CN110614120A - Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation - Google Patents

Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation Download PDF

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CN110614120A
CN110614120A CN201810637977.2A CN201810637977A CN110614120A CN 110614120 A CN110614120 A CN 110614120A CN 201810637977 A CN201810637977 A CN 201810637977A CN 110614120 A CN110614120 A CN 110614120A
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noble metal
dehydrogenation catalyst
zsm
isobutane dehydrogenation
molecular sieve
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刘红梅
薛琳
亢宇
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
China Petrochemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petrochemical Corp
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    • 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
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    • 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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • 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
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    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • 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
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    • 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
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Abstract

The invention relates to the field of catalysts, and discloses a non-noble metal isobutane dehydrogenation catalyst, a preparation method thereof, the non-noble metal isobutane dehydrogenation catalyst prepared by the method, and a method for preparing isobutene by isobutane dehydrogenation. The non-noble metal isobutane dehydrogenation catalyst comprises a carrier, and a first active non-noble metal component, a second active non-noble metal component and a sulfur component which are loaded on the carrier, wherein the carrier is a ZSM-5 molecular sieve carrier, the content of the first active non-noble metal component calculated by the first active non-noble metal element is 1-25 wt%, the content of the second active non-noble metal component calculated by the second active non-noble metal element is 0.1-10 wt%, the content of the sulfur component is 0.1-5 wt%, and the content of the ZSM-5 molecular sieve carrier is 60-98.8 wt%. The non-noble metal isobutane dehydrogenation catalyst has good catalytic activity.

Description

Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation
Technical Field
The invention relates to the field of catalysts, in particular to a non-noble metal isobutane dehydrogenation catalyst, a preparation method thereof, the non-noble metal isobutane dehydrogenation catalyst prepared by the method, and a method for preparing isobutene by isobutane dehydrogenation.
Background
Isobutene is the most important basic petrochemical raw material except ethylene and propylene, and is mainly used for synthesizing various organic raw materials and fine chemicals such as methyl tert-butyl ether, ethyl tert-butyl ether, butyl rubber, polyisobutylene, methacrylate, methyl methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. However, isobutene is of no natural origin, mainly from C in catalytically cracked liquefied petroleum gas4Component C and byproduct C in ethylene preparation by naphtha steam cracking4C in olefins and natural gas4And (4) components. In the above-mentioned background, the dehydrogenation of isobutane to isobutene becomes one of the important ways to increase the source of isobutene. At present, there are three main reaction routes developed in the research field of isobutene preparation by isobutane dehydrogenation: (1) directly dehydrogenating isobutane; (2) carrying out oxidative dehydrogenation on isobutane; (3) dehydrogenation of isobutane by membrane catalytic reaction. Wherein, the direct catalytic dehydrogenation reaction of isobutane realizes the industrial production at the earliest; oxidative dehydrogenation is an exothermic reaction, and can be carried out at a relatively low temperature due to no limitation of thermodynamic equilibrium, so that the alkane conversion is effectively improvedThe rate, but the oxidation depth is not easy to control, so that the deep oxidation is easy to cause, and the selectivity of isobutene is reduced; the membrane catalytic reaction of isobutane is still in the exploration and development stage.
The technology for preparing isobutene by direct catalytic dehydrogenation of isobutane has realized industrial production in 90 s of 20 th century, and the main technologies comprise a Catofin process developed by ABB Lummus company, an Oleflex process developed by UOP company, a Star process developed by Phillips company, an FBD-4 process developed by Snamprogetti-Yarsintez company and a Linde process developed by Linde company. The five processes all use Pt (Oleflex and Star process) or Cr (Catofin, FBD-4 and Linde process) catalysts. The noble metal catalyst has high activity, good selectivity and environment friendliness. However, the Pt-based catalyst has disadvantages of complicated operation process, high operation requirement and high cost. Relatively speaking, Cr series catalysts are low in price, but the catalysts are easy to deposit carbon, are quick in deactivation and need frequent regeneration, once leakage happens, environmental pollution is caused, and carcinogen Cr is generated6+It is not favorable for environmental protection. Therefore, for various processes for preparing isobutene by isobutane dehydrogenation, the development of a catalyst which does not use a nonmetal component with serious environmental pollution, has high dehydrogenation catalytic activity and good stability is a main technical problem to be solved at present.
In order to improve various performance indexes of Cr-based propane dehydrogenation catalysts, researchers have made many improvements. Such as: the catalytic performance of the Cr catalyst is improved by adding an auxiliary agent (CN104549220A), the addition of Cr components is avoided by developing a multi-component catalyst formula (CN102451677B, CN104607168A), and the reaction performance of the non-noble metal dehydrogenation catalyst is improved by improving a preparation method of the catalyst (ACS Catal.2015, 5, 3494-. Although the prior art improves the industrial application of Cr catalysts to a certain extent, the problems of complex catalyst components, complex preparation process and catalyst performance to be improved still exist.
Disclosure of Invention
The invention aims to overcome the defects of high preparation cost and environmental pollution easily caused by isobutane dehydrogenation catalysts in the prior art, and provides a non-noble metal isobutane dehydrogenation catalyst, a preparation method thereof and a method for preparing isobutene by isobutane dehydrogenation.
In order to achieve the above object, in one aspect, the present invention provides a non-noble metal isobutane dehydrogenation catalyst, where the non-noble metal isobutane dehydrogenation catalyst includes a carrier, and a first active non-noble metal component, a second active non-noble metal component and a sulfur component loaded on the carrier, where the carrier is a ZSM-5 molecular sieve carrier, and based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, the content of the first active non-noble metal component calculated by the first active non-noble metal element is 1 to 25 wt%, the content of the second active non-noble metal component calculated by the second active non-noble metal element is 0.1 to 10 wt%, the content of the sulfur component is 0.1 to 5 wt%, and the content of the ZSM-5 molecular sieve carrier is 60 to 98.8 wt%.
The second aspect of the present invention provides a method for preparing a non-noble metal isobutane dehydrogenation catalyst, comprising the steps of:
(a) under the ultrasonic condition, dipping a ZSM-5 molecular sieve carrier in a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, and then sequentially removing a solvent, drying and roasting to obtain an initial non-noble metal isobutane dehydrogenation catalyst;
(b) treating the non-noble metal isobutane dehydrogenation catalyst obtained in step (a) with a sulfur-containing gas.
In a third aspect, the invention provides a non-noble metal isobutane dehydrogenation catalyst prepared by the method.
The fourth aspect of the invention provides a method for preparing isobutene by dehydrogenating isobutane, which comprises the following steps: and carrying out dehydrogenation reaction on the isobutane in the presence of a catalyst and inert gas, wherein the catalyst is the non-noble metal isobutane dehydrogenation catalyst.
Compared with the Pt-based dehydrogenation catalyst, the Cr-based catalyst is lower in cost, but is inferior in stability and serious in pollution. In order to maintain low catalyst cost and also consider environmental requirements, non-noble metal elements are adopted to replace Cr to prepare the isobutane dehydrogenation catalyst in the prior art. Research on substituting isobutane catalysts has been continued for nearly two decades, but the performances of isobutane catalysts still cannot completely reach the level of Cr-based catalysts, mainly expressed in the aspects of low 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 alkane dehydrogenation reaction. While pure metal components have very strong dehydrogenation properties, resulting in deep dehydrogenation or hydrogenolysis of the alkane, the selectivity of the desired olefin is severely reduced.
The inventor of the invention finds that in the prior art, when the preparation research of the isobutane dehydrogenation catalyst is carried out, the defects of poor olefin selectivity and poor stability exist when the dehydrogenation catalyst is prepared by taking gamma-alumina or silicon oxide as a carrier and loading a non-noble metal component. If the non-noble metal catalyst is subjected to sulfurization treatment, S elements exist on the surface of the catalyst, and the S elements can be combined with active metal components in the reducing atmosphere of dehydrogenation reaction to generate sulfides. The existence of the non-noble metal sulfide can effectively avoid deep reduction of metal components, thereby reducing pure metal components on the surface of the catalyst and obviously inhibiting 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 isobutane dehydrogenation are obviously improved. For non-noble metal alkane dehydrogenation catalysts, the S element content on the surface of the catalyst has a significant effect on the performance of the catalyst. If the S content is too low, the protection effect on the active metal component is limited, and the partially oxidized metal component is still completely reduced to be in a pure metal state in the reaction process; if the S content is too high, the "oxidation-reduction" cycle rate of the active sites on the surface of the catalyst is slowed, resulting in a slower reaction rate, which is manifested by lower catalyst activity.
In addition, the inventor of the invention also finds that an ultrasonic auxiliary method is introduced in the preparation process of the non-noble metal isobutane dehydrogenation catalyst provided by the invention, so that the active component can be better dispersed on the surface of the ZSM-5 carrier, and the non-noble metal isobutane dehydrogenation catalyst with better catalytic activity is obtained.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the isobutane dehydrogenation catalyst disclosed by the invention does not contain precious metals, so that the preparation cost of the dehydrogenation catalyst can be effectively reduced;
(2) the isobutane dehydrogenation catalyst provided by the preferred scheme of the invention does not contain chromium elements and is environment-friendly.
(3) The isobutane dehydrogenation catalyst shows good catalytic performance when used for preparing isobutene by isobutane dehydrogenation, and has high isobutane conversion rate, high isobutene selectivity and good catalyst stability;
(4) the preparation method of the isobutane dehydrogenation catalyst is simple in process, easy to control conditions and good in product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a non-noble metal isobutane dehydrogenation catalyst, where the non-noble metal isobutane dehydrogenation catalyst includes a carrier, and a first active non-noble metal component, a second active non-noble metal component and a sulfur component supported on the carrier, where the carrier is a ZSM-5 molecular sieve carrier, and based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, the content of the first active non-noble metal component calculated by the first active non-noble metal element is 1 to 25 wt%, the content of the second active non-noble metal component calculated by the second active non-noble metal element is 0.1 to 10 wt%, the content of the sulfur component is 0.1 to 5 wt%, and the content of the ZSM-5 molecular sieve carrier is 60 to 98.8 wt%.
Because the sulfur component with the specific content exists in the non-noble metal isobutane dehydrogenation catalyst and is matched with the first active non-noble metal component and the second active non-noble metal component with the specific content, in the process of catalyzing isobutane to dehydrogenate to prepare isobutene in the non-noble metal isobutane dehydrogenation catalyst, the sulfur element can be combined with the first active non-noble metal component and the second active non-noble metal component to produce sulfides, so that the first active non-noble metal component and the second active non-noble metal component are effectively prevented from being deeply reduced, the pure metal components in the catalyst are reduced, the occurrence of side reactions such as hydrogenolysis and the like is effectively inhibited, and the selectivity of target isobutene and the stability of the non-noble metal isobutane dehydrogenation catalyst are improved.
According to the invention, if the relative content of the elemental sulfur component is too low, the protective effect on the first active non-noble metal component and the second active non-noble metal component is limited, and the partially oxidized metal component is still completely reduced to a pure metal state in the reaction process; if the relative amount of the elemental sulfur component is too high, the rate of the "oxidation-reduction" cycle of the active sites on the surface of the catalyst will be slowed, resulting in a slower reaction rate, indicative of less catalyst activity. In order to better exert the synergistic effect of the components, in the non-noble metal isobutane dehydrogenation catalyst provided by the invention, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, the content of the first active non-noble metal component calculated by the first active non-noble metal element is preferably 3-20 wt%, the content of the second active non-noble metal component calculated by the second active non-noble metal element is preferably 0.5-5 wt%, the content of the sulfur element component is preferably 0.2-2 wt%, and the content of the ZSM-5 molecular sieve carrier is preferably 73-96.3 wt%.
According to the invention, in order to reduce acid sites on the surface of the ZSM-5 molecular sieve carrier as much as possible and reduce the risk of carbon deposition in the catalytic process, the ZSM-5 molecular sieve carrier is preferably a full-silicon ZSM-5 molecular sieve carrier and/or an aluminum-containing ZSM-5 molecular sieve carrier, the Si/Al molar ratio in the aluminum-containing ZSM-5 molecular sieve carrier is 20-250, and more preferably the specific surface area of the ZSM-5 molecular sieve carrier is 300-450 m-2/g。
The size of the ZSM-5 molecular sieve support is not particularly limited in the present invention, and the ZSM-5 molecular sieve support is preferably a nanoscale ZSM-5 molecular sieve support or a micron-sized ZSM-5 molecular sieve support in order to increase the specific surface area of the ZSM-5 molecular sieve support as much as possible.
According to the invention, the preparation cost and the environmental friendliness are considered, and the dehydrogenation activity and selectivity of the prepared non-noble metal isobutane dehydrogenation catalyst are considered, wherein the first active non-noble metal component is preferably selected from at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper components; the second active non-noble metal component is preferably selected from at least one of the alkali metals (e.g., alkali metals such as sodium, potassium, rubidium, and cesium) and the alkaline earth metals (e.g., alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium).
In a second aspect, the present invention provides a method for preparing the aforementioned non-noble metal-based isobutane dehydrogenation catalyst, which comprises the following steps:
(a) under the ultrasonic condition, dipping a ZSM-5 molecular sieve carrier in a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, and then sequentially removing a solvent, drying and roasting to obtain an initial non-noble metal isobutane dehydrogenation catalyst;
(b) and (b) carrying out vulcanization treatment on the non-noble metal isobutane dehydrogenation catalyst obtained in the step (a) by using sulfur-containing gas.
In the method for preparing the non-noble metal isobutane dehydrogenation catalyst, the ZSM-5 molecular sieve carrier is preferably a full-silicon ZSM-5 molecular sieve carrier and/or an aluminum-containing ZSM-5 molecular sieve carrier, and the Si/Al molar ratio in the aluminum-containing ZSM-5 molecular sieve carrier is 20-250, more preferably 20-250The specific surface area of the ZSM-5 molecular sieve carrier is 300-450m2/g。
In the method for preparing the non-noble metal isobutane dehydrogenation catalyst, the solution containing the first active non-noble metal component precursor can be at least one of soluble salt solutions of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper; the solution containing the precursor of the second active non-noble metal component is at least one of soluble salt solutions of alkali metals or alkaline earth metals.
According to the present invention, the concentrations of the soluble salt of the first active metal and the soluble salt of the second active metal in the solution containing the first active non-noble metal component precursor and the solution containing the second active non-noble metal component precursor are not particularly limited, and for example, the concentration of the soluble salt of the first active metal in the solution containing the first active non-noble metal component precursor may be 0.05 to 0.25mol/L, and the concentration of the soluble salt of the second active metal in the solution containing the second active non-noble metal component precursor may be 0.025 to 0.15 mol/L. The soluble salt in the present invention preferably means a water-soluble salt.
According to the present invention, when the concentrations of the solution containing the first active non-noble metal component precursor and the solution containing the second active non-noble metal component precursor are within the above ranges, the amount of the solution containing the first active non-noble metal component precursor may be 50 to 150mL, and the amount of the solution containing the second active non-noble metal component precursor may be 50 to 150 mL.
In the method for preparing the non-noble metal isobutane dehydrogenation catalyst, in the step (a), the impregnation treatment enables a first active non-noble metal component and a second active non-noble metal component to enter a pore channel of the ZSM-5 molecular sieve carrier by means of capillary pressure of a pore channel structure of the carrier, and the first active non-noble metal component and the second active non-noble metal component are adsorbed on the surface of the ZSM-5 molecular sieve carrier until the first active non-noble metal component and the second active non-noble metal component reach adsorption balance on the surface of the ZSM-5 molecular sieve carrier. The dipping treatment may be a co-dipping treatment or a stepwise dipping treatment.
When the impregnation treatment is a co-impregnation treatment, the conditions of the impregnation treatment include: under the condition of ultrasonic assistance, a ZSM-5 molecular sieve carrier is mixed and contacted with a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, the impregnation temperature can be 25-50 ℃, and the impregnation time can be 0.5-2 h.
When the impregnation treatment is a step impregnation treatment, the conditions of the impregnation treatment include: under the condition of ultrasonic assistance, firstly, carrying out first mixing contact on a ZSM-5 molecular sieve carrier and a solution containing a first active non-noble metal component precursor, and then sequentially carrying out solvent removal, drying and roasting to obtain a ZSM-5 molecular sieve carrier loaded with a first metal component; and then carrying out second mixing contact on the ZSM-5 molecular sieve carrier loaded with the first metal component and a solution containing a second active non-noble metal component precursor, and then sequentially carrying out solvent removal, drying and roasting to obtain the ZSM-5 molecular sieve carrier loaded with the first metal component and the second active non-noble metal component, namely the initial isobutane catalyst. The step-by-step dipping treatment sequence can also be adjusted to dip and load the second active non-noble metal component on the ZSM-5 molecular sieve carrier, and then dip and load the first active non-noble metal component. In the step impregnation treatment, the conditions of each impregnation treatment may include: the dipping temperature is 25-50 ℃, and the dipping time is 0.5-2 h.
In the method for preparing a non-noble metal-based isobutane dehydrogenation catalyst provided by the present invention, in step (a), in order to promote uniform dispersion of the first active non-noble metal component and the second active non-noble metal component, the ultrasonic conditions preferably include: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-; more preferably, the ultrasonic conditions comprise: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
In the method for preparing the non-noble metal-based isobutane dehydrogenation catalyst provided by the present invention, in step (a), the solvent removal treatment may be performed by a method conventional in the art, for example, a rotary evaporator may be used to remove the solvent in the system.
In the method for preparing the non-noble metal isobutane dehydrogenation catalyst, in the step (a), the drying may be performed in a drying oven, and the roasting may be performed in a muffle furnace. The drying conditions may include: the temperature is 60-150 ℃, preferably 80-130 ℃, and the time is 1-20h, preferably 3-5 h; the conditions for the firing may include: the temperature is 400-700 ℃, preferably 500-650 ℃, and the time is 2-15h, preferably 3-10 h.
In the method for preparing the non-noble metal-based isobutane dehydrogenation catalyst, in the step (b), the sulfur-containing gas is preferably at least one of nitrogen, helium and argon containing hydrogen sulfide.
According to the present invention, in order to obtain a good catalytic effect by controlling the content of elemental sulfur in the obtained non-noble metal isobutane dehydrogenation catalyst to 0.1 to 5 wt% based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, the volume content of hydrogen sulfide in the sulfur-containing gas is preferably 0.1 to 5%, and more preferably 0.3 to 2%.
More preferably, the conditions of the vulcanization treatment include: the temperature is 400-700 ℃, and the time is 1-15 h; preferably, the conditions of the vulcanization treatment include: the temperature is 450-650 ℃, and the time is 2-8 h.
In the non-noble metal isobutane dehydrogenation catalyst obtained by the method for preparing the non-noble metal isobutane dehydrogenation catalyst, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, the content of a first active non-noble metal component calculated by a first active non-noble metal element is 1-25 wt%, preferably 3-20 wt%, the content of a second active non-noble metal component calculated by a second active non-noble metal element is 0.1-10 wt%, preferably 0.5-5 wt%, and the content of the ZSM-5 molecular sieve carrier is 60-98.8 wt%, preferably 73-96.3 wt%.
The third aspect of the invention provides a method for preparing isobutene by dehydrogenating isobutane, which comprises the following steps: and carrying out dehydrogenation reaction on the isobutane in the presence of a catalyst and an inert gas, wherein the catalyst is the non-noble metal isobutane dehydrogenation catalyst or the non-noble metal isobutane dehydrogenation catalyst prepared by the method.
In the method for preparing isobutene by dehydrogenating isobutane, in order to improve the isobutane conversion rate and prevent the catalyst from coking, inert gas is preferably added into the reaction raw materials to serve as a diluent, so that the partial pressure of isobutane in a reaction system is reduced. Wherein the inert gas comprises at least one of nitrogen, helium and argon. The molar ratio of the consumption of the isobutane to the consumption of the inert gas is 0.2-5: 1; preferably, the dehydrogenation reaction conditions include: the reaction temperature is 500-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 5-10h, and the mass space velocity of isobutane is 1-10h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the reagents used were all commercially available analytical reagents.
In the following examples and comparative examples, nitrogen desorption experiments of samples were carried out on a fully automatic physicochemical adsorption analyzer model ASAP2000 manufactured by Micromeritics, usa. The samples were degassed at 350 ℃ for 4 hours under vacuum prior to assay. Calculating the specific surface area of the sample by adopting a BET method; the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A; the muffle furnace is manufactured by CARBOLITE corporation, and is of a model CWF 1100; the ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by ultrasonic instruments Limited in Kunshan, the ultrasonic frequency is 80kHz, and the working voltage is 220V; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the isobutane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, available from parnacco, netherlands, model No. Axios-Advanced; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A.
In the following experimental examples and experimental comparative examples, the conversion (%) of isobutane was ═ amount of isobutane-content of isobutane in the reaction product ÷ amount of isobutane × 100%;
selectivity (%) of isobutylene is the amount of isobutane consumed to produce isobutylene ÷ total consumption of isobutane × 100%.
Example 1
(1) Preparation of initial non-noble metal isobutane dehydrogenation catalyst
8.66g of ferric nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100ml of deionized water, and 10g of a micron-sized all-silicon ZSM-5 molecular sieve carrier A (obtained from Ziboziqi scientific and technology development Co., Ltd., brand name: micron ZSM-5, and specific surface area of 369m2/g), stirring and immersing at 50 ℃ for 60 minutes under the assistance of ultrasonic waves with the power of 200W, and then evaporating solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 6 hours. Then roasting the mixture for 5 hours in a muffle furnace at the temperature of 550 ℃ to obtain the initial non-noble metal isobutane dehydrogenation catalyst C1.
(2) Method for preparing non-noble metal isobutane dehydrogenation catalyst by sulfurizing initial non-noble metal isobutane dehydrogenation catalyst
Taking 10g of the initial non-noble metal isobutane dehydrogenation catalyst C1, and using H at 550 DEG C2And carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst C1 for 5 hours by using nitrogen gas flow with the volume content of S being 1.5%, so as to obtain a non-noble metal isobutane dehydrogenation catalyst Cat-1.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-1, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-1, the content of an iron component in terms of iron elements is 11.2 wt%, the content of a sodium component in terms of sodium elements is 2.5 wt%, the content of a sulfur component in terms of sulfur elements is 1 wt%, and the balance is a micron-sized all-silicon ZSM-5 molecular sieve carrier A.
Example 2
(1) Preparation of initial non-noble metal isobutane dehydrogenation catalyst
0.53g of magnesium nitrate hexahydrate was dissolved in 70ml of deionized water, and 10g of nanoscale all-silicon ZSM-5 sample B (obtained from Ziboziqi scientific and technology development Co., Ltd., under the brand name of NanoZSM-5,specific surface area of 392m2/g) and the mixture is immersed under stirring at 80 ℃ for 30 minutes with the aid of ultrasonic waves at a power of 250W, and then the solvent water in the system is distilled off by a rotary evaporator to obtain a solid product A1. The solid product A1 was placed in a drying cabinet at a temperature of 80 ℃ and dried for 15 hours. Then roasting the mixture for 3 hours in a muffle furnace at the temperature of 650 ℃ to obtain a Mg-ZSM-5 sample loaded with a magnesium component. 9.20g of zinc nitrate hexahydrate is dissolved in 150ml of deionized water, mixed with the Mg-ZSM-5 sample, immersed under stirring at 80 ℃ for 30 minutes with the assistance of ultrasonic waves with the power of 250W, and then the solvent water in the system is distilled off by a rotary evaporator to obtain a solid product A2. The solid product A2 was placed in a drying cabinet at a temperature of 80 ℃ and dried for 15 hours. Then roasting the mixture in a muffle furnace at the temperature of 650 ℃ for 3 hours to obtain the initial non-noble metal isobutane dehydrogenation catalyst C2.
(2) Method for preparing non-noble metal isobutane dehydrogenation catalyst by sulfurizing initial non-noble metal isobutane dehydrogenation catalyst
Taking 10g of the initial non-noble metal isobutane dehydrogenation catalyst C2, and using H at 450 DEG C2And carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst C2 for 8 hours by using nitrogen gas flow with the volume content of S being 2% to obtain a non-noble metal isobutane dehydrogenation catalyst Cat-2.
Measured by an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-2, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-2, the content of the zinc component calculated by zinc element is 19.9 wt%, the content of the magnesium component calculated by magnesium element is 0.5 wt%, the content of the sulfur component calculated by sulfur element is 1.8 wt%, and the balance is the nano-scale all-silicon ZSM-5 molecular sieve carrier B.
Example 3
(1) Preparation of initial non-noble metal isobutane dehydrogenation catalyst
1.52g of nickel nitrate hexahydrate is dissolved in 100ml of deionized water, and mixed with 10g of ZSM-5 molecular sieve carrier C (purchased from catalyst works of southern Kao university and having the brand number of H-type ZSM-5, the Si/Al molar ratio of 100 and the specific surface area of 341 m)2/g) mixing at powerThe product was immersed with stirring at 20 ℃ for 2 hours with the aid of ultrasonic waves of 150W, and then the solvent water in the system was distilled off by a rotary evaporator to obtain a solid product B1. The solid product was dried in a drying oven at 130 ℃ for 3 hours. Then, the mixture is roasted in a muffle furnace at the temperature of 500 ℃ for 10 hours to obtain a Ni-ZSM-5 sample loaded with a nickel component. 0.98g of potassium chloride is dissolved in 100ml of deionized water, mixed with the Ni-ZSM-5 sample, continuously stirred and immersed for 2 hours at the temperature of 20 ℃ under the assistance of ultrasonic waves with the power of 150W, and then solvent water in the system is distilled off by a rotary evaporator to obtain a solid product B2. The solid product B2 was placed in a drying oven at 130 ℃ and dried for 3 hours. Then roasting the mixture in a muffle furnace at the temperature of 500 ℃ for 10 hours to obtain the initial non-noble metal isobutane dehydrogenation catalyst C3.
(2) Method for preparing non-noble metal isobutane dehydrogenation catalyst by sulfurizing initial non-noble metal isobutane dehydrogenation catalyst
Taking 10g of the initial non-noble metal isobutane dehydrogenation catalyst C3, and using H at 650 DEG C2And carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst C3 for 2 hours by using nitrogen gas flow with the volume content of S being 0.3%, so as to obtain a non-noble metal isobutane dehydrogenation catalyst Cat-3.
Measured by an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-3, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-3, the content of the nickel component is 3 wt% calculated by nickel element, the content of the potassium component is 4.9 wt% calculated by potassium element, the content of the sulfur component is 0.2 wt% calculated by sulfur element, and the balance is micron-grade high-silicon-aluminum ratio silicon ZSM-5 molecular sieve carrier C.
Comparative example 1
The non-noble metal isobutane dehydrogenation catalyst Cat-D1 was prepared according to the method of example 1, except that step (2) was omitted, the initial non-noble metal isobutane dehydrogenation catalyst was not sulfided with a sulfur-containing gas, and the surface of the non-noble metal isobutane dehydrogenation catalyst Cat-D1 did not contain an S component.
In the non-noble metal isobutane dehydrogenation catalyst Cat-D1, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-D1, the content of an iron component in terms of iron element is 11.3 wt%, the content of a sodium component in terms of sodium element is 2.5 wt%, and the balance is a micron-sized all-silicon ZSM-5 molecular sieve carrier a.
Comparative example 2
A non-noble metal-based isobutane dehydrogenation catalyst Cat-D2 was prepared according to the method of example 1, except that the ultrasonic dispersion in step (1) was eliminated.
In the non-noble metal isobutane dehydrogenation catalyst Cat-D2, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-D2, the content of an iron component calculated by an iron element is 11 wt%, the content of a sodium component calculated by a sodium element is 2.4 wt%, the content of a sulfur component calculated by a sulfur element is 1 wt%, and the balance is a micron-sized all-silicon ZSM-5 molecular sieve carrier a.
Comparative example 3
An isobutane dehydrogenation catalyst, Cat-D3, was prepared according to the method of example 3, except that, in step (2), 2.9g of chromium sulfate (Cr)2(SO4)3) And replacing the nickel nitrate hexahydrate, namely taking an active component loaded by the micron-level high silica-alumina ratio ZSM-5 molecular sieve carrier C as a noble metal Cr component to obtain the isobutane dehydrogenation catalyst Cat-D3.
Measured by an X-ray fluorescence spectrometer, in the isobutane dehydrogenation catalyst Cat-D3, based on the total weight of the Cat-D3, the content of a chromium component is 3 wt% in terms of chromium element, the content of a potassium component is 4.9 wt% in terms of potassium element, the content of a sulfur component is 0.2 wt% in terms of sulfur element, and the balance is a micron-grade high-silica-alumina ratio silicon ZSM-5 molecular sieve carrier C.
Test examples 1 to 7:
test of performance of isobutane dehydrogenation catalyst in reaction for preparing isobutene through isobutane dehydrogenation
0.5g of the isobutane dehydrogenation catalysts prepared in the above examples and comparative examples were respectively charged into a fixed bed quartz reactor, the reaction temperature was controlled to 580 ℃, the reaction pressure was 0.1MPa, and the reaction pressure was controlled to be isobutane: the molar ratio of helium is 1: 1, the mass space velocity of the isobutane is 2.0h-1The reaction time is 6 h. By Al2O3Separated by a column of-S molecular sievesThe reaction product was directly sent to an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis. And (3) calculating the isobutane conversion rate and the isobutene selectivity according to the reaction data, and judging the stability of the catalyst according to the gradual reduction amplitude of the isobutane conversion rate and the isobutene selectivity along with the prolonging of the reaction time in the reaction process.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the non-noble metal isobutane dehydrogenation catalyst prepared by the method provided by the invention has excellent performance when used for catalyzing the reaction of preparing isobutene by isobutane dehydrogenation. The experimental results of the test example 1 and the test example 4 are compared to find that the performance of the sulfur-containing non-noble metal isobutane dehydrogenation catalyst Cat-1 is obviously superior to that of the sulfur-free non-noble metal isobutane dehydrogenation catalyst Cat-D1, the initial isobutane conversion rate is improved by 6%, and the initial isobutene selectivity is improved from 62.1% to 89.2%; in the reaction process of 6 hours, the conversion rate of the non-noble metal isobutane dehydrogenation catalyst Cat-1 to isobutane and the selectivity of isobutene are hardly reduced, while the selectivity of the non-noble metal isobutane dehydrogenation catalyst Cat-D1 is obviously reduced. The results show that the existence of sulfur on the surface of the sulfur-containing non-noble metal isobutane dehydrogenation catalyst can effectively improve the dehydrogenation activity, isobutene selectivity and stability of the non-noble metal isobutane dehydrogenation catalyst.
In addition, the experimental results of comparative test example 1 and test example 5 show that the non-noble metal isobutane dehydrogenation catalyst with better performance can be obtained by promoting the dispersion of the active metal component by using an ultrasonic auxiliary method in the metal component element loading process.
In addition, the experimental results of comparative test example 1 and test example 6 show that the catalytic performance of the isobutane dehydrogenation catalyst obtained by loading the non-noble metal active component on the ZSM-5 molecular sieve carrier is equivalent to that of the isobutane dehydrogenation catalyst obtained by loading the toxic metal active component Cr on the ZSM-5 molecular sieve carrier.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. The non-noble metal isobutane dehydrogenation catalyst is characterized by comprising a carrier, and a first active non-noble metal component, a second active non-noble metal component and a sulfur component which are loaded on the carrier, wherein the carrier is a ZSM-5 molecular sieve carrier, the content of the first active non-noble metal component calculated by a first active non-noble metal element is 1-25 wt%, the content of the second active non-noble metal component calculated by a second active non-noble metal element is 0.1-10 wt%, the content of the sulfur component is 0.1-5 wt%, and the content of the ZSM-5 molecular sieve carrier is 60-98.8 wt%.
2. The non-noble metal-based isobutane dehydrogenation catalyst according to claim 1, wherein the content of the first active non-noble metal component calculated as the first active non-noble metal element is 3-20 wt%, the content of the second active non-noble metal component calculated as the second active non-noble metal element is 0.5-5 wt%, the content of the sulfur element component is 0.2-2 wt%, and the content of the ZSM-5 molecular sieve support is 73-96.3 wt%, based on the total weight of the non-noble metal-based isobutane dehydrogenation catalyst.
3. Non-noble metal-based isobutane dehydrogenation catalyst according to claim 1, wherein the ZSM-5 molecular sieve support is an all-silicon ZSM-5 molecular sieve support and/or an aluminium-containing ZSM-5 molecular sieve support, the Si/Al molar ratio in the aluminium-containing ZSM-5 molecular sieve support is between 20 and 250, preferably the specific surface of the ZSM-5 molecular sieve supportVolume 300-450m2/g。
4. The non-noble metal-based isobutane dehydrogenation catalyst of claim 1, wherein said first active non-noble metal component is selected from at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper components; the second active non-noble metal component is selected from at least one of an alkali metal and an alkaline earth metal.
5. A method for preparing a non-noble metal isobutane dehydrogenation catalyst is characterized by comprising the following steps:
(a) under the ultrasonic condition, dipping a ZSM-5 molecular sieve carrier in a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, and then sequentially removing a solvent, drying and roasting to obtain an initial non-noble metal isobutane dehydrogenation catalyst;
(b) and (b) carrying out vulcanization treatment on the non-noble metal isobutane dehydrogenation catalyst obtained in the step (a) by using sulfur-containing gas.
6. The process as claimed in claim 5, wherein the ZSM-5 molecular sieve support is an all-silicon ZSM-5 molecular sieve support and/or an aluminum-containing ZSM-5 molecular sieve support, the Si/Al molar ratio in the aluminum-containing ZSM-5 molecular sieve support is 20-250, preferably the ZSM-5 molecular sieve support has a specific surface area of 300-450m2/g。
7. The method of claim 5, wherein the solution containing the first active non-noble metal component precursor is at least one of a soluble salt solution of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, and copper; the solution containing the second active non-noble metal component precursor is at least one of a soluble salt solution of an alkali metal or an alkaline earth metal.
8. The method according to claim 5, wherein the first active non-noble metal component precursor, the second active non-noble metal component precursor and the ZSM-5 molecular sieve support are used in amounts such that the resulting non-noble metal isobutane dehydrogenation catalyst has a first active non-noble metal component content of 1-25 wt.%, preferably 3-20 wt.%, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, a second active non-noble metal component content of 0.1-10 wt.%, preferably 0.5-5 wt.%, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, and a ZSM-5 molecular sieve support content of 60-98.8 wt.%, preferably 73-96.3 wt.%.
9. The method of claim 5, wherein in step (a), the ultrasound conditions comprise: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-; preferably, the ultrasound conditions comprise: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-;
the drying conditions include: the temperature is 60-150 ℃, preferably 80-130 ℃; the time is 1 to 20 hours, preferably 3 to 15 hours;
the roasting conditions comprise: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10 h.
10. The method of claim 5, wherein in step (b), the sulfur-containing gas is at least one of nitrogen, helium, and argon containing hydrogen sulfide;
preferably, the hydrogen sulphide is present in the sulphur-containing gas in an amount of 0.1-5% by volume, more preferably 0.3-2%;
more preferably, the conditions of the vulcanization treatment include: the temperature is 400-700 ℃, and the time is 1-15 h; preferably, the conditions of the vulcanization treatment include: the temperature is 450-650 ℃, and the time is 2-8 h;
further preferably, the condition of the sulfurization treatment is such that the content of elemental sulfur in the non-noble metal-based isobutane dehydrogenation catalyst is 0.1 to 5 wt%, preferably 0.2 to 2 wt%, based on the total weight of the non-noble metal-based isobutane dehydrogenation catalyst.
11. A non-noble metal based isobutane dehydrogenation catalyst prepared by the process according to any of claims 5-10.
12. A method for preparing isobutene by dehydrogenating isobutane, comprising the following steps: the dehydrogenation of isobutane in the presence of a catalyst, characterized in that said catalyst is a non-noble metal-based isobutane dehydrogenation catalyst according to any of the claims 1-4 and 11.
13. The process according to claim 12, preferably the conditions of the dehydrogenation reaction comprise: the reaction temperature is 500-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the isobutane is 1-10h-1。
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Application publication date: 20191227