplatinic acid aqueous solution (0.053g +25mL of water) and 0.024g of tin chloride, soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting in a muffle furnace at 500 ℃ for 4h to obtain the catalyst Pt-Sn/Na-ZSM-5 (the mass content of Pt is 0.1%, and the molar ratio of Pt to Sn is 1: 1).
Application example 3
The synthesized Pt-Sn/Na-ZSM-5 catalyst is filled in a fixed bed reactor, N-dodecane is used as a raw material, and N2-H2(volume ratio is 4:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 435 ℃, the pressure is 0.1MPa, and the mass space velocity of the n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 13.4% and the selectivity to dodecamonoolefin was 88.9%. The catalyst can stably operate for 320 hours, the conversion rate of n-dodecane is 9.8% after the catalyst operates for 320 hours, and the selectivity of the dodecamonoene is 92.5%.
Example 4
Weighing 20g of Na-type ZSM-5 molecular sieve, adding chloroplatinic acid aqueous solution (0.053g +25mL of water) and 0.048g of tin chloride, soaking for 24h in an equal volume, drying overnight at 80 ℃, and roasting for 4h in a muffle furnace at 540 ℃ to obtain the catalyst Pt-Sn/Na-ZSM-5 (the mass content of Pt is 0.1%, and the molar ratio of Pt to Sn is 1: 2).
Application example 4
The Pt-Sn/Na-ZSM-5 catalyst synthesized in example 4 was filled in a fixed bed reactor, N-dodecane was used as a raw material2-H2(volume ratio 6:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 13.6% and the selectivity to dodecamonoolefin was 92.7%. The catalyst can stably operate for 450 hours, the conversion rate of n-dodecane is 8.6% after the catalyst operates for 450 hours, and the selectivity of the dodecamonoene is 93.4%.
Example 5
Weighing 20g of Na-type ZSM-5 molecular sieve, adding a sodium chloroplatinate aqueous solution (0.14g of water and 25mL of water) and 0.144g of gallium nitrate, soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting in a muffle furnace at 520 ℃ for 3h to obtain the catalyst Pt-Ga/Na-ZSM-5 (the mass content of Pt is 0.3%, and the molar ratio of Pt to Ga is 1: 1).
Application example 5
The Pt-Ga/Na-ZSM-5 catalyst synthesized in example 5 was filled in a fixed bed reactor, N-dodecane was used as a raw material2-H2(volume ratio 10:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 15.6% and the selectivity to dodecamonoolefin was 86.2%. The catalyst can stably operate for 390 hours, the conversion rate of n-dodecane is 12.3% after the catalyst operates for 390 hours, and the selectivity of the dodecamonoene is 91.6%.
Example 6
Weighing 20g of Na-type ZSM-5 molecular sieve, adding a sodium chloroplatinate aqueous solution (0.093g +25mL of water) and 0.163g of cerium nitrate, soaking for 24h in the same volume, drying overnight at 80 ℃, and roasting for 5h in a muffle furnace at 530 ℃ to obtain the catalyst Pt-Ce/Na-ZSM-5 (the mass content of Pt is 0.2%, and the molar ratio of Pt to Ce is 1: 1).
Application example 6
The Pt-Ce/Na-ZSM-5 catalyst synthesized in example 6 was charged in a fixed bed reactor, N-dodecane was used as the starting material, and N2-H2(volume ratio 3:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 17.8% and the selectivity to dodecamonoolefin was 91.5%. The catalyst can stably operate for 440h, the conversion rate of n-dodecane is 14.6% after the catalyst operates for 440h, and the selectivity of the dodecamonoene is 93.7%.
Example 7
Weighing 20g of Na-type ZSM-5 molecular sieve, adding a sodium chloroplatinate aqueous solution (0.047g of water and 25mL of water) and 0.172g of cerium nitrate, soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting in a muffle furnace at 510 ℃ for 3h to obtain the catalyst Pt-Ce/Na-ZSM-5 (the mass content of Pt is 0.1%, and the molar ratio of Pt to Ce is 1: 2).
Application example 7
The Pt-Ce/Na-ZSM-5 catalyst synthesized in example 7 was charged in a fixed bed reactor, N-dodecane was used as the starting material, and N2-H2(volume ratio is 4:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 19.4% and the selectivity to dodecamonoolefin was 85.1%. The catalyst can stably operate for 310h, the conversion rate of n-dodecane is 13.1% after the catalyst operates for 310h, and the selectivity of the dodecamonoene is 90.4%.
Example 8
Weighing 20g of Na-type ZSM-5 molecular sieve, adding tetramine platinum dichloride aqueous solution (0.034g +25mL of water) and 0.223g of tin chloride, soaking for 24h in the same volume, drying overnight at 80 ℃, and roasting for 5h in a muffle furnace at 520 ℃ to obtain the catalyst Pt-Sn/Na-ZSM-5 (the mass content of Pt is 0.1%, and the molar ratio of Pt to Sn is 1: 5).
Application example 8
The Pt-Sn/Na-ZSM-5 catalyst synthesized in example 8 was charged in a fixed bed reactor, N-dodecane was used as the starting material2-H2(volume ratio 6:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 17.9% and the selectivity to dodecamonoolefin was 86.4%. The catalyst can stably operate for 350h, the conversion rate of n-dodecane is 12.3% after the catalyst operates for 350h, and the selectivity of the dodecamonoene is 90.5%.
Example 9
Weighing 20g of Na-type ZSM-5 molecular sieve, adding tetramine platinum dichloride aqueous solution (0.103g +25mL of water) and 0.186g of zinc nitrate, soaking for 24h in the same volume, drying overnight at 80 ℃, and roasting for 4h in a muffle furnace at 510 ℃ to obtain the catalyst Pt-Zn/Na-ZSM-5 (the mass content of Pt is 0.3%, and the molar ratio of Pt to Zn is 1: 2).
Application example 9
The Pt-Zn/Na-ZSM-5 catalyst synthesized in example 9 was charged in a fixed bed reactor, N-dodecane was used as the starting material, and N2-H2(volume ratio 8:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 18.7% and the selectivity to dodecamonoolefin was 88.3%. The catalyst can stably operate for 400 hours, the conversion rate of n-dodecane is 13.8% after the catalyst operates for 400 hours, and the selectivity of the dodecamonoene is 93.6%.
Example 10
Weighing 20g of Na-type ZSM-5 molecular sieve, adding tetramine platinum dichloride aqueous solution (0.069g +25mL of water) and 0.398g of gallium nitrate, soaking for 24h in the same volume, drying overnight at 80 ℃, and roasting for 4h in a muffle furnace at 540 ℃ to obtain the catalyst Pt-Ga/Na-ZSM-5 (the mass content of Pt is 0.2%, and the molar ratio of Pt to Ga is 1: 4).
Application example 10
The Pt-Ga/Na-ZSM-5 catalyst synthesized in example 10 was charged in a fixed bed reactor, N-dodecane was used as a raw material2-H2(volume ratio 5:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 20.3% and the selectivity to dodecamonoolefin was 88.0%. The catalyst can stably operate for 360 hours, the conversion rate of n-dodecane is 14.0% after the catalyst operates for 360 hours, and the selectivity of the dodecamonoene is 94.2%.
Example 11
Weighing 20g of Na-type ZSM-5 molecular sieve, adding 0.224g of tetrammine platinum nitrate aqueous solution (0.02g +25mL of water) and 0.675g of cerium nitrate, soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting for 2h in a muffle furnace at 500 ℃ to obtain the catalyst Pt-Ce/Na-ZSM-5 (the mass content of Pt is 0.05%, and the molar ratio of Pt to Ce is 1: 2).
Application example 11
The Pt-Ce/Na-ZSM-5 catalyst synthesized in example 11 was charged in a fixed bed reactor, N-dodecane was used as the starting material, and N2-H2(volume ratio is 7:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 23.5% and the selectivity to dodecamonoolefin was 85.1%. The catalyst can stably operate for 340h, the conversion rate of n-dodecane is 16.1% after 340h operation, and the selectivity of the dodecamonoene is 92.9%.
Example 12
Weighing 20g of Na-type ZSM-5 molecular sieve, adding tetrammine platinum nitrate aqueous solution (0.04g +25mL of water) and 0.236g of ferric nitrate, soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting for 5h in a muffle furnace at 530 ℃ to obtain the catalyst Pt-Fe/Na-ZSM-5 (the mass content of Pt is 0.1%, and the molar ratio of Pt to Fe is 1: 3).
Application example 12
The Pt-Fe/Na-ZSM-5 catalyst synthesized in example 12 was charged in a fixed bed reactor, N-dodecane was used as the starting material, and N2-H2(volume ratio 2:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 14.5% and the selectivity to dodecamonoolefin was 89.9%. The catalyst can stably run for 380h, the conversion rate of n-dodecane is 9.6% after the catalyst runs for 380h, and the selectivity of the dodecamonoene is 92.3%.
Example 13
Weighing 20g of Na-type ZSM-5 molecular sieve, adding tetrammine platinum nitrate aqueous solution (0.079g +25mL of water) and 0.456g of ferric nitrate, soaking for 24h in the same volume, drying overnight at 80 ℃, and roasting for 3h in a muffle furnace at 510 ℃ to obtain the catalyst Pt-Fe/Na-ZSM-5 (the mass content of Pt is 0.2%, and the molar ratio of Pt to Fe is 1: 3).
Application example 13
The synthesized Pt-Fe/Na-ZSM-5 catalyst is filled in a fixed bed reactor, N-dodecane is used as a raw material, and N2-H2(volume ratio 9:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 445 ℃, the pressure is 0.1MPa, and the mass space velocity of n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 18.1% and the selectivity to dodecamonoolefin was 93.8%. The catalyst can stably operate for 400 hours, the conversion rate of n-dodecane is 13.3% after the catalyst operates for 400 hours, and the selectivity of the dodecamonoene is 95.4%.
Example 14
Weighing 20g of Na-type ZSM-5 molecular sieve, adding tetrammine platinum nitrate aqueous solution (0.079g +25mL of water), soaking for 24h in the same volume, drying at 80 ℃ overnight, and roasting in a muffle furnace at 550 ℃ for 6h to obtain the catalyst Pt/Na-ZSM-5 (the Pt mass content is 0.2%).
Application example 14
The synthesized Pt/Na-ZSM-5 catalyst is filled in a fixed bed reactor, N-dodecane is used as a raw material, and N is2-H2(volume ratio 10:1) mixed gas is used as carrier gas to carry out dehydrogenation reaction. The process conditions are as follows: the temperature is 435 ℃, the pressure is 0.1MPa, and the mass space velocity of the n-dodecane is 1.2h-1The total carrier gas flow rate was 50 mL/min. The liquid phase product is analyzed by off-line gas chromatography, and the gas phase product is analyzed by on-line gas chromatography. Under the reaction conditions, the conversion of n-dodecane was 20.1% and the selectivity to dodecamonoolefin was 89.7%. The catalyst can stably operate for 350h, the conversion rate of n-dodecane is 15.1% after the catalyst operates for 350h, and the selectivity of the dodecamonoene is 92.7%.
It can be seen from the above examples and comparative examples that the present invention provides a dehydrogenation catalyst, a method for preparing the same, and applications thereof, the catalyst of the present invention reduces the content of the active noble metal Pt, saves the catalyst preparation cost, has an ultra-long service life in the reaction of preparing dodecamonoolefin by dehydrogenating n-dodecane, and can also improve the selectivity of the dodecamonoolefin.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A dehydrogenation catalyst comprising a support and an active component supported on the support; the carrier is Na-type ZSM-5 molecular sieve; the active component is noble metal Pt; the mass content of active components in the dehydrogenation catalyst is 0.05-0.3%.
2. The dehydrogenation catalyst of claim 1 further comprising a promoter supported on the support, the promoter comprising a metal oxide.
3. The dehydrogenation catalyst of claim 3, wherein the metal oxide comprises ZnO, Ga2O3、CeO2、Fe2O3And SnO2One or more of (a).
4. The dehydrogenation catalyst according to claim 2 or 3, wherein the molar ratio of the noble metal Pt to the metal element in the promoter is 1 (1-5).
5. The dehydrogenation catalyst according to any one of claims 1 to 3, wherein the Na-type ZSM-5 molecular sieve has a specific surface area of 300 to 400m2/g。
6. A process for preparing a dehydrogenation catalyst according to any of claims 1 to 5, comprising the steps of:
dipping a Na-type ZSM-5 molecular sieve into a solution containing a Pt precursor, drying, and roasting to obtain a dehydrogenation catalyst;
the mass of Pt in the solution corresponds to the content of noble metal Pt in the dehydrogenation catalyst.
7. The production method according to claim 5, wherein when the dehydrogenation catalyst further comprises a promoter, the Pt-containing precursor solution further contains a promoter precursor;
the content of the auxiliary metal element in the auxiliary precursor corresponds to the content of the metal element in the auxiliary in the dehydrogenation catalyst.
8. The preparation method according to claim 6 or 7, wherein the roasting temperature is 500-550 ℃, and the holding time is 2-5 h.
9. Use of the dehydrogenation catalyst according to any one of claims 1 to 5 or the dehydrogenation catalyst prepared by the preparation method according to any one of claims 6 to 8 in the dehydrogenation of n-dodecane to produce n-dodemomonoolefin.
10. The use of claim 9, wherein the dehydrogenation reaction is carried out at a temperature of 400 to 500 ℃ and a mass space velocity of 0.8 to 2 hours-1。
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