CN115337955B - Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation - Google Patents

Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation Download PDF

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CN115337955B
CN115337955B CN202110517357.7A CN202110517357A CN115337955B CN 115337955 B CN115337955 B CN 115337955B CN 202110517357 A CN202110517357 A CN 202110517357A CN 115337955 B CN115337955 B CN 115337955B
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dehydrogenation catalyst
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CN115337955A (en
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刘红梅
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J35/635—0.5-1.0 ml/g
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    • 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
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    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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    • 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
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Abstract

The invention relates to the field of catalysts, and discloses a novel dehydrogenation catalyst, a preparation method thereof and application thereof in preparing isobutene by isobutane dehydrogenation. The novel dehydrogenation catalyst comprises a support, a first metal component, a second metal component and a non-metal component supported on the support; wherein the carrier is Al 2 O 3 -KIT-6 cubic structured composite material, and based on the total weight of the novel dehydrogenation catalyst, the content of the first metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the non-metal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%. The novel dehydrogenation catalyst can achieve better isobutane dehydrogenation activity, isobutene selectivity and stability under the condition of not using noble metals and metal components with serious pollution.

Description

Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation
Technical Field
The invention relates to the field of catalysts, in particular to a novel dehydrogenation catalyst, a preparation method thereof and application thereof in preparing isobutene by isobutane dehydrogenation.
Background
Isobutene is an important basic petrochemical raw material, has wide application, and can be used for synthesizing various organic raw materials and fine chemicals such as methyl tertiary butyl ether, ethyl tertiary butyl ether, butyl rubber, polyisobutylene, methacrylate, methyl methacrylate, isoprene, tertiary butylphenol, tertiary butylamine, 1, 4-butanediol, ABS resin and the like. However, isobutene has no natural source and is mainly derived from C in catalytically cracked liquefied petroleum gas 4 Component and byproduct C in ethylene preparation by naphtha steam cracking 4 C in olefins and natural gas 4 The components are as follows. In the above background, the dehydrogenation of isobutane to isobutene is one of the important ways to increase the isobutene source. At present, three reaction pathways developed in the research field of preparing isobutene by isobutane dehydrogenation are mainly: (1) direct dehydrogenation of isobutane; (2) oxidative dehydrogenation of isobutane; (3) membrane-catalyzed reaction dehydrogenation of isobutane. The technology for preparing isobutene by direct catalytic dehydrogenation of isobutane has realized industrial production in the 90 th century, and the main technologies comprise a Catofin process developed by ABB Lummes company, an Oleflex process developed by UOP company, a Star process developed by Phillips company, an FBD-4 process developed by Snamprogetti-Yarstez company and a Linde process developed by Linde company. The five processes described above all employ catalysts of the Pt (Oleflex and Star processes) or Cr (Catofin, FBD-4 and Linde processes). The noble metal catalyst has higher activity, better selectivity and more environment-friendly property. However, pt-based catalysts have the disadvantages of complicated operation process, high operation requirements, and high cost. Relatively speaking, cr-based catalysts are low in price, but the catalysts are easy to accumulate carbon and quick in deactivation, need frequent regeneration, cause environmental pollution once leaked and generate cancerogenic substances Cr 6+ Is not beneficial to environmental protection. Therefore, various processes for producing isobutene by dehydrogenating isobutane have been developed without causing any problemsThe non-metal components with serious environmental pollution, the catalyst with higher dehydrogenation catalytic activity and better stability are all main technical problems to be solved currently and urgently.
In order to improve various performance indexes of Cr-based dehydrogenation catalysts, researchers have made many efforts. Such as: the catalytic performance of the Cr catalyst is improved by adding an auxiliary agent (CN 104549220A), the addition of Cr components is avoided by developing a multicomponent catalyst formula (CN 102451677B, CN 104607168A), and the reactivity of the non-noble metal dehydrogenation catalyst is improved by improving the catalyst preparation method (ACS catalyst.2015, 5, 3494-3503).
Although the prior art improves the Cr-based catalyst for industrial application to a certain extent, the problems of complex catalyst components, complicated preparation process and further improvement of catalyst performance still exist.
Disclosure of Invention
The invention aims to overcome the defects of high cost or easiness in causing environmental pollution of the existing catalyst for preparing isobutene through isobutane dehydrogenation, and provides a novel dehydrogenation catalyst, a preparation method thereof and application thereof in preparing isobutene through isobutane dehydrogenation.
In order to achieve the above object, a first aspect of the present invention provides a novel dehydrogenation catalyst, wherein the novel dehydrogenation catalyst comprises a support, and a first metal component, a second metal component and a non-metal component supported on the support; wherein the carrier is Al 2 O 3 -KIT-6 cubic structured composite material, and based on the total weight of the novel dehydrogenation catalyst, the content of the first metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the non-metal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%.
The second aspect of the present invention provides a preparation method of the novel dehydrogenation catalyst, wherein the preparation method comprises the following steps: in ultrasonic auxiliary stripUnder the condition, the solution containing the first metal component precursor and the second metal component precursor is mixed with Al 2 O 3 The KIT-6 cubic structure composite material is contacted and subjected to impregnation treatment, and then the solvent is removed, dried and roasted to obtain an initial catalyst; and then the initial catalyst is contacted with sulfur-containing gas for vulcanization treatment, so that the novel dehydrogenation catalyst is obtained.
The third aspect of the invention provides an application of the novel dehydrogenation catalyst in the reaction of preparing isobutene by dehydrogenating isobutane.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) The novel dehydrogenation catalyst disclosed by the invention does not contain noble metals, so that the preparation cost of the dehydrogenation catalyst can be effectively reduced;
(2) The novel dehydrogenation catalyst disclosed by the invention does not contain chromium element and is environment-friendly;
(3) The novel dehydrogenation catalyst provided by the invention has good catalytic performance when used for the reaction of preparing isobutene by dehydrogenating isobutane, and has the advantages of high isobutane conversion rate, high isobutene selectivity and good catalyst stability;
(4) The preparation method of the novel dehydrogenation catalyst has the advantages of simple process, easy control of conditions and good product repeatability.
Drawings
FIG. 1 is Al prepared in example 1 2 O 3 -small angle XRD spectrum of KIT-6 cubic structure composite a;
FIG. 2 is Al prepared in example 1 2 O 3 -wide angle XRD spectrum of KIT-6 cubic structure composite a;
FIG. 3 is Al prepared in example 1 2 O 3 -pore size distribution map of KIT-6 cubic structure composite a.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a novel dehydrogenation catalyst, wherein the novel dehydrogenation catalyst comprises a support and a first metal component, a second metal component and a non-metal component supported on the support; wherein the carrier is Al 2 O 3 -KIT-6 cubic structured composite material, and based on the total weight of the novel dehydrogenation catalyst, the content of the first metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the non-metal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%.
The inventors of the present invention have found when conducting a study of preparation of an isobutane dehydrogenation catalyst: compared with Pt-based dehydrogenation catalysts, cr-based catalysts are lower in cost, but are inferior in stability and severe in pollution. In order to maintain low catalyst cost while considering environmental requirements, the dehydrogenation catalyst is prepared by substituting Cr with a non-noble metal element in the prior art. However, the performance of the alternative catalyst still cannot completely reach the level of the Cr-based catalyst, and the performance is mainly represented in the aspects of lower selectivity, poor stability and the like. For non-noble metal catalysts, pure metal components are readily formed if the oxidized metal component is deeply reduced in the reducing atmosphere of the isobutane dehydrogenation reaction. The pure metal component has very strong dehydrogenation performance, so that the selectivity of isobutene is severely reduced due to deep dehydrogenation or hydrogenolysis of isobutane. In addition, the prior art uses gamma-alumina or silicon oxide as a carrier to load non-noble metal components for preparing the isobutane dehydrogenation catalyst, and has the defects of poor olefin selectivity and poor stability.
The inventors of the present invention unexpectedly found that: commercially available alumina carriers or silica carriers are low in cost, but the pore size distribution is uneven, the specific surface area is small, and the dispersion of active metal components on the surface of the carrier and the diffusion of raw materials and products in the reaction process are not facilitated. In comparison, the mesoporous molecular sieve KIT-6 has large specific surface area, large pore volume and pore canal sizeUniform and more favorable for the diffusion of reactant molecules and product molecules in the reaction. However, the bulk density of the KIT-6 molecular sieve is small, and the volume of the KIT-6 molecular sieve is too large after the KIT-6 molecular sieve is prepared into a catalyst, so that the industrial application of the KIT-6 molecular sieve is limited. The inventor of the present invention found that the shaped Al is prepared by combining structural characteristics of alumina and KIT-6 molecular sieve by utilizing the advantage of good cohesiveness of alumina 2 O 3 The KIT-6 cubic structure composite material is further prepared into an isobutane dehydrogenation catalyst, so that the current situation that the isobutane dehydrogenation catalyst in the prior art is poor in performance can be effectively improved.
Further, the inventors of the present invention found that: if the non-noble metal catalyst is subjected to sulfuration treatment, S element exists on the surface of the catalyst, and the S element can be combined with the active metal component to generate sulfide in the reducing atmosphere of dehydrogenation reaction. The existence of the non-noble metal sulfide can effectively avoid the deep reduction of the metal component, thereby reducing the pure metal component on the surface of the catalyst and obviously inhibiting the occurrence of side reactions such as hydrogenolysis and the like. The selectivity and stability of the dehydrogenation catalyst after vulcanization treatment in the reaction of preparing isobutene by dehydrogenating isobutane are obviously improved.
Still further, the inventors of the present invention found that: if a small amount of alkali metal or alkaline earth metal is introduced on the surface of the isobutane dehydrogenation catalyst, a small amount of acid centers on the surface of the catalyst carrier can be effectively balanced, so that side reactions are reduced, and the selectivity of a target product is improved.
According to the present invention, preferably, the first metal component is contained in an amount of 5 to 20 wt%, the second metal component is contained in an amount of 0.5 to 5 wt%, the nonmetallic component is contained in an amount of 0.2 to 2 wt%, and the support is contained in an amount of 72 to 95 wt%, based on the total weight of the novel dehydrogenation catalyst; more preferably, the first metal component is present in an amount of from 6.2 to 19.2 wt%, the second metal component is present in an amount of from 0.5 to 3.9 wt%, the non-metal component is present in an amount of from 0.7 to 1.7 wt%, and the support is present in an amount of from 75.2 to 92.6 wt%, based on the total weight of the novel dehydrogenation catalyst. In the invention, the contents of the first metal component, the second metal component, the nonmetallic component and the carrier are limited to be within the range, so that the number and quality requirements of the surface active centers of the catalyst can be met, and the diffusion of reactant molecules and product molecules can be promoted through a special carrier pore channel structure.
According to the invention, the Al 2 O 3 The specific surface area of the-KIT-6 cubic structure composite material is 300-700m 2 The pore volume is 0.6-1.4mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 7-9nm and 10-15nm respectively; preferably, the Al 2 O 3 The specific surface area of the-KIT-6 composite material is 483-545m 2 And/g, wherein the pore volume is 0.9-1.1mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 7.8-8.2nm and 11.8-12.5nm respectively.
According to the present invention, the first metal component is selected from one or more of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper; preferably, the first metal component is selected from one or more of iron, nickel, zinc, molybdenum and tin; more preferably, the non-noble metal is selected from one or more of iron, nickel and zinc.
According to the invention, the second metal component is an alkali metal and/or an alkaline earth metal; preferably, the second metal component is selected from one or more of sodium, magnesium, potassium, calcium and lithium; more preferably, the second metal component is selected from one or more of sodium, magnesium and potassium.
According to the invention, the nonmetallic component is S.
According to the invention, the Al 2 O 3 The preparation method of the KIT-6 cubic structure composite material comprises the following steps:
(1) Under the condition of preparing an adhesive tape piece by hydrolysis, contacting and mixing a template solvent, a silicon source, n-butanol and hydrochloric acid to obtain a gel mixture; crystallizing the gel mixture; then filtering, washing, first drying and first roasting the crystallized product to obtain the KIT-6 mesoporous molecular sieve;
(2) Mixing the KIT-6 mesoporous molecular sieve, the alumina precursor and the extrusion aid in the presence of dilute nitric acid, extruding to form, and performing second drying and second bakingFiring to obtain Al 2 O 3 KIT-6 cubic structure composite material.
According to the invention, the template agent is a nonionic surfactant; preferably, the template agent is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer; more preferably P123 (EO 20 PO 70 EO 20 )。
According to the invention, the silicon source is a silicon-containing organic compound and/or a silicon-containing inorganic compound; preferably a silicon-containing organic compound; more preferably one or more of ethyl orthosilicate, methyl orthosilicate or butyl orthosilicate.
According to the invention, the molar ratio of the amounts of the plate agent, the silicon source, the n-butanol, the hydrochloric acid and the water is 1: (10-150): (20-200): (200-1200): (5000-20000); preferably 1: (30-100): (50-120): (500-900): (8000-13500).
According to the invention, the conditions for preparing the glue by hydrolysis comprise: the temperature is 20-50 ℃ and the time is 5-30h.
According to the present invention, the crystallization conditions include: the temperature is 80-120 ℃ and the time is 10-40h. As is well known to those skilled in the art, the crystallization is generally performed in a hydrothermal kettle, and will not be described herein.
According to the present invention, there is no particular requirement for the filtration process, and filtration means known in the art may be used, including gravity filtration, pressure filtration, vacuum filtration or centrifugal filtration. Preferably, the filtering process specifically includes: vacuum-pumping the bottom of the funnel by using a suction bottle or filtering by using a centrifugal filter.
According to the present invention, the washing process may include: after filtration, a solid product is obtained, which is repeatedly washed with distilled water (the washing times may be 2 to 10 times), and then suction filtration is performed.
According to the present invention, the first drying conditions include: the temperature is 70-140 ℃ and the time is 4-20h.
According to the present invention, the conditions for the first firing include: the temperature is 400-600 ℃ and the time is 8-60h.
According to the invention, the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite; the extrusion aid is one or more of sesbania powder, polyacrylamide or cellulose, preferably sesbania powder.
According to the invention, the mass concentration of the dilute nitric acid may be 1-20%, preferably 2-10%.
According to the invention, the weight ratio of the dosages of the KIT-6 mesoporous molecular sieve, the alumina precursor, the extrusion aid and the dilute nitric acid is 1: (0.3-5): (0.02-0.5): (0.2-5), preferably 1: (0.5-3): (0.05-0.2): (0.5-2).
According to the present invention, the second drying conditions include: the temperature is 70-150 ℃ and the time is 3-16h.
According to the present invention, the conditions for the second firing include: the temperature is 450-650 ℃ and the time is 3-15h.
The second aspect of the present invention provides a preparation method of the novel dehydrogenation catalyst, wherein the preparation method comprises the following steps: under the ultrasonic auxiliary condition, the solution containing the first metal component precursor and the second metal component precursor is mixed with Al 2 O 3 The KIT-6 cubic structure composite material is contacted and subjected to impregnation treatment, and then the solvent is removed, dried and roasted to obtain an initial catalyst; and then the initial catalyst is contacted with sulfur-containing gas for vulcanization treatment, so that the novel dehydrogenation catalyst is obtained.
According to the invention, the ultrasound-assisted conditions include: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W; preferably, the ultrasound-assisted conditions include: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
According to the invention, the conditions of the impregnation include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.5-10h, preferably 2-8h. In the present invention, co-impregnation and/or stepwise impregnation methods may be employed.
According to the invention, the first metal component precursor is selected from the group consisting of nitrates, sulfites, sulfates or metal chlorides containing one or more elements of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper.
According to the invention, the second metal component precursor is selected from the group consisting of alkali metal and/or alkaline earth metal containing nitrates, sulfites, sulfates or metal chlorides.
According to the present invention, the solution containing the first metal component precursor and the second metal component precursor is an aqueous solution or an ethanol solution containing the metal component precursors; the mass concentration of the solution is preferably 0.5-10%.
The method for removing the solvent according to the present invention is not particularly limited, and may be a method known in the art, such as: the solvent is removed by evaporation using a rotary evaporator or by heating and stirring.
According to the invention, the drying conditions include: the temperature is 60-150deg.C, preferably 80-130deg.C; the time is 1-20h, preferably 3-15h.
According to the invention, the conditions of the calcination include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15 hours, preferably 3-10 hours.
According to the invention, the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide; the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1-5%, preferably 0.3-2%.
According to the invention, the conditions of the vulcanization treatment include: the temperature is 400-700 ℃ and the time is 1-15h; preferably, the processing conditions include: the temperature is 450-650 ℃ and the time is 2-8h.
According to the present invention, the novel dehydrogenation catalyst may be in the form of spheres, pellets, strips, cylinders, etc.
The third aspect of the invention provides an application of the novel dehydrogenation catalyst in the reaction of preparing isobutene by dehydrogenating isobutane.
According to the invention, the application comprises: the reaction raw material isobutane is contacted with the novel dehydrogenation catalyst.
According to the invention, the contact conditions include: the contact temperature is 500-650 ℃, the partial pressure of raw material gas is 0.02-0.5MPa, and the mass of propane is emptyThe speed is 1.0-10.0h -1 。
The present invention will be described in detail by examples.
In the following examples and comparative examples:
(1) The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model.
(2) Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
(3) The ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner manufactured by Kunshan ultrasonic instrument Co., ltd, the ultrasonic frequency is 80kHz, and the working voltage is 220V;
(4) The rotary evaporator is manufactured by IKA corporation in Germany, and the model is RV10 digital;
(5) The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
(6) The muffle furnace is available from CARBOLITE company under the model CWF1100.
(7) The reagents used in examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
(8) The isobutane conversion was calculated as follows:
isobutane conversion = amount of isobutane consumed by the reaction/initial amount of isobutane x 100%;
the isobutene selectivity was calculated as follows:
isobutene selectivity = amount of isobutane consumed to produce isobutene/total amount of isobutane consumed x 100%.
Example 1
This example is a description of a support, supported catalyst and use made by the method of the invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
11.6g of triblock copolymer surfactant P123 was dissolved in 4113.9M hydrochloric acid solution at 35℃and stirred for 4h until P123 was completely dissolved to form a clear solution; then 11.8g of n-butanol was added to the solution and stirring was continued for 1h; then, 25g of ethyl orthosilicate was slowly dropped into the solution, and the mixture was stirred at 35℃for 24 hours to obtain a gel mixture. The gel mixture is transferred to a hydrothermal reaction kettle and crystallized for 24 hours at the temperature of 100 ℃. And repeatedly washing the crystallized product with deionized water and carrying out suction filtration to obtain a KIT-6 mesoporous material filter cake. Drying the KIT-6 mesoporous material filter cake at 100 ℃ for 12 hours, and calcining at 500 ℃ for 24 hours to remove the template agent, thus obtaining the KIT-6 mesoporous molecular sieve A.
250g of KIT-6 mesoporous molecular sieve A prepared in the steps is uniformly mixed with 300g of pseudo-boehmite and 25g of sesbania powder, then 380g of 5% dilute nitric acid is added, and after uniform stirring, the mixture is extruded and formed and cut into cylinders with the diameter of 2mm and the length of 1-2 mm; drying at 100deg.C for 10 hr, and roasting at 600deg.C for 6 hr to obtain Al 2 O 3 KIT-6 cubic structure composite a.
For Al 2 O 3 The characterization of KIT-6 cubic structure composite A was carried out, with the pore structure parameters listed in Table 1.
FIG. 1 is Al prepared in example 1 2 O 3 -small angle XRD pattern of KIT-6 cubic structure mesoporous molecular sieve a; from the small angle spectrum peaks appearing in XRD spectra, al 2 O 3 The ordered mesoporous portion of the KIT-6 cubic structure mesoporous molecular sieve a has a typical three-dimensional cubic mesoporous structure.
FIG. 2 is Al prepared in example 1 2 O 3 The wide angle XRD pattern of the mesoporous molecular sieve A of the KIT-6 cubic structure can be seen from FIG. 2: the typical gamma-alumina diffraction pattern is shown in the wide-angle XRD spectrum, which shows that the disordered pore canal part of the alumina-two-dimensional hexagonal mesoporous molecular sieve composite material A consists of alumina, and the crystal phase structure of the alumina is gamma-alumina.
FIG. 3 is Al prepared in example 1 2 O 3 -pore size distribution diagram of KIT-6 cubic structure composite material a, pore size of the sample is in bimodal distribution, first most probable pore size is 8nm, and the first most probable pore size is mainly contributed by mesoporous molecular sieve; the second most probable pore diameter is 12nm, and is mainly composed of aluminaAnd donation.
(2) Novel dehydrogenation catalyst preparation
10.4g of ferric nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100g of absolute ethanol, together with 10g of Al 2 O 3 Mixing the KIT-6 cubic structure composite material A, and stirring and reacting for 60min under the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. And after the reaction is finished, evaporating solvent ethanol in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5h. Then roasting in a muffle furnace at 550 ℃ for 5 hours to obtain the initial catalyst A.
10g of the initial catalyst A was taken and used in H 2 And (3) treating the mixture for 5 hours at 550 ℃ in a nitrogen gas stream with the S content of 1.5% to obtain the novel dehydrogenation catalyst A.
The specific gravity of each component of the novel dehydrogenation catalyst A is as follows: 13.4 wt% of iron element, 2.5 wt% of sodium element, 1.3 wt% of sulfur element and the balance of carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The reactivity of the catalyst was evaluated on a fixed bed reactor. 2.0 g of catalyst A is filled into a fixed bed quartz reactor, the reaction temperature is controlled to be 580 ℃, the reaction pressure is controlled to be 0.1MPa, and the isobutane is prepared by the following steps: the molar ratio of helium is 1:1, the mass space velocity of the isobutane is 2.0h < -1 >, and the reaction time is 6h. Through Al 2 O 3 The reaction product separated by the S molecular sieve column was directly fed to an agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis.
The reaction results are shown in Table 3. The isobutane conversion and the isobutene selectivity were calculated from the reaction data, and the stability of the catalyst was judged from the magnitudes of the isobutane conversion and the isobutene selectivity gradually decreasing with the extension of the reaction time during the reaction.
Example 2
This example is a description of a support, supported catalyst and use made by the method of the invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 Each parameter in the preparation process of the KIT-6 cubic structure composite material is performed in example 2 to obtain Al 2 O 3 KIT-6 cubic structure composite B.
Al 2 O 3 The structural parameters of the KIT-6 cubic structure composite B are listed in table 1.
(2) Novel dehydrogenation catalyst preparation
10.4g of ferric nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100g of absolute ethanol, together with 10g of Al 2 O 3 Mixing the KIT-6 cubic structure composite material A, and stirring and reacting for 60min under the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. And after the reaction is finished, evaporating solvent ethanol in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5h. Then roasting in a muffle furnace at 550 ℃ for 5 hours to obtain the initial catalyst A.
0.53g of magnesium nitrate hexahydrate was dissolved in 70ml of deionized water, combined with 10g of Al 2 O 3 Mixing the KIT-6 cubic structure composite material B, and stirring and reacting for 30min under the assistance of ultrasonic waves with the power of 250W, wherein the temperature is 80 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 80℃and dried for 15h. Then roasting for 3 hours in a muffle furnace at 650 ℃ to obtain Mg-Al 2 O 3 -KIT-6 sample. 9.20g of zinc nitrate hexahydrate was dissolved in 150mL of deionized water, combined with the Mg-Al described above 2 O 3 Mixing KIT-6 sample, stirring and reacting for 30min under the assistance of ultrasonic wave with power of 250W, and the temperature is 80 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 80℃and dried for 15h. Then roasting for 3 hours in a muffle furnace at 650 ℃ to obtain the initial catalyst B.
10g of the initial catalyst B was taken and reacted in H 2 The novel dehydrogenation catalyst B is obtained by treating the mixture for 8 hours at 450 ℃ in a nitrogen gas stream with the S content of 2.0 percent.
The specific gravity of each component of the novel dehydrogenation catalyst B is as follows: 19.2 wt% zinc, 0.5 wt% magnesium, 1.7 wt% sulfur, and the balance being a carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The test of the reaction performance of catalyst B in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Example 3
This example is a description of a support, supported catalyst and use made by the method of the invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 Each parameter in the preparation process of the 3-KIT-6 cubic structure composite material is performed in example 3 to obtain Al 2 O 3 KIT-6 cubic structure composite material C. Al (Al) 2 O 3 The structural parameters of the KIT-6 cubic structure composite C are listed in Table 1.
(2) Novel dehydrogenation catalyst preparation
10.4g of ferric nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100g of absolute ethanol, mixed with 10g of A and reacted for 60 minutes with stirring at 50℃under the assistance of ultrasonic waves with a power of 200W. And after the reaction is finished, evaporating solvent ethanol in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5h. Then roasting in a muffle furnace at 550 ℃ for 5 hours to obtain the initial catalyst A.
3.12g of nickel nitrate hexahydrate was dissolved in 100mL of deionized water, with 10g of Al 2 O 3 Mixing the composite material C with the KIT-6 cubic structure, and stirring and reacting for 120min under the assistance of ultrasonic waves with the power of 150W, wherein the temperature is 20 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a dry box at 130 ℃ and dried for 3h. Then roasting for 10 hours in a muffle furnace at 500 ℃ to obtain Ni-Al 2 O 3 -KIT-6 sample. 0.79g of potassium chloride was dissolved in 100mL of deionized water, and mixed with the above Ni-Al 2 O 3 KIT-6 sample mixAnd mixing and reacting for 120min under the assistance of ultrasonic waves with the power of 150W, wherein the temperature is 20 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a dry box at 130 ℃ and dried for 3h. Then, the mixture was calcined in a muffle furnace at 500℃for 10 hours to obtain an initial catalyst C.
10g of the initial catalyst C was treated at 650℃for 2 hours in a nitrogen stream having an H2S content of 1.0% to give a novel dehydrogenation catalyst C.
The specific gravity of each component of the novel dehydrogenation catalyst C is as follows: 6.2 wt% of nickel element, 3.9 wt% of potassium element, 0.7 wt% of sulfur element and the balance of carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The test of the reaction performance of catalyst C in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Example 4
This example is a description of a support, supported catalyst and use made by the method of the invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 Each parameter in the preparation process of the KIT-6 cubic structure composite material is performed in example 4 to obtain Al 2 O 3 KIT-6 cubic structure composite D.
Al 2 O 3 The structural parameters of the KIT-6 cubic structure composite D are listed in table 1.
(2) Novel dehydrogenation catalyst preparation
The conditions in the preparation of the novel dehydrogenation catalyst in step (2) of example 1 were changed so that the specific gravity of each component of the novel dehydrogenation catalyst D prepared was: 4.2 wt% of iron element, 7.3 wt% of sodium element, 3.4 wt% of sulfur element and the balance of carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The test of the reaction performance of catalyst D in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Example 5
This example is a description of a support, supported catalyst and use made by the method of the invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 Each parameter in the preparation process of the KIT-6 cubic structure composite material is performed in example 5 to obtain Al 2 O 3 KIT-6 cubic structure composite E.
Al 2 O 3 The structural parameters of the KIT-6 cubic structure composite E are listed in Table 1.
(2) Novel dehydrogenation catalyst preparation
The conditions in the preparation of the novel dehydrogenation catalyst in step (2) of example 1 were changed so that the specific gravity of each component of the novel dehydrogenation catalyst D prepared was: 27.1% by weight of elemental iron, 0.4% by weight of elemental sodium, 0.3% by weight of elemental sulfur, the remainder being a carrier.
(3) Evaluation of catalyst Performance in the reaction of producing isobutene by dehydrogenation of isobutane
The test of the reaction performance of catalyst E in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in the step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 1
A supported catalyst D1 was prepared in the same manner as in example 1 except that: step (1) of example 1 was omitted and in step (2), commercially available alumina was used in place of Al 2 O 3 -KIT-6 cubic structure composite a as catalyst carrier; and the content of metallic element iron is 13.4 wt%, the content of metallic element sodium is 2.5 wt%, the content of S is 1.3 wt%, and the rest is carrier alumina, based on the total weight of the catalyst D1.
The test of the reaction performance of catalyst D1 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 2
A supported catalyst D2 was prepared in the same manner as in example 1 except that: the catalyst preparation conditions were adjusted so that the content of elemental iron was 1.5 wt%, the content of elemental sodium was 0.3 wt%, the content of S was 3.0 wt%, and the balance was a carrier, based on the total weight of catalyst D2.
The test of the reaction performance of catalyst D2 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 3
Supported catalyst D3 was prepared in the same manner as in example 1, except that: the sulfidation treatment of the initial catalyst was omitted so that the content of elemental iron was 13.4 wt.%, the content of elemental sodium was 2.5 wt.%, and the remainder was carrier, based on the total weight of catalyst D3.
The test of the reaction performance of catalyst D3 in the preparation of isobutene by dehydrogenation of isobutane was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
TABLE 1
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TABLE 2
As can be seen from Table 3, the novel dehydrogenation catalyst prepared by the method of the present invention has excellent performance when used in the reaction of preparing isobutene by dehydrogenating isobutane. As can be seen from the experimental results of comparative test example 1 and comparative example 1, al was used 2 O 3 The performance of the catalyst A prepared by the KIT-6 cubic structure composite material is obviously better than that of a catalyst prepared by using commercial alumina as a carrierThe conversion rate of alkane, the selectivity of alkene and the stability of the catalyst are greatly improved. The above results indicate that Al 2 O 3 The KIT-6 cubic structure composite material is more beneficial to the reaction of preparing isobutene by dehydrogenating isobutane. The experimental results of the comparative test example 1 and the comparative example 3 show that the performance of the catalyst A after the vulcanization treatment is obviously better than that of the catalyst D3 without sulfur, and the isobutene conversion rate and the isobutene selectivity are obviously improved; the performance of catalyst a was hardly degraded during the 6 hours reaction, whereas both the isobutene conversion and the isobutene selectivity of the D1 catalyst were significantly reduced. The above results demonstrate that the presence of the S element on the catalyst surface can effectively improve the dehydrogenation activity of the catalyst, the selectivity of the target olefin, and the stability of the catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (18)

1. A novel dehydrogenation catalyst, characterized in that the novel dehydrogenation catalyst comprises a support and a first metal component, a second metal component and a non-metal component supported on the support; wherein the carrier is Al 2 O 3 -KIT-6 cubic structured composite material, and based on the total weight of the novel dehydrogenation catalyst, the content of the first metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the non-metal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%;
the first metal component is selected from one or more of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper;
the second metal component is alkali metal and/or alkaline earth metal;
the nonmetallic component is S;
the Al is 2 O 3 The specific surface area of the-KIT-6 cubic structure composite material is 300-700m 2 The pore volume is 0.6-1.4mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 7-9nm and 10-15nm respectively;
the Al is 2 O 3 The preparation method of the KIT-6 cubic structure composite material comprises the following steps:
(1) Under the condition of preparing an adhesive tape piece by hydrolysis, contacting and mixing a template solvent, a silicon source, n-butanol and hydrochloric acid to obtain a gel mixture; crystallizing the gel mixture; then filtering, washing, first drying and first roasting the crystallized product to obtain the KIT-6 mesoporous molecular sieve;
(2) Mixing the KIT-6 mesoporous molecular sieve, the alumina precursor and the extrusion aid in the presence of dilute nitric acid, extruding to form, and performing secondary drying and secondary roasting to obtain Al 2 O 3 KIT-6 cubic structure composite material.
2. The novel dehydrogenation catalyst of claim 1 wherein the first metal component is present in an amount of from 5 to 20 weight percent, the second metal component is present in an amount of from 0.5 to 5 weight percent, the non-metal component is present in an amount of from 0.2 to 2 weight percent, and the support is present in an amount of from 72 to 95 weight percent, based on the total weight of the novel dehydrogenation catalyst.
3. The novel dehydrogenation catalyst of claim 2 wherein the first metal component is present in an amount of from 6.2 to 19.2 weight percent, the second metal component is present in an amount of from 0.5 to 3.9 weight percent, the non-metal component is present in an amount of from 0.7 to 1.7 weight percent, and the support is present in an amount of from 75.2 to 92.6 weight percent, based on the total weight of the novel dehydrogenation catalyst.
4. The novel dehydrogenation catalyst of claim 1, wherein the Al 2 O 3 The specific surface area of the-KIT-6 composite material is 483-545m 2 Per gram, pore volume of 0.9-1.1mL/g, pore size distribution of bimodal distributionThe maximum several pore diameters corresponding to the double peaks are 7.8-8.2nm and 11.8-12.5nm respectively.
5. The novel dehydrogenation catalyst of claim 1, wherein the templating agent is a nonionic surfactant; the silicon source is a silicon-containing organic compound and/or a silicon-containing inorganic compound.
6. The novel dehydrogenation catalyst of claim 1, wherein the molar ratio of the amounts of the template, the silicon source, the n-butanol, the hydrochloric acid, and water is 1: (10-150): (20-200): (200-1200): (5000-20000).
7. The novel dehydrogenation catalyst of claim 1, wherein the conditions for hydrolysis gum making comprise: the temperature is 20-50 ℃ and the time is 5-30h.
8. The novel dehydrogenation catalyst of claim 1, wherein the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite, and boehmite.
9. The novel dehydrogenation catalyst of claim 1, wherein the KIT-6 mesoporous molecular sieve, the alumina precursor, the extrusion aid, and the dilute nitric acid are used in an amount in a weight ratio of 1: (0.3-5): (0.02-0.5): (0.2-5).
10. A process for the preparation of a novel dehydrogenation catalyst according to any one of claims 1 to 9, characterized in that the process comprises: under the ultrasonic auxiliary condition, the solution containing the first metal component precursor and the second metal component precursor is mixed with Al 2 O 3 The KIT-6 cubic structure composite material is contacted and subjected to impregnation treatment, and then the solvent is removed, dried and roasted to obtain an initial catalyst; and then the initial catalyst is contacted with sulfur-containing gas for vulcanization treatment, so that the novel dehydrogenation catalyst is obtained.
11. The method of preparation of claim 10, wherein the ultrasound-assisted conditions comprise: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W.
12. The method of manufacturing according to claim 10, wherein the conditions of the impregnation include: the temperature is 20-100deg.C, and the time is 0.5-10h.
13. The method of claim 10, wherein the first metal component precursor is selected from a nitrate, sulfite, sulfate, or metal chloride containing one or more elements of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, and copper.
14. The method of claim 10, wherein the second metal component precursor is selected from the group consisting of alkali metal and/or alkaline earth metal containing nitrates, sulfites, sulfates, or metal chlorides.
15. The production method according to claim 10, wherein the conditions of firing include: the temperature is 400-700 ℃ and the time is 2-15h.
16. The production method according to claim 10, wherein the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide; the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1-5%.
17. The production method according to claim 10, wherein the conditions of the vulcanization treatment include: the temperature is 400-700 ℃ and the time is 1-15h.
18. Use of a novel dehydrogenation catalyst according to any one of claims 1-9 in a reaction for producing isobutene by dehydrogenation of isobutane.
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