CN113797956B - Supported catalyst and preparation method and application thereof - Google Patents

Supported catalyst and preparation method and application thereof Download PDF

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CN113797956B
CN113797956B CN202010547574.6A CN202010547574A CN113797956B CN 113797956 B CN113797956 B CN 113797956B CN 202010547574 A CN202010547574 A CN 202010547574A CN 113797956 B CN113797956 B CN 113797956B
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supported catalyst
carrier
precursor
temperature
methane
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CN113797956A (en
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武洁花
邵芸
赵清锐
张明森
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract

The invention relates to the field of catalysis, and discloses a supported catalyst, a preparation method and application thereof, wherein the supported catalyst comprises a carrier and an active component supported on the carrier, and the carrier is a mesoporous molecular sieve SBA-15; the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1. The supported catalyst has a larger specific surface area, can uniformly disperse active components on the surface of a carrier, and is more beneficial to the diffusion of raw materials and products by controlling the pore diameter structure of a mesoporous molecular sieve; the method for preparing the supported catalyst by adopting the microwave method greatly shortens the reaction time, improves the reaction efficiency, reduces the energy consumption and is easy for large-scale production and application.

Description

Supported catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysis, in particular to a supported catalyst, a preparation method and application thereof.
Background
Ethylene is the largest fundamental component of commodity chemicals and chemicals in the world. For example, ethylene derivatives may be found in food packaging, spectacles, automobiles, medical devices, lubricants, engine coolants and liquid crystal displays. For industrial scale applications, commercial production of ethylene may involve heating natural gas condensate and petroleum fractions, including ethane and higher hydrocarbons. The ethylene produced can be separated from the product mixture using a gas separation process.
Ethylene and other c2+ hydrocarbon products may also be produced from methane by Oxidative Coupling (OCM) reactions of methane. The technology is used for reducing ethylene (C 2 H 4 ) The method has great potential in the aspects of cost, energy and environmental emission in production, and meanwhile, because the methane oxidative coupling reaction is a strong exothermic reaction and is carried out at high temperature and is limited by the reaction temperature and the technical difficulty of the reaction process, no industrial-scale production is yet developed so far, and therefore, the development of the methane oxidative coupling catalyst with excellent performance has practical significance.
In order to reduce the reaction temperature of the methane oxidative coupling catalyst, researchers have made much work, such as Hou Saicong and the like, to couple Li-ZnO/La by low-temperature methane oxidation 2 O 3 Catalysts (prepared by doping lanthanum oxide with lithium and zinc oxide, journal of physical chemistry, hou Saicong, etc.), CN103118777A discloses that it can be used asA nanowire of a heterogeneous catalyst comprising an inorganic catalytic polycrystalline nanowire having an effective length to actual length ratio of less than 1 and an aspect ratio of greater than 10, as determined by TEM in bright field mode at 5keV, wherein the nanowire comprises one or more elements of any one of groups 1 to 7, a lanthanide series element, an actinide series element, or a combination thereof. The preparation of these polycrystalline nanowires involves the use of biological templates, such as phages in the M13 family comprising protein pVIII. CN101385982A discloses a mesoporous molecular sieve catalyst for preparing ethylene by oxidative coupling of methane, which is prepared by modifying a mesoporous molecular sieve (mesoporous molecular sieve SBA-15) serving as a catalyst carrier by using Na 2 WO 4 And Mn or Na 2 WO 4 The catalytic active components such as Mn, M (M= Li, ce, zr, la or Sr) are assembled into the holes of the mesoporous molecular sieve, so that the catalytic active components are highly isolated and dispersed, the activity and stability of the catalyst are improved, the preparation process of the catalyst is complex, the preparation period is long, and the catalytic reaction temperature is 850 ℃. The prepared catalyst has the problems of high reaction temperature, complex catalyst preparation process and long preparation period, and brings difficulty to industrial scale-up production.
Disclosure of Invention
The invention aims to solve the problems of high reaction temperature, complex catalyst preparation process and poor reaction stability in the prior art, and provides a supported catalyst, a preparation method and application thereof, wherein the supported catalyst has larger specific surface area, can uniformly disperse active components on the surface of a carrier, and is more beneficial to the diffusion of raw materials and products by controlling the pore diameter structure of a mesoporous molecular sieve; the method for preparing the supported catalyst by adopting the microwave method greatly shortens the reaction time, improves the reaction efficiency, reduces the energy consumption and is easy for large-scale production and application; the supported catalyst can enable the reaction of preparing more than two carbon atoms from methane to be carried out at a lower temperature (such as within the range of 500-650 ℃), reduces the requirements on a reactor and operating conditions, has higher methane conversion rate and higher selectivity of more than two carbon atoms, and is more beneficial to industrialized amplified production.
In order to achieve the above object, a first aspect of the present invention provides a supported catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is a mesoporous molecular sieve SBA-15; the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1.
The supported catalyst provided by the invention has a larger specific surface area, can uniformly disperse active components on the surface of a carrier, and is more beneficial to the diffusion of raw materials and products by controlling the pore diameter structure of a mesoporous molecular sieve, so that the oxidation coupling reaction of methane is promoted.
In a second aspect of the present invention, there is provided a method of preparing a supported catalyst, the method comprising:
(1) Under an acidic condition, contacting a template agent with a silicon source, carrying out first microwave treatment on the mixture obtained after the contact, and then sequentially carrying out solid-liquid separation, drying and roasting after the treatment is finished, so as to obtain the mesoporous molecular sieve SBA-15 after the template agent is removed;
(2) Loading active components on a mesoporous molecular sieve SBA-15, wherein the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1.
In a third aspect of the invention, a supported catalyst is provided, and the supported catalyst is prepared by the method.
In a fourth aspect of the invention, there is provided a process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the supported catalyst in the presence of oxygen;
alternatively, a supported catalyst is prepared as described above, and then methane is contacted with the resulting supported catalyst in the presence of oxygen.
The method for preparing the supported catalyst provided by the invention adopts a microwave method, can greatly shorten the reaction time, improve the reaction efficiency, reduce the energy consumption and is easy for large-scale production and application.
The method for preparing the hydrocarbon with more than two carbon atoms from the methane provided by the invention is characterized in that the methane is contacted with the supported catalyst in the presence of oxygen to prepare the hydrocarbon with more than two carbon atoms, the supported catalyst can enable the reaction for preparing the hydrocarbon with more than two carbon atoms from the methane to be carried out at a lower temperature (such as a temperature range of 500-650 ℃), the requirements on a reactor and operating conditions are reduced, and the method has higher methane conversion rate and higher hydrocarbon selectivity with more than two carbon atoms, thereby being more beneficial to industrialized scale-up production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a mesoporous molecular sieve SBA-15 obtained in accordance with one embodiment of the present invention;
FIG. 2 is a transmission electron microscopy image of a mesoporous molecular sieve SBA-15 obtained according to another embodiment of the invention.
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 invention provides a supported catalyst, which comprises a carrier and an active component supported on the carrier, wherein the carrier is a mesoporous molecular sieve SBA-15; the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1.
In some embodiments of the invention, preferably, the molar ratio of La, ba and Li is 1:0.08-0.3:0.14-0.65.
In some embodiments of the present invention, the specific surface area, pore volume and pore diameter of the supported catalyst may be measured according to a nitrogen adsorption method, the specific surface area is calculated by a BET method, and the pore volume is calculated by a BJH model. The specific surface area of the carrier can be 700-1000m 2 Preferably 750-900m 2 And/g. The pore volume of the support may be 0.5-1.5cm 3 /g，Preferably 0.8-1.2cm 3 And/g. The average pore size of the support may be from 2 to 5nm, preferably from 2.5 to 4nm.
In some embodiments of the present invention, the carrier is preferably present in an amount of 79.5 to 94.8 wt%, more preferably 84.7 to 91.4 wt%, based on the total weight of the supported catalyst, in order to further secure the catalytic effect of the catalyst. The La content may be 5 to 18% by weight, preferably 8 to 15% by weight. The content of Ba may be 0.1 to 5% by weight, preferably 0.5 to 4% by weight. The content of Li may be 0.01 to 1% by weight, preferably 0.05 to 0.8% by weight.
In some embodiments of the invention, the active component is present in an oxidized form.
In a second aspect of the present invention, there is provided a method of preparing a supported catalyst, the method comprising:
(1) Under an acidic condition, a template agent is contacted with a silicon source, the mixture obtained after the contact is subjected to first microwave treatment, then solid-liquid separation, drying and roasting are sequentially carried out after the treatment is completed, a mesoporous molecular sieve SBA-15 is obtained after the template agent is removed (2), and active components are loaded on the mesoporous molecular sieve SBA-15, wherein the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1.
In some embodiments of the invention, in step (1), the molecular sieve bond long bond angle and framework oxygen are controlled using an acidic substance, and the pH value of the acidic condition is controlled to be 1-6, preferably 1-5; the acidic substance may be at least one of phosphoric acid, nitric acid, hydrochloric acid and acetic acid, preferably hydrochloric acid.
In some embodiments of the present invention, in step (1), the template agent mainly plays a role of structural template, a role of structural guiding, a role of space filling and a role of balancing framework charges in the preparation process, and may be a nonionic surfactant; preferably having the general formula EO a PO b EO a Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of (a); more preferably, wherein a has a value of 10 to 100 and b has a value of 40 to 80; further preferred is EO 20 PO 70 EO 20 The method comprises the steps of carrying out a first treatment on the surface of the Concrete embodimentsThe source of the templating agent is not limited and may be obtained commercially (e.g., from Sigma-Aldrich under the trade name P123, molecular formula EO) 20 PO 70 EO 20 ) Can also be prepared by adopting a method in the prior art, and is not repeated here.
In some embodiments of the present invention, in step (1), the kind of the silicon source is not particularly limited as long as the silicon element can be provided, and preferably, the silicon source is sodium silicate and/or tetraethyl silicate, and more preferably, tetraethyl silicate.
In some embodiments of the invention, preferably, the molar ratio of La, ba and Li is 1:0.08-0.3:0.14-0.65.
In some embodiments of the invention, in step (1), the templating agent is used in an amount of 3.3X10 s based on 1L of the mixture -3 -5.8×10 -3 mol; the molar ratio of the template agent to the silicon source calculated as Si is preferably 0.01-0.1:1.
in some embodiments of the invention, in step (1), the temperature of the contacting may be from 20 to 80 ℃, preferably from 25 to 60 ℃. The contact time is 12 to 36 hours, preferably 12 to 25 hours.
In some embodiments of the present invention, to further promote the formation of mesoporous molecular sieve SBA-15, in step (1), the contacting is performed by adding a silicon source to the templating agent, more preferably at a rate of 0.1 to 1g/min, and still more preferably 0.1 to 0.5g/min, based on 1g of templating agent.
In some embodiments of the present invention, the power of the microwave reactor used for the first microwave treatment in step (1) is preferably 400-800W in order to further shorten the reaction time, improve the reaction efficiency and reduce the energy consumption.
In some embodiments of the invention, in step (1), the time of the first microwave treatment is preferably from 0.5 to 6 hours, preferably from 1 to 5 hours, in order to allow the reaction to proceed more thoroughly. The temperature of the first microwave treatment is 45-55 ℃.
In some embodiments of the invention, in step (1), the firing temperature is 300-700 ℃, preferably 400-600 ℃; the calcination time is 2 to 10 hours, preferably 3 to 8 hours.
In the present invention, the solid-liquid separation method is not limited as long as the solid-liquid separation can be achieved, and a filtration method is preferable.
In the present invention, the solid after solid-liquid separation may be washed, and the manner of washing is not limited, and preferably, after filtration is completed, washing with water (preferably deionized water) may be performed, and after washing to neutrality, washing with ethanol is performed once.
In some embodiments of the present invention, in step (1), the drying may be performed in a drying apparatus using methods conventional in the art, and the drying conditions include a drying temperature preferably ranging from 80 to 120 ℃. The drying time is preferably 10 to 20 hours.
In some embodiments of the present invention, in step (2), there is no limitation on the manner of loading, and conventional technical means in the prior art may be adopted, preferably, the manner of loading is: impregnating the carrier with impregnating solution containing lanthanum precursor, barium precursor and lithium precursor, performing microwave treatment for the second time on the obtained impregnating system, and then sequentially drying and roasting to obtain the supported catalyst. Specifically, the capillary pressure of the pore channel structure of the carrier is relied on to enable the metal component to enter the pore channel of the mesoporous structure, and meanwhile, the metal component can be adsorbed on the surface of the mesoporous structure material until the metal component reaches adsorption equilibrium in the carrier. The impregnation may be co-impregnation or may be a stepwise impregnation, preferably co-impregnation.
In some embodiments of the present invention, in the impregnation system, the lanthanum precursor weight concentration in terms of lanthanum element is preferably 0.01 to 0.5 wt%, the barium precursor concentration in terms of barium element is preferably 0.001 to 0.3 wt%, the lithium precursor concentration in terms of lithium element is preferably 0.0004 to 0.007 wt%, and the impregnation solution is preferably used in an amount of 80 to 120g per g of carrier.
In some embodiments of the present invention, there is no particular limitation on the lanthanum precursor, preferably, the lanthanum precursor is a water-soluble lanthanum salt, more preferably at least one selected from lanthanum nitrate, lanthanum chloride, and lanthanum chlorate, and still more preferably lanthanum nitrate.
In some embodiments of the present invention, there is no particular limitation on the barium precursor, preferably, the barium precursor is a water-soluble barium salt, more preferably selected from barium nitrate and/or barium chloride;
in some embodiments of the present invention, there is no particular limitation on the lithium precursor, preferably, the lithium precursor is a water-soluble lithium salt, more preferably selected from lithium nitrate and/or lithium acetate, and further preferably lithium nitrate.
In some embodiments of the invention, the temperature of the impregnation in step (2) is preferably 30-80 ℃ in order to make the contact of the support with the precursor solution more sufficient. The time of the impregnation is preferably 1 to 6 hours, more preferably 1 to 3 hours.
In some embodiments of the invention, to facilitate contact of the support with the precursor solution, in step (2), the power of the microwave reactor used for the second microwave treatment is preferably 400-800W, and the time of the microwave reactor used for the second microwave treatment is preferably 0.5-6h. The temperature of the second microwave treatment is 35-80 ℃.
In the present invention, in the step (2), the treatment process of removing the solvent after the completion of the impregnation may be a conventional method in the art, and for example, a rotary evaporator may be used to remove the solvent in the impregnation system.
In the present invention, in the step (2), the drying may be performed by a method conventional in the art, preferably, the drying is performed in a drying apparatus, and the drying conditions may include a drying temperature preferably ranging from 120 to 140 ℃. The drying time is preferably 2 to 6 hours.
In some embodiments of the invention, in step (2), the calcination temperature is preferably 550-650 ℃ in order to promote the formation of the supported catalyst. The calcination time is preferably 4 to 5 hours.
In the present invention, the method may further include the step of molding the resulting supported catalyst. The molding method is not limited, and a conventional extrusion molding may be employed, and the shape of the resulting molded supported catalyst may be cylindrical, honeycomb or sheet. And then crushing and sieving the formed supported catalyst, wherein the particle size of the obtained supported catalyst is 40-60 meshes.
In a third aspect of the invention, a supported catalyst is provided, and the supported catalyst is prepared by the method.
In a fourth aspect of the invention, there is provided a process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the supported catalyst in the presence of oxygen;
alternatively, a supported catalyst is prepared as described above, and then methane is contacted with the resulting supported catalyst in the presence of oxygen.
In the present invention, the contacting may be performed in a continuous flow reactor, and the present invention is not limited to the type of continuous flow reactor, and may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or an ebullated bed reactor. In particular, the supported catalyst may be layered in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullated bed).
In some embodiments of the invention, to facilitate the catalytic reaction, to increase the conversion of methane and to increase the selectivity to hydrocarbons with more than two carbons, the molar ratio of methane to the oxygen may be from 2 to 8:1, preferably 3-8:1.
In the present invention, the conditions of the contact are not particularly limited, and may be selected conventionally in the art, and preferably the contact temperature is 500 to 750 ℃. The time of the contacting may be 1 to 20 hours; the pressure of the contact is 0.0005-0.03MPa, and the space velocity of methane is 10000-100000 mL/(g.h), preferably 25000-80000 mL/(g.h).
In the present invention, the unit "mL/(g.h)" is the amount of the total gas of methane and oxygen (mL) used for 1 hour with respect to 1g of the catalyst.
In the present invention, the hydrocarbon having two or more carbon atoms may be ethane, ethylene, propylene, propane, butene, butane, and a small amount of higher hydrocarbons.
In the present invention, the pressures refer to gauge pressure.
The present invention will be described in detail by examples.
In both examples and comparative examples, the reagents used were commercially available analytically pure reagents. The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A. The muffle furnace is available from CARBOLITE company under the model CWF1100. Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer was purchased from Sigma-Aldrich under the trade name P123 and the molecular formula EO 20 PO 70 EO 20 Molecular weight 5800. Tetraethyl silicate, analytically pure, purchased from Shanghai Ala Biotechnology Co., ltd. The pH value during the experiment was measured using a Metler pH meter S220.
Example 1
24g (0.004 mol) of template P123 is added into a solution (pH value is 3.5) consisting of 720mL of hydrochloric acid with the concentration of 2mol/L and 200g of deionized water, the solution is stirred to dissolve the P123 completely, then 51g of tetraethyl silicate is added into the solution at the speed of 0.1g/min, the solution is stirred for 18 hours at the temperature of 40 ℃, then the solution is transferred into a microwave reactor with the power of 500W, the reaction time is 2 hours and the temperature is 45 ℃, then filtration and washing with deionized water are carried out for 3 times, ethanol is used for washing once, then the solution is dried in an oven at the temperature of 100 ℃ for 10 hours, the solution is baked at the temperature of 500 ℃ for 4 hours in a muffle furnace, and the obtained product is the mesoporous molecular sieve SBA-15 through XRD detection.
Weighing 0.58g (0.001 mol) of lanthanum nitrate hexahydrate, 0.1g (0.0004 mol) of barium nitrate and 0.06g (0.0009 mol) of lithium nitrate, adding into 100g of deionized water, mixing and stirring uniformly, adding 1g of mesoporous molecular sieve SBA-15 prepared in preparation example 1 into the uniformly mixed solution, treating for 2 hours under the microwave condition at the temperature of 35 ℃ with the power of a microwave reactor, removing solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a baking oven at the temperature of 110 ℃, drying for 2 hours, placing in a muffle furnace, setting the temperature to 650 ℃, and roasting for 4 hours to obtain the supported catalyst.
Example 2
16g (0.0034 mol) of template P123 is added into a solution (pH value is 3.6) consisting of 280mL of hydrochloric acid with the concentration of 2mol/L and 196g of deionized water, the solution is stirred to dissolve the P123 completely, then 50g of tetraethyl silicate is added into the solution at the speed of 0.12g/min, the solution is stirred for 20 hours at the temperature of 50 ℃, then the solution is transferred into a microwave reactor with the power of 600W, the reaction time is 1 hour, the temperature is 45 ℃, then filtration and washing with deionized water are carried out for 3 times, ethanol is used for washing once, then the solution is dried in an oven at the temperature of 100 ℃ for 10 hours, the solution is baked at the temperature of 550 ℃ for 3 hours in a muffle furnace, and the obtained product is the mesoporous molecular sieve SBA-15 through XRD detection.
Weighing 0.32g (0.0007 mol) of lanthanum nitrate hexahydrate, 0.02g (0.002 mol) of barium nitrate and 0.04g (0.0006 mol) of lithium nitrate, adding into 100g of deionized water, mixing and stirring uniformly, adding 1g of mesoporous molecular sieve SBA-15 prepared in preparation example 1 into the uniformly mixed solution, treating for 1.5h under the microwave condition at the temperature of 45 ℃, removing solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a baking oven at the temperature of 100 ℃, drying for 3h, placing in a muffle furnace at the set temperature of 550 ℃, and roasting for 4h to obtain the supported catalyst.
Example 3
13g (0.002 mol) of template P123 is added into a solution (pH value is 4.2) consisting of 220mL hydrochloric acid with the concentration of 2mol/L and 198g deionized water, the solution is stirred to dissolve the P123 completely, 38g of tetraethyl silicate is added into the solution at the speed of 0.15g/min, the solution is stirred for 16 hours at the temperature of 55 ℃, then the solution is transferred into a microwave reactor with the power of 600W, the reaction time is 1 hour, the temperature is 45 ℃, the filtration and the washing with deionized water are carried out for 3 times, the washing with ethanol is carried out once, the drying is carried out in an oven at the temperature of 100 ℃ for 18 hours, the roasting is carried out at the temperature of 550 ℃ for 3 hours in a muffle furnace, and the obtained product is mesoporous molecular sieve SBA-15 through XRD detection.
Weighing 0.7g (0.0016 mol) of lanthanum nitrate hexahydrate, 0.018g (6.8X10) -5 mol) barium nitrate and 0.01g (1.3X10) -4 mol) lithium nitrate is added into 200g deionized water, mixed and stirred uniformly, 2g mesoporous molecular sieve SBA-15 prepared in preparation example 1 is added into the uniformly mixed solution, the power of a microwave reactor is 600W, the treatment is carried out for 3 hours under the microwave condition, the temperature is 55 ℃, and then the solution is subjected to spinAnd removing solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a 110 ℃ oven, drying for 2 hours, placing in a muffle furnace, setting the temperature to 650 ℃, and roasting for 5 hours to obtain the supported catalyst.
Example 4
11g (0.002 mol) of template P123 is added into a solution (pH value is 4.1) consisting of 400mL of hydrochloric acid with the concentration of 2mol/L and 168g of deionized water, the solution is stirred to dissolve the P123 completely, then 25g of tetraethyl silicate is added into the solution at the speed of 0.15g/min, the solution is stirred for 16 hours at the temperature of 55 ℃, then the solution is transferred into a microwave reactor with the power of 400W, the reaction time is 1.5 hours, the temperature is 45 ℃, then filtration and washing with deionized water are carried out for 3 times, ethanol is used for washing once, then the solution is dried in an oven at the temperature of 100 ℃ for 20 hours, roasting is carried out at the temperature of 500 ℃ for 3 hours in a muffle furnace, and the obtained product is mesoporous molecular sieve SBA-15 through XRD detection.
0.23g (0.0005 mol) lanthanum nitrate hexahydrate, 0.012g (4.6X10) were weighed out -5 mol) barium nitrate and 0.005g (7.2X10) -5 mol) lithium nitrate is added into 100g deionized water, the mixture is uniformly mixed, 1g mesoporous molecular sieve SBA-15 prepared in preparation example 1 is added into the uniformly mixed solution, the power of a microwave reactor is 600W, the temperature is 80 ℃ after treatment under the microwave condition, then a rotary evaporator is used for removing solvent water in the system to obtain a solid product, the solid product is placed into a 110 ℃ oven, dried for 2 hours, placed into a muffle furnace, and baked for 5 hours at the set temperature of 650 ℃ to obtain the supported catalyst.
Example 5
A supported catalyst was prepared as in example 1, except that the microwave reactor power at the time of preparation of the mesoporous molecular sieve SBA-15 was 300W and the microwave reactor power at the time of preparation of the supported catalyst was 900W.
Comparative example 1
A supported catalyst was prepared as in example 1, except that silica was used in place of the mesoporous molecular sieve SBA-15 prepared during the preparation.
Comparative example 2
Preparation of Supported according to the procedure of example 1Catalyst except that during the preparation 0.7g (0.0016 mol) lanthanum nitrate hexahydrate, 0.018g (6.8X10) -5 mol) barium nitrate, no lithium element was added.
Comparative example 3
The catalyst was prepared by the method of comparative example 1, except that barium nitrate was replaced with equimolar zinc nitrate and lanthanum nitrate was replaced with equimolar cerium nitrate.
Comparative example 4
The catalyst was prepared by the method of comparative example 1, using the same amount of lanthanum nitrate hexahydrate as used in the preparation process, except that lanthanum nitrate, barium nitrate and lithium nitrate were used in amounts such that the molar ratio of La, ba and Li was 1:4:2.
test example 1
0.1g of the supported catalyst obtained in the examples and comparative examples was charged into a fixed bed reactor to prepare hydrocarbons having more than two carbons by oxidative coupling of methane at a reaction pressure of 0.015MPa, methane: the molar ratio of oxygen is 7:1, the contact temperature is 600 ℃, the reaction time is 12h, the space velocity of methane is 60000 mL/(g.h), and the reaction product is collected after the reaction.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under the model number 7890A. Wherein hydrocarbons such as methane, ethane, ethylene, propane and propylene are detected by an alumina column FID detector, methane, carbon monoxide, carbon dioxide and oxygen are detected by a carbon molecular sieve column TCD detector, and calculated by a carbon balance method.
The calculation method of methane conversion rate and the like is as follows:
methane conversion = amount of methane consumed by the reaction/initial amount of methane x 100%
Ethylene selectivity = amount of methane consumed by ethylene produced/total amount of methane consumed x 100%
Ethane selectivity = amount of methane consumed by ethane produced/total amount of methane consumed x 100%
Propane selectivity = amount of methane consumed by propane produced/total amount of methane consumed x 100%
Propylene selectivity = amount of methane consumed by propylene produced/total amount of methane consumed x 100%
Carbon di-and above hydrocarbon selectivity = ethane selectivity + ethylene selectivity + propylene selectivity + propane selectivity
The results obtained are shown in Table 1.
Test example 2
The nitrogen adsorption and desorption experiments of the mesoporous molecular sieve SBA-15 samples obtained in the examples and the comparative examples were performed on an ASAP2020M+C fully automatic physical and chemical adsorption analyzer manufactured by Micromeritics Co., USA. The samples were vacuum degassed at 350 ℃ for 4 hours prior to measurement. The specific surface area of the sample was calculated by the BET method, and the pore volume and average pore diameter were calculated by the BJH model, and the results are shown in Table 1.
Test example 3
The mesoporous molecular sieve SBA-15 sample obtained in the example was subjected to an X-ray powder diffractometer test using a copper target on a Bruker D8 addition diffractometer, the copper target being characterized by a wavelength CuAs can be seen from XRD patterns, the mesoporous molecular sieve SBA-15 has characteristic peaks with 2 theta angles at 100 degrees, 110 degrees and 200 degrees, which illustrate that the mesoporous molecular sieve SBA-15 has the basic characteristics of SBA-15. Similarly, the mesoporous molecular sieves SBA-15 obtained in examples 2-5 also show characteristic peaks of 2 theta angles at 100 degrees, 110 degrees and 200 degrees through XRD detection, which shows that the mesoporous molecular sieves SBA-15 have the basic characteristics of SBA-15. The X-ray diffraction pattern obtained in example 1 is shown in FIG. 1.
Test example 4
Transmission electron microscopy was performed on the mesoporous molecular sieves SBA-15 obtained in examples and comparative examples, and TEM imaging was performed using JEOL for 2100F FEG TEM with schottky field emission source. Acceleration voltage 200kv, energy dispersive X-ray (EDX) analysis using low background double-tilting mount and INCAX-Sight silicon (lithium) detector for EDX, 25 ° Area at time of 50mm 2 130eV. The transmission electron microscope obtained in example 1 is shown in FIG. 2. As can be seen from FIG. 2, the mesoporous molecular sieve SBA-15 has a typical 1D pore structure. Similarly, the results of examples 2-5 were examined by transmission electron microscopyThe mesoporous molecular sieves SBA-15 all have typical 1D pore structures.
Test example 5
The elemental content of the supported catalysts in examples and comparative examples was determined by inductively coupled plasma atomic emission spectroscopy (ICP-OES), the instrument model of which is a fisher iCAP 6500 analyzer, and the test results are shown in table 1, wherein the lanthanum content, the barium content and the lithium content are shown in table 1 on the basis of 100wt%, with the balance being the carrier content.
TABLE 1
As can be seen from Table 1, when the supported catalysts obtained in examples 1 to 5 and comparative examples 1 to 4 were used in the oxidative coupling reaction of methane, examples 1 to 5 had a large methane conversion rate and selectivity to hydrocarbons having more than two carbons, and after 12 hours of reaction, the high methane conversion rate and selectivity to hydrocarbons having more than two carbons could still be maintained, while the reaction time was shortened in the production process of the present invention; the methane conversion rate, ethane selectivity, ethylene selectivity and other hydrocarbon selectivities of comparative examples 1-4 are all lower than those of examples 1-5, which shows that the supported catalyst of the invention has excellent catalytic performance when used for the oxidative coupling reaction of methane.
As can be seen from comparing example 4 with other examples, the preparation of the supported catalyst capable of obtaining particularly excellent catalytic performance was carried out in the following manner:
adding template agent P123 into a solution (pH value is 4-4.1) formed by hydrochloric acid and deionized water, stirring to dissolve the P123 completely, adding tetraethyl silicate into the solution at a rate of 0.15-0.17g/min, stirring for 15-16h at a temperature of 55-58 ℃, transferring the solution into a microwave reactor with a power of 400-600W, a reaction time of 1.5-2h, a temperature of 45-50 ℃, filtering, washing with deionized water for 3 times, washing with ethanol once, drying at 100-103 ℃ for 20-22h, and roasting at 500-510 ℃ for 2.8-3h to obtain mesoporous molecular sieve SBA-15, wherein the dosage of deionized water is 165-170g, the dosage of tetraethyl silicate is 24-25g, the concentration of hydrochloric acid is 2-2.2mol/L, and the dosage of hydrochloric acid is 400-402mL relative to 0.002mol template agent P123;
adding lanthanum nitrate hexahydrate, barium nitrate and lithium nitrate into deionized water, mixing and stirring uniformly, adding the obtained mesoporous molecular sieve SBA-15 into the uniformly mixed solution, treating the solution for 3-4 hours under the microwave condition with the power of 600-700W and the temperature of 75-80 ℃, then removing solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product into a baking oven at 110-112 ℃, drying for 2.1-2.5 hours, placing the solid product into a muffle furnace, setting the temperature to 648-650 ℃, and roasting for 4.8-5 hours to obtain the supported catalyst, wherein the dosage of barium nitrate is 0.012-0.013g, the dosage of lithium nitrate is 0.005-0.0053g, and the dosage of deionized water is 100-105g, and the dosage of mesoporous molecular sieve SBA-15 is 1-1.2g.
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 (24)

1. The supported catalyst is characterized by comprising a carrier and an active component supported on the carrier, wherein the carrier is a mesoporous molecular sieve SBA-15; the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1.
2. The supported catalyst according to claim 1, wherein the specific surface area of the carrier is 700-1000m 2 /g；
And/or the pore volume of the carrier is 0.5-1.5cm 3 /g；
And/or the average pore diameter of the carrier is 2-5nm;
and/or, the mole ratio of La, ba and Li is 1:0.08-0.3:0.14-0.65.
3. The supported catalyst according to claim 1, wherein the specific surface area of the carrier is 750-900m 2 /g；
And/or the pore volume of the carrier is 0.8-1.2cm 3 /g；
And/or the average pore diameter of the carrier is 2.5-4nm.
4. A supported catalyst according to any one of claims 1 to 3 wherein the support is present in an amount of 79.5 to 94.8 wt% based on the total weight of the supported catalyst;
and/or La in an amount of 5 to 18 wt%;
and/or, the content of Ba is 0.1-5 wt%;
and/or Li content of 0.01-1 wt%;
and/or the active component is present in an oxidized form.
5. A supported catalyst according to any one of claims 1 to 3 wherein the support is present in an amount of 84.7 to 91.4 wt% based on the total weight of the supported catalyst;
and/or La in an amount of 8 to 15 wt%;
and/or, the content of Ba is 0.5-4 wt%;
and/or the content of Li is 0.05 to 0.8 wt.%.
6. A method of preparing a supported catalyst, the method comprising:
(1) Under an acidic condition, contacting a template agent with a silicon source, performing first microwave treatment on the mixture obtained after the contact, and then sequentially performing solid-liquid separation, drying and roasting to obtain a mesoporous molecular sieve SBA-15;
(2) Loading active components on a mesoporous molecular sieve SBA-15, wherein the active components comprise La, ba and Li; wherein, the mole ratio of La, ba and Li is 1:0.04-0.3:0.08-1.
7. The method according to claim 6, wherein in the step (1), the pH of the acidic condition is controlled to 1 to 6 using an acidic substance; the acidic substance is at least one of phosphoric acid, nitric acid, hydrochloric acid and acetic acid;
and/or the template agent is a nonionic surfactant; and/or, the silicon source is sodium silicate and/or tetraethyl silicate;
and/or, the mole ratio of La, ba and Li is 1:0.08-0.3:0.14-0.65.
8. The method according to claim 6, wherein in the step (1), the pH of the acidic condition is controlled to 1 to 5 using an acidic substance; the acidic substance is hydrochloric acid;
and/or the template agent is EO with a general formula a PO b EO a Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer of (a);
and/or, the silicon source is tetraethyl silicate.
9. The method of claim 6, wherein in step (1), the templating agent is EO a PO b EO a Polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymers of formula (I), wherein a has a value of 10-100 and b has a value of 40-80.
10. The method of claim 6, wherein in step (1), the templating agent is EO 20 PO 70 EO 20 。
11. The method according to any one of claims 7 to 10, wherein in step (1), the template is used in an amount of 3.3 x 10 based on 1L of the mixture -3 -5.8×10 -3 mol; the molar ratio of the template to the silicon source, calculated as Si, was 0.01-0.1：1。
12. The method according to any one of claims 6-10, wherein in step (1), the contacting is at a temperature of 20-80 ℃;
and/or, the contact time is 12-36h;
and/or the contact is carried out by adding a silicon source into the template agent, wherein the adding rate of the silicon source is 0.1-1g/min based on 1g of the template agent;
and/or the power of the microwave reactor used for the first microwave treatment is 400-800W; the time of the first microwave treatment is 0.5-6h, and the temperature is 45-55 ℃;
and/or, in the step (1), the roasting temperature is 300-700 ℃; the roasting time is 2-10h.
13. The method according to any one of claims 6-10, wherein in step (1), the temperature of the contacting is 25-60 ℃;
and/or, the contact time is 12-25h;
and/or the contact is carried out by adding a silicon source into the template agent, wherein the adding rate of the silicon source is 0.1-0.5g/min based on 1g of the template agent;
and/or the time of the first microwave treatment is 1-5h;
and/or, in the step (1), the roasting temperature is 400-600 ℃; the roasting time is 3-8h.
14. The method of claim 6, wherein in step (2), the loading is performed by:
impregnating the carrier with impregnating solution containing lanthanum precursor, barium precursor and lithium precursor, performing microwave treatment for the second time on the obtained impregnating system, and then sequentially drying and roasting to obtain the supported catalyst.
15. The method according to claim 14, wherein in the impregnation system, the concentration of the lanthanum precursor in terms of lanthanum element is 0.01-0.5 wt%, the concentration of the barium precursor in terms of barium element is 0.001-0.3 wt%, the concentration of the lithium precursor in terms of lithium element is 0.0004-0.007 wt%, and the impregnation liquid is used in an amount of 80-120g per g of carrier.
16. The method of claim 14 or 15, wherein the lanthanum precursor is a water-soluble lanthanum salt;
and/or, the barium precursor is a water-soluble barium salt;
and/or, the lithium precursor is a water-soluble lithium salt.
17. The method of claim 14 or 15, wherein the lanthanum precursor is selected from at least one of lanthanum nitrate, lanthanum chloride, and lanthanum chlorate;
and/or the barium precursor is selected from barium nitrate and/or barium chloride;
and/or the lithium precursor is selected from lithium nitrate and/or lithium acetate.
18. The method of claim 14 or 15, wherein the lanthanum precursor is selected to be lanthanum nitrate;
and/or the lithium precursor is selected as lithium nitrate.
19. The method of claim 14, wherein in step (2), the temperature of the impregnation is 30-80 ℃; the time is 1-6h;
and/or the power of the microwave reactor used in the second microwave treatment is 400-800W, the time is 0.5-6h, and the temperature is 35-80 ℃;
and/or, in the step (2), the roasting temperature is 550-650 ℃; the roasting time is 4-5h.
20. The method of claim 14, wherein in step (2), the time of the impregnating is 1-3 hours.
21. A supported catalyst prepared by the method of any one of claims 6-20.
22. A process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the supported catalyst of any one of claims 1-5 and 21 in the presence of oxygen;
or a supported catalyst is prepared according to the process of any one of claims 6 to 20 and then methane is contacted with the resulting supported catalyst in the presence of oxygen.
23. The method of claim 22, wherein the molar ratio of methane to oxygen is from 2 to 8:1, a step of;
and/or, the contact temperature is 500-750 ℃; the contact time is 1-20h; the pressure of the contact is 0.0005-0.03MPa, and the space velocity of methane is 10000-100000 mL/(g.h).
24. The method of claim 22, wherein the molar ratio of methane to oxygen is 3-8:1;
and/or, the space velocity of methane is 25000-80000 mL/(g.h).
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