CN116059991A - Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method and application thereof - Google Patents

Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method and application thereof Download PDF

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CN116059991A
CN116059991A CN202111273296.0A CN202111273296A CN116059991A CN 116059991 A CN116059991 A CN 116059991A CN 202111273296 A CN202111273296 A CN 202111273296A CN 116059991 A CN116059991 A CN 116059991A
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catalyst
oxide
metal element
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马静怡
纪中海
刘昌呈
王杰广
王春明
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention relates to a catalyst for preparing olefin by dehydrogenating light alkane, a preparation method and application thereof, wherein the catalyst comprises 20-50 wt% of ZnO,20-65 wt% of first auxiliary agent component, 0.1-10 wt% of second auxiliary agent component and 10-50 wt% of binder based on the dry basis weight of the catalyst; the first auxiliary component comprises zirconium dioxide and silicon dioxide composite oxide and a first metal element, wherein the first metal element is selected from one or more of titanium, manganese, tin and tungsten; the second auxiliary component contains a second metal element, and the second metal element is one or more selected from lithium, sodium, potassium, magnesium, barium and calcium. The catalyst of the invention has higher reactivity, and has higher conversion rate and selectivity of target products when being used for preparing olefin by dehydrogenating low-carbon olefin.

Description

Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method and application thereof
Technical Field
The invention relates to a catalyst for preparing olefin by dehydrogenating low-carbon alkane, a preparation method and application thereof.
Background
Propylene is one of the basic chemical raw materials and is widely applied to the synthesis of various chemical products such as polypropylene, propylene oxide, acrylic acid, acrylonitrile and the like. At present, propylene is mainly derived from co-production or byproducts of processes such as naphtha cracking and catalytic cracking, but with the annual increase of propylene consumption, the conventional propylene production cannot meet the requirements, so that the technology for preparing propylene by propane dehydrogenation is rapidly developed. The technology of propylene preparation by catalytic dehydrogenation of propane, which is already industrialized at present, mainly comprises Oleflex technology of UOP company and Catofin technology of Lummes company. The Oleflex process adopts a moving bed reactor with continuously regenerated catalyst, and adopts Pt-Sn/Al 2 O 3 K, li or the like is added as a catalyst for modification; the Catofin process adopts a fixed bed reactor, and uses Cr 2 O 3 /Al 2 O 3 The catalyst is deactivated fast and needs to be regenerated once every 15 minutes.
Compared with the two processes, the fluidized bed propane dehydrogenation process adopts a single reactor design, can realize continuous input and output of solid materials, is convenient for continuous regeneration and cyclic operation of the catalyst, has flexible operation device and better operation elasticity and raw material adaptability. In addition, the catalyst and the raw materials are vigorously stirred, so that the mass transfer and heat transfer process is promoted, the movement of fluid and particles enables the bed layer to have good heat transfer performance, the temperature inside the bed layer is uniform, and the full play of the activity of the catalyst is facilitated. The FBD fluidized bed dehydrogenation process developed by Russian Luo Siya Laval institute and Italy Snamprogetti engineering company is industrialized in 1964, and the catalyst is microsphere Cr 2 O 3 /Al 2 O 3 However, the catalyst is also a serious environmental pollution and difficult to treat. Because ofThe development of the propane dehydrogenation catalyst with high activity, low cost and environmental protection has important significance.
CN102451677B discloses a catalyst for isobutane dehydrogenation, which is prepared from MgO, P 2 O 5 、ZrO 2 、Al 2 O 3 Or SiO 2 One or more oxides of Ti, nb, ta, W, re, in or Ga are used as carriers, and one or more oxides of Ti, nb, ta, W, re, in or Ga are used as active components, and a continuous reaction-regeneration device is adopted to carry out isobutane dehydrogenation to prepare olefin. However, the catalyst is easy to deactivate, the cost of the reaction device is high, and the loss of the device is large because of the existence of sulfur.
CN105618026a discloses a catalyst for alkane dehydrogenation, and a preparation method and a use method thereof. The catalyst comprises a dehydrogenation active component, a carrier and a second auxiliary agent. The dehydrogenation active component is one or more metals or oxides of Fe, zn, cu, ga and Pb, and the content is 0.1-60 parts, preferably 2-20 parts; the carrier is SiO 2 、Al 2 O 3 、ZrO 2 、MgAl 2 O 4 And ZnAl 2 O 4 The mixed oxide or composite oxide formed by one or more of the above components can also be molecular sieve, and the content is 40-99.9 parts, preferably 80-98 parts.
CN108727148B discloses a highly dispersed ZnO-based catalyst, a preparation method thereof and a propane anaerobic dehydrogenation method. The catalyst takes Silicalite-1 as a carrier, ZIF-8 as a precursor of ZnO and a precursor of a carbon material, and forms high-dispersion ZnO nano particles coated by the carbon material in the high-temperature pyrolysis process; further nitric acid pickling can obtain smaller ZnO nano particles, so that the stability of the catalyst is improved.
CN110614092a discloses a non-noble metal propane dehydrogenation catalyst and a preparation method thereof. The active component of the catalyst is at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, copper and oxides thereof, and the catalyst is impregnated on a sulfur-modified alumina carrier to obtain the non-noble metal propane dehydrogenation catalyst.
CN112619686a discloses a supported non-noble metal dehydrogenation catalyst, a preparation method and application thereof. The active component of the catalyst is zinc and/or zinc oxide, the auxiliary agent is phosphorus and/or phosphorus oxide, and the carrier is MFI molecular sieve. The MFI molecular sieve synthesized by the hydrothermal method improves the pore structure through alkali treatment, and simultaneously increases the contents of active components, auxiliary agents and other species in the molecular sieve pore channels through vacuum impregnation. By utilizing the limiting effect of the pore canal size, the aggregation of active components Zn and the like can be reduced, and the service life of the catalyst can be prolonged.
CN110801861 discloses a catalyst for preparing propylene by directly dehydrogenating environment-friendly propane, and a preparation method of the catalyst. The catalyst comprises 30 to 70 percent of Zn doped H beta molecular sieve, 15 to 50 percent of Al 2 O 3 3% to 30% of multielement activity modifier. The modifier uses at least one element in W, mo, mn, zr, ni, fe, co as a first modifier, uses at least one element in Ga, in, P, la, ce as a second modifier and uses any element in Sr, ba, ca, mg, na, li as a third modifier. The fluidized bed dehydrogenation catalyst has low cost and good wear resistance, and has good dehydrogenation activity and stability when used for propane dehydrogenation.
Disclosure of Invention
The invention aims to provide a catalyst for preparing olefin by dehydrogenating low-carbon alkane, a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for preparing olefin by dehydrogenating light alkane, which comprises 20 to 50% by weight of ZnO,20 to 65% by weight of a first auxiliary component, 0.1 to 10% by weight of a second auxiliary component and 10 to 50% by weight of a binder, based on the dry weight of the catalyst;
the first auxiliary component comprises zirconium dioxide and silicon dioxide composite oxide and a first metal element, wherein the first metal element is selected from one or more of titanium, manganese, tin and tungsten;
the second auxiliary component contains a second metal element, and the second metal element is one or more selected from lithium, sodium, potassium, magnesium, barium and calcium.
Optionally, the catalyst contains 20-45 wt% of the ZnO,20-50 wt% of the first auxiliary component, 0.1-8 wt% of the second auxiliary component, and 10-40 wt% of the binder.
Alternatively, the silica content of the zirconium dioxide and silica composite oxide is 0.1 to 50% by weight, preferably 0.1 to 30% by weight.
Optionally, the first auxiliary component contains a zirconium dioxide and silicon dioxide composite oxide and an oxide of the first metal element; the second auxiliary component contains a chloride of the second metal element.
Optionally, the binder is one or more selected from aluminum sol, silica sol and SB powder.
In a second aspect, the present invention provides a method for preparing the catalyst provided in the first aspect, the method comprising: after mixing the zinc source, the zirconium dioxide and silicon dioxide composite oxide, the first metal source, the second metal source, the binder and the solvent, the resulting mixture is dried and calcined.
Optionally, the zinc source is a soluble zinc salt and/or an oxide of zinc;
the first metal source contains an oxide of a first metal element, preferably one or more of titanium oxide, manganese oxide, tin oxide and tungsten oxide;
the second metal source contains an oxide of a second metal element, preferably one or more of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, barium chloride and calcium chloride;
the solvent is selected from one or more of methanol, ethanol and water.
Optionally, the mixing conditions include: the temperature is 20-40deg.C, and the time is 10-60min; preferably, the temperature is 20-30deg.C for 20-40min.
Optionally, the drying conditions include: the temperature is 30-180 ℃ and the time is 1-24 hours; preferably, the temperature is 90-130℃for a period of 5-15 hours.
Optionally, the firing conditions include: the temperature is 600-1100 ℃ and the time is 1-10 hours; preferably 600-850 ℃ for 1-7 hours;
more preferably, the firing includes a first firing and a second firing that are sequentially performed; the conditions of the first firing include: the temperature is 600-850 ℃ and the time is 1-7 hours; the conditions of the second firing include: the temperature is 800-1100 ℃ and the time is 1-7 hours.
The third aspect of the invention provides a method for preparing olefin by dehydrogenating light alkane, which comprises the following steps: the dehydrogenation reaction is carried out by contacting the lower alkane with the catalyst provided in the first aspect of the present invention.
Optionally, the dehydrogenation reaction conditions include: the mass airspeed of the low-carbon alkane is 0.1 to 10h -1 The reaction temperature is 550-650 ℃, and the reaction pressure is 0.01-0.1MPa; the lower alkane is selected from propane, butane or isobutane.
Compared with the prior art, the invention has the following beneficial effects:
(1) Zinc is used as a propane dehydrogenation active component of the catalyst, the activity and the selectivity of the catalyst can be improved through the cooperation of the first auxiliary agent and the second auxiliary agent, and the catalyst can be used for preparing olefin by dehydrogenating light alkane to improve the yield of the target product olefin;
(2) The catalyst has no strict requirement on a carrier, has low price advantage, and has good industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a catalyst for preparing olefin by dehydrogenating light alkane, which comprises 20-50 wt% of ZnO,20-65 wt% of first auxiliary agent component, 0.1-10 wt% of second auxiliary agent component and 10-50 wt% of binder based on the dry weight of the catalyst; the first auxiliary component comprises zirconium dioxide and silicon dioxide composite oxide and a first metal element, wherein the first metal element is selected from one or more of titanium, manganese, tin and tungsten; the second auxiliary component contains a second metal element, and the second metal element is one or more selected from lithium, sodium, potassium, magnesium, barium and calcium.
The catalyst disclosed by the invention takes zinc as the propane dehydrogenation active component of the catalyst, the activity and the selectivity of the catalyst can be improved through the matched use of the first auxiliary agent and the second auxiliary agent, and the selectivity of a target product can be improved when the catalyst is used in the process of preparing propane by dehydrogenating low-carbon olefin.
In one embodiment of the invention, the catalyst comprises 20-45 wt% of the ZnO,20-50 wt% of the first auxiliary component, 0.1-8 wt% of the second auxiliary component, and 10-40 wt% of the binder.
In one embodiment of the present invention, the silica content of the zirconia and silica composite oxide is 0.1 to 50 wt%, preferably 0.1 to 30 wt%, more preferably 0.1 to 20 wt%.
In a specific embodiment of the present invention, the first auxiliary component contains a composite oxide of zirconium dioxide and silicon dioxide and an oxide of the first metal element, and the oxide of the first metal element may be, for example, one or more of titanium oxide, manganese oxide, tin oxide and tungsten oxide; the second auxiliary component contains an oxide of the second metal element, and may be lithium chloride, sodium chloride, potassium chloride, magnesium chloride, barium chloride, and calcium chloride, for example.
In one embodiment of the invention, the binder is selected from one or more of an aluminum sol, a silica sol and SB powder, preferably an aluminum sol and/or SB powder.
In a second aspect, the present invention provides a process for preparing the catalyst provided in the first aspect of the invention, the process comprising: after mixing the zinc source, the zirconium dioxide and silicon dioxide composite oxide, the first metal source, the second metal source, the binder and the solvent, the resulting mixture is dried and calcined.
The method has simple production process and environmental protection, and can prepare the catalyst with better reaction activity.
In a preferred embodiment of the present invention, the mixing conditions include: the temperature is 20-40deg.C, and the time is 10-60min; preferably, the temperature is 20-30deg.C for 20-40min.
In a preferred embodiment of the invention, the method comprises: firstly, a zinc source, zirconium dioxide and silicon dioxide composite oxide, a first metal source, a second metal source and a solvent are subjected to first mixing, and then a binder is added for second mixing. The conditions of the first mixing include: the temperature is 20-40deg.C, and the time is 1-30min; the conditions of the second mixing include: the temperature is 20-40deg.C, and the time is 1-30min.
In a specific embodiment of the present invention, the zinc source is a soluble zinc salt and/or zinc oxide, for example, one or more selected from zinc oxide, zinc chloride, zinc nitrate, zinc acetate and zinc carbonate; the first metal source contains an oxide of a first metal element, preferably one or more of titanium oxide, manganese oxide, tin oxide and tungsten oxide; the second metal source contains an oxide of a second metal element, preferably one or more of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, barium chloride and calcium chloride; the solvent is water.
In one embodiment of the present invention, the mixing conditions include: the temperature is 20-40deg.C, and the time is 10-60min; preferably, the temperature is 20-30deg.C for 20-40min. More preferably, the mixing is carried out under stirring, which may be carried out by means conventionally employed by those skilled in the art, for example by means of a mechanical stirrer.
In one embodiment of the present invention, the drying conditions include: the temperature is 30-180 ℃ and the time is 1-24 hours; preferably, the temperature is 90-130℃for a period of 5-15 hours. Drying is well known to those skilled in the art and can be carried out, for example, in a thermostatted oven, a tube furnace.
In one embodiment of the present invention, the firing conditions include: the temperature is 600-1100 ℃ and the time is 1-10 hours; preferably at 600-850 deg.c for 1-7 hours. The firing atmosphere is not particularly limited, and may be, for example, an air atmosphere. Calcination is well known to those skilled in the art and may be carried out in equipment conventionally employed by those skilled in the art, for example, a muffle furnace or a tube furnace may be employed. In a preferred embodiment, the firing comprises a first firing and a second firing that are performed sequentially; the temperature of the first firing is lower than the temperature of the second firing. Preferably, the conditions of the first firing include: the temperature is 600-850 ℃ and the time is 1-7 hours; the conditions of the second firing include: the temperature is 800-1100 ℃ and the time is 1-7 hours. The catalyst with better reaction activity is prepared by roasting in stages.
The third aspect of the invention provides a method for preparing olefin by dehydrogenating light alkane, which comprises the following steps: the dehydrogenation reaction is carried out by contacting the lower alkane with the catalyst provided in the first aspect of the invention. The method has better selectivity of the low-carbon alkane.
In one embodiment of the present invention, the dehydrogenation reaction conditions include: the mass airspeed of the low-carbon alkane is 0.1 to 10h -1 The reaction temperature is 550-650 ℃ and the reaction pressure is 0.01-0.1MPa; the lower alkane is selected from propane, butane or isobutane.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
In the following examples and comparative examples, all reagents used were commercially available unless otherwise specified. Wherein the silicon dioxide and zirconium dioxide composite oxide is prepared by the following method:
(1) Zirconium hydroxide is prepared.
Zirconium oxychloride (ZrOCl) was taken at a concentration of 5 mass% 2 ·8H 2 O) aqueous solution, adding ammonia water with a concentration of 25 mass% slowly while stirring, adjusting the pH value to 9, transferring the obtained zirconium hydroxide precipitate together with the solution to an autoclave for sealing, and carrying out hydrothermal treatment at 100 ℃ for 24 hours. Filtering and removing the solidWashing with ionized water until the filtrate is free of Cl - Drying at 110 ℃ for 24 hours to obtain zirconium hydroxide powder.
(2) Preparation of zirconium dioxide and silicon dioxide composite oxide
40 g of the zirconium hydroxide powder prepared above was taken and added to 150 ml of an aqueous solution, followed by stirring, and 16.8 g of silica sol (produced by Jinfeng chemical Co., ltd.) was added to the mixture, which was SiO 2 The content was 42 mass%, the particle diameter of the colloidal particles was 10nm, the pH value was 8.5, na 2 O content is 0.05 mass%, and after being mixed uniformly, the mixture is dried at 110 ℃ for 24 hours and baked at 800 ℃ for 3 hours.
Example 1
6g of zinc oxide, 6g of titanium oxide, 1.4g of silicon dioxide and zirconium dioxide composite oxide (the content of the silicon dioxide is 1.5 weight percent) and 0.3812g of magnesium chloride are added into 35mL of deionized water to be uniformly stirred, 21.21g of aluminum sol is added into slurry to be mixed and stirred for 40min at 30 ℃ until the mixture is shaped, the obtained mixture is dried at 120 ℃ for 12h, then the mixture is roasted for 1h in an air atmosphere at 600 ℃, and then the mixture is roasted for 4h in an air atmosphere at 815 ℃ to prepare a catalyst A, wherein the composition of the catalyst is shown in the table 1.
Example 2
Adding 6g of zinc oxide, 6g of titanium oxide, 1.4g of silicon dioxide and zirconium dioxide composite oxide (the content of silicon dioxide is 1.5 weight percent) and 0.1288g of calcium chloride into 35mL of deionized water, uniformly stirring, adding 21.21g of aluminum sol into slurry, mixing and stirring for 40min at 30 ℃, drying the obtained mixture at 120 ℃ for 12h, roasting at 600 ℃ for 1h in air atmosphere, and roasting at 815 ℃ for 4h in air atmosphere to obtain the catalyst B.
Example 3
Catalyst C was prepared in the same manner as in example 1 except that magnesium chloride was added in a mass of 0.2300g.
Example 4
Catalyst D was prepared in the same manner as in example 1 except that magnesium chloride was added in a mass of 0.4577g.
Example 5
Catalyst E was prepared in the same manner as in example 1 except that 6g of tungsten oxide was used instead of 6g of titanium oxide and 0.0869g of potassium chloride was used instead of 0.3812g of magnesium chloride.
Example 6
Catalyst F was prepared in the same manner as in example 1 except that 6g of manganese oxide was used instead of 6g of titanium oxide.
Example 7
Catalyst G was prepared in the same manner as in example 1 except that the content of silica in the composite oxide of silica and zirconia was 35% by weight.
Comparative example 1
Adding 6g of zinc oxide, 6g of titanium oxide and 1.4g of silicon dioxide and zirconium dioxide composite oxide (the content of silicon dioxide is 1.5 wt%) into 35mL of deionized water, uniformly stirring, adding 21.21g of aluminum sol into the slurry, mixing and stirring at 30 ℃ for 40min to fix, drying the obtained mixture sample at 120 ℃ for 12h, roasting at 600 ℃ for 1h in air atmosphere, and roasting at 815 ℃ for 4h in a muffle furnace to obtain the catalyst a. The catalyst a prepared contained 33.4 wt% zinc oxide, 41.2 wt% of the first auxiliary component, 25.4 wt% of the binder, and no second auxiliary component.
Comparative example 2
Catalyst b was prepared in the same manner as in example 1 except that 1.4g of silica was used in place of 1.4g of the silica and zirconium dioxide composite oxide. Catalyst b was prepared to contain 33.4 wt% zinc oxide, 41.2 wt% of the first adjunct component, 0.4 wt% of the second adjunct component, 25.4 wt% of the binder.
Comparative example 3
2.0476g of zinc nitrate and 20mL of deionized water are mixed to prepare an impregnating solution, and the impregnating solution is impregnated to prepare the catalyst. 15g of zirconia is used as a carrier, and is contacted and impregnated with an impregnating solution, the mass ratio of liquid to solid is 1.2, the impregnated carrier is rotationally evaporated to dryness under the conditions of 75 ℃ and the vacuum degree of-0.08 MPa, and the carrier is dried for 12 hours at 120 ℃, and then baked for 4 hours at 700 ℃ to prepare the catalyst c. The catalyst c thus prepared contained 3% by weight of zinc.
Comparative example 4
2.6g of zinc nitrate and 1.7g of anhydrous zirconium chloride are dissolved in 500mL of chilled water, 24mL of titanium tetrachloride is added with stirring, ammonia water is added dropwise at 55 ℃ until the pH value of the solution is neutral, the solution is aged for 2 hours, the precipitate is filtered and dried for 12 hours, and then the catalyst d is prepared by roasting at 700 ℃ for 4 hours. The catalyst d thus prepared contained 6.1% by weight of zinc oxide, 86.3% by weight of titanium oxide and 7.7% by weight of zirconium oxide.
Comparative example 5
Catalyst e was prepared in the same manner as in example 1 except that zinc oxide was added in an amount of 12.23g.
Test case
In a micro-reaction device, 3g of catalyst is filled, propane is taken as raw material, and the feeding mass space velocity of propane is 3.5h at 620 ℃ and normal pressure -1 And (3) carrying out propane dehydrogenation reaction under the condition of (1) introducing propane for 5min for sampling. The propane conversion and propylene selectivity were calculated. Changes in propane dehydrogenation conversion the changes in propylene selectivity and propylene yield and carbon content are shown in Table 2.
TABLE 1
Figure BDA0003329348540000111
TABLE 2
Figure BDA0003329348540000112
Figure BDA0003329348540000121
From the above results, it is clear that the dehydrogenation catalyst prepared by the method of the present invention has both high propane conversion and propylene selectivity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (12)

1. The catalyst for preparing olefin by dehydrogenation of low-carbon alkane contains 20-50 wt% of ZnO,20-65 wt% of first auxiliary component, 0.1-10 wt% of second auxiliary component and 10-50 wt% of binder based on the dry weight of the catalyst;
the first auxiliary component comprises zirconium dioxide and silicon dioxide composite oxide and a first metal element, wherein the first metal element is selected from one or more of titanium, manganese, tin and tungsten;
the second auxiliary component contains a second metal element, and the second metal element is one or more selected from lithium, sodium, potassium, magnesium, barium and calcium.
2. The catalyst of claim 1, wherein the catalyst comprises 20-45 wt% of the ZnO,20-50 wt% of the first promoter component, 0.1-8 wt% of the second promoter component, and 10-40 wt% of the binder.
3. Catalyst according to claim 1, wherein the silica content of the zirconium dioxide and silica composite oxide is 0.1-50 wt%, preferably 0.1-30 wt%.
4. The catalyst according to claim 1, wherein the first auxiliary component contains a zirconium dioxide and silicon dioxide composite oxide and an oxide of the first metal element;
the second auxiliary component contains a chloride of the second metal element.
5. A catalyst according to claim 1, wherein the binder is selected from one or more of an aluminium sol, a silica sol and SB powder.
6. A process for preparing the catalyst of any one of claims 1-5, the process comprising: after mixing the zinc source, the zirconium dioxide and silicon dioxide composite oxide, the first metal source, the second metal source, the binder and the solvent, the resulting mixture is dried and calcined.
7. The method of claim 6, wherein the zinc source is a soluble zinc salt and/or an oxide of zinc;
the first metal source contains an oxide of a first metal element, preferably one or more of titanium oxide, manganese oxide, tin oxide and tungsten oxide;
the second metal source contains an oxide of a second metal element, preferably one or more of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, barium chloride and calcium chloride;
the solvent is selected from one or more of methanol, ethanol and water.
8. The method of claim 6, wherein the mixing conditions comprise: the temperature is 20-40deg.C, and the time is 10-60min; preferably, the temperature is 20-30deg.C for 20-40min.
9. The method of claim 6, wherein the drying conditions comprise: the temperature is 30-180 ℃ and the time is 1-24 hours; preferably, the temperature is 90-130℃for a period of 5-15 hours.
10. The method of claim 6, wherein the firing conditions include: the temperature is 600-1100 ℃ and the time is 1-10 hours; preferably 600-850 ℃ for 1-7 hours;
more preferably, the firing includes a first firing and a second firing that are sequentially performed; the conditions of the first firing include: the temperature is 600-850 ℃ and the time is 1-7 hours; the conditions of the second firing include: the temperature is 800-1100 ℃ and the time is 1-7 hours.
11. A method for preparing olefin by dehydrogenating light alkane, comprising the following steps: contacting a lower alkane with the catalyst of any one of claims 1-5 to effect dehydrogenation.
12. The method of claim 11, wherein the dehydrogenation reaction conditions comprise:
the mass airspeed of the low-carbon alkane is 0.1 to 10h -1 The reaction temperature is 550-650 ℃, and the reaction pressure is 0.01-0.1MPa;
the lower alkane is selected from propane, butane or isobutane.
CN202111273296.0A 2021-10-29 2021-10-29 Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method and application thereof Pending CN116059991A (en)

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