CN113797913B - Magnesium lanthanum composite oxide and preparation method and application thereof - Google Patents

Magnesium lanthanum composite oxide and preparation method and application thereof Download PDF

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CN113797913B
CN113797913B CN202010535500.0A CN202010535500A CN113797913B CN 113797913 B CN113797913 B CN 113797913B CN 202010535500 A CN202010535500 A CN 202010535500A CN 113797913 B CN113797913 B CN 113797913B
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magnesium
composite oxide
lanthanum composite
lanthanum
precursor
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CN113797913A (en
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武洁花
冯英杰
冯静
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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China Petroleum and Chemical Corp
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Abstract

The invention relates to the field of methane catalytic oxidation, and discloses a magnesium lanthanum composite oxide, a preparation method and application thereof. The molar ratio of Mg to La in the magnesium-lanthanum composite oxide is 1:0.02-1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has a characteristic peak at the position of 23.05±0.3、25.83±0.3、26.01±0.3、27.45±0.3、31.02±0.3、33.74±0.3、43.26±0.3、45.02±0.3、46.3±0.3、47.75±0.3、50.86±0.3、56.3±0.3、57.75±0.3、58.01±0.3、64.1±0.3、8±0.3、71.5±0.3、3.2±0.3、76±0.3 of 2 theta. The magnesium lanthanum composite oxide has larger pore volume, pore diameter and specific surface area, and is more beneficial to the generation of active oxygen sites.

Description

Magnesium lanthanum composite oxide and preparation method and application thereof
Technical Field
The invention relates to the field of methane catalytic oxidation, in particular to a magnesium lanthanum composite oxide and a preparation method and application thereof.
Background
One of the most basic materials for petrochemical industry. In the aspect of synthetic materials, the method is widely used for producing polyethylene, chloroethylene, polyvinyl chloride, ethylbenzene, styrene, polystyrene, ethylene propylene rubber and the like; in the aspect of organic synthesis, the method is widely used for synthesizing various basic organic synthesis raw materials such as ethanol, ethylene oxide, ethylene glycol, acetaldehyde, acetic acid, propionaldehyde, propionic acid, derivatives thereof and the like; by halogenation, chloroethylene, chloroethane and bromoethane can be prepared; alpha-olefin can be prepared by oligomerization, and higher alcohol, alkylbenzene and the like are further produced. In recent years, the discovery and exploitation of shale gas brings revolutionary promotion to the development and utilization of natural gas. Therefore, the method is also receiving more and more attention as the most direct and effective natural gas utilization method with high economic competitiveness, namely, the method for preparing ethane and ethylene by oxidative coupling of methane. Since the oxidative coupling reaction of methane is a strong exothermic reaction and is carried out at high temperature, no industrial production has been developed so far, and therefore, the development of a methane oxidative coupling catalyst with excellent performance has practical significance.
To improve the reactivity of the oxidative coupling catalyst for methane, researchers have done much work, such as in CN103764276a, to prepare a catalyst comprising: formula Ln 14-xLn2xO6, wherein Ln1 and Ln2 are each independently a different lanthanide and x is a number from greater than 0 to less than 4; and at least one doping element from groups 1-6, 8, 11, 13-15, or a combination thereof, wherein the doping element is present at a maximum concentration of 75 wt% of the catalyst; also contains doping metal element ：Na、Mg、Ca、Sr、Ga、Sc、Y、Zr、In、Nd、Eu、Sm、Ce、Gd、Hf、Ho、Tm、W、La、K、Dy、Cs、S、Rb、Ba、Yb、Ni、Lu、Ta、P、Pt、Bi、Sn、Nb、Sb、Ge、Ag、Au、Pb、Re、Fe、Al、Tl、Pr、Co、Rh、Ti、V、Cr、Mn、Ir、As、Li、Tb、Er、Te or Mo. The catalyst has catalytic activity such that the selectivity of hydrocarbons of more than two carbons is 50% or more and the methane conversion is 20% or more when the catalyst is used as a heterogeneous catalyst in the oxidative coupling of methane at a temperature of 850 ℃ or less, 800 ℃ or less, e.g., 750 ℃ or less or 700 ℃ or less. In the mesoporous molecular sieve catalyst for preparing ethylene by oxidative coupling of methane and the preparation method thereof, mesoporous molecular sieve is adopted as a catalyst carrier for modification, and catalytic active components such as Na 2WO4 and Mn or Na 2WO4, mn and 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, and the preparation period is long. CN109569565A is used for preparing a methane oxidative coupling non-stoichiometric defect fluorite catalyst, adopts a defect structure to reduce the reaction temperature in the application, and utilizes a traditional citric acid sol-gel preparation method to prepare the non-stoichiometric defect fluorite catalyst. The prepared catalyst has the problems of high catalytic activation 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 overcome the defects of low reaction activity, complex preparation process, long preparation period, high catalytic activation reaction temperature and difficult industrial application of a methane oxidative coupling catalyst in the prior art, and provides a magnesium-lanthanum composite oxide and a preparation method and application thereof, wherein the magnesium-lanthanum composite oxide has larger pore volume, pore diameter and specific surface area, is more beneficial to the generation of active oxygen sites, and the preparation method of the magnesium-lanthanum composite oxide is simple and environment-friendly, has short preparation period and low raw material price, and is easy for large-scale production and application; the magnesium-lanthanum composite oxide can enable the reaction of preparing more than two carbon atoms from methane to be carried out at a lower temperature (such as in the range of 400-450 ℃), reduces the requirements on a reactor and operating conditions, has higher methane conversion rate and higher more than two carbon atoms selectivity, and is more beneficial to industrialized amplified production.
In order to achieve the above object, according to one aspect of the present invention, there is provided a magnesium lanthanum composite oxide in which the molar ratio of Mg to La is 1:0.02-1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has a characteristic peak at the position of 23.05±0.3、25.83±0.3、26.01±0.3、27.45±0.3、31.02±0.3、33.74±0.3、43.26±0.3、45.02±0.3、46.3±0.3、47.75±0.3、50.86±0.3、56.3±0.3、57.75±0.3、58.01±0.3、64.1±0.3、8±0.3、71.5±0.3、3.2±0.3、76±0.3 of 2 theta.
In the invention, the magnesium lanthanum composite oxide is of a layered nano structure, has larger pore volume, pore diameter and specific surface area, and is beneficial to the generation of active oxygen sites, thereby promoting the oxidation coupling reaction of methane.
In a second aspect of the present invention, there is provided a method for preparing a magnesium lanthanum composite oxide, the method comprising: in the presence of a solvent, mixing a magnesium precursor, a lanthanum precursor and a precipitant in a gradual contact manner, wherein the gradual contact manner controls the pH value of a mixed system to be 9-13, aging is carried out after the gradual contact is finished, a solid phase is separated from an aged product, and drying and roasting are sequentially carried out.
In a third aspect of the invention, there is provided a method as hereinbefore described.
In a fourth aspect of the invention, there is provided a process for producing more than two carbon hydrocarbons from methane, the process comprising: in the presence of oxygen, contacting methane with the magnesium-lanthanum composite oxide to perform catalytic reaction; or preparing the magnesium-lanthanum composite oxide according to the method, and then contacting methane with the obtained magnesium-lanthanum composite oxide in the presence of oxygen to perform catalytic reaction.
The method for preparing the magnesium-lanthanum composite oxide is simple and environment-friendly, short in preparation period, low in raw material price and easy to produce and apply on a large scale.
The method for preparing the hydrocarbon with more than two carbon atoms from the methane comprises the steps of contacting the methane with the magnesium-lanthanum composite oxide in the presence of oxygen to perform catalytic reaction so as to prepare the hydrocarbon with more than two carbon atoms, wherein the magnesium-lanthanum composite oxide can enable the reaction for preparing the hydrocarbon with more than two carbon atoms from the methane to be performed at a lower temperature (such as in a range of 400-450 ℃), thereby reducing the requirements on a reactor and operating conditions, and being beneficial to industrialized amplified production.
In summary, the beneficial effects of the invention compared with the prior art are as follows:
(1) The magnesium lanthanum oxide is prepared by adopting a coprecipitation method, and then the magnesium lanthanum composite oxide is prepared by roasting, and the magnesium lanthanum composite oxide prepared by the method has larger pore volume, pore diameter and specific surface area, is more beneficial to the generation of active oxygen sites, thereby ensuring the excellent performance of the methane oxidative coupling catalyst.
(2) The magnesium lanthanum composite oxide provided by the invention has good catalytic performance when being used for methane oxidative coupling reaction, namely, the catalytic activation reaction temperature is low, the methane conversion rate is high, and the hydrocarbon selectivity is high more than two carbon atoms, so that the magnesium lanthanum composite oxide is beneficial to industrial scale-up production.
Drawings
FIG. 1 is an X-ray diffraction chart of a magnesium lanthanum composite oxide obtained according to example 1;
fig. 2 is a transmission electron microscope TEM image of the magnesium lanthanum composite oxide obtained according to example 1.
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 magnesium-lanthanum composite oxide, wherein the molar ratio of Mg to La in the magnesium-lanthanum composite oxide is 1:0.02-1.2; wherein the XRD pattern of the magnesium lanthanum composite oxide has a characteristic peak at the position of 23.05±0.3、25.83±0.3、26.01±0.3、27.45±0.3、31.02±0.3、33.74±0.3、43.26±0.3、45.02±0.3、46.3±0.3、47.75±0.3、50.86±0.3、56.3±0.3、57.75±0.3、58.01±0.3、64.1±0.3、8±0.3、71.5±0.3、3.2±0.3、76±0.3 of 2 theta.
In the invention, preferably, the molar ratio of Mg to La in the magnesium lanthanum composite oxide is 1:0.05-0.1.
In the present invention, preferably, the magnesium lanthanum composite oxide is a layered nano structure.
In the invention, the specific surface area, the pore volume and the pore diameter of the magnesium lanthanum composite oxide can be measured according to a nitrogen adsorption method, the specific surface area is calculated by adopting a BET method, and the pore volume is calculated by adopting a BJH model. The specific surface area of the magnesium lanthanum composite oxide is preferably 40 to 500m 2/g, more preferably 50 to 200m 2/g. The pore volume of the magnesium lanthanum composite oxide is preferably 0.1 to 0.5cm 3/g, more preferably 0.2 to 0.4cm 3/g. The average pore diameter of the magnesium lanthanum composite oxide is preferably 8 to 20nm, more preferably 10 to 15nm.
In the invention, in order to further reduce the catalytic activation reaction temperature and improve the conversion rate of methane, the magnesium-lanthanum composite oxide can further comprise other metal elements, and the other metal elements are preferably at least one selected from Li, na, ca, cs, ce, W, mn, ru, rh, ni and Pt. The method of supporting other metals on the above magnesium lanthanum composite oxide is not particularly limited in the present invention, and those skilled in the art can use methods in the prior art, for example: mixing, precipitation/co-precipitation, impregnation, sol-gel, template/surface derived metal oxide synthesis, solid state synthesis of mixed metal oxides, microemulsion technology, solvothermal synthesis, sonochemical synthesis or combustion synthesis, etc., to achieve doping of other metals.
In the present invention, it is preferable that the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.01 to 50wt%, for example, 0.01wt%, 1wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, or any value between the above values. More preferably 0.1 to 20wt%, for example, 0.1wt%, 0.5wt%, 1wt%, 5wt%, 8wt%, 10wt%, 15wt%, 20wt% or any value between the above values. Further preferably 1-5wt%, for example 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% or any value in between the above values.
In the present invention, other metal elements exist in the form of oxides.
At a reaction pressure of 0.004MPa, methane: the molar ratio of oxygen is 5: 1. under the reaction conditions that the space velocity of methane is 40000 mL/(g.h) and the reaction time is 100h, the reaction activation temperature of the magnesium lanthanum composite oxide of the present invention is preferably 500℃or less, more preferably 455℃or less, and still more preferably 400 to 450 ℃. The "reaction activation temperature" refers to the temperature of the catalyst bed when the gas chromatography detects the formation of any hydrocarbon of two or more carbon atoms in the reaction product.
In a second aspect of the present invention, there is provided a method for preparing a magnesium lanthanum composite oxide, the method comprising: in the presence of a solvent, mixing a magnesium precursor, a lanthanum precursor and a precipitant in a gradual contact manner, wherein the gradual contact manner controls the pH value of a mixed system to be 9-13, aging is carried out after the gradual contact is finished, a solid phase is separated from an aged product, and drying and roasting are sequentially carried out.
In the invention, the mixing can be carried out in a gradual contact mode, wherein the gradual contact mode is as follows: the precipitant solution is prepared in advance so that the pH value of the precipitant solution is 12-13, and then the magnesium precursor and the lanthanum precursor are mixed with the precipitant solution in a gradual contact manner. According to a preferred embodiment of the invention, the magnesium precursor and the lanthanum precursor are dissolved in a solvent to form a solution A, the precipitant is dissolved in the solvent to form a solution B, the solution B is dropwise added into water until the pH value of the formed solution is 12-13, the solution A is dropwise added until the pH value of the formed mixed solution is 10-11, the dropping speeds of the solution A and the solution B are controlled so that the pH value of the formed mixed system is controlled within the range of 9-11, the solution A and the solution B are completely dropped, aging is carried out, solid phases are separated from the aged products, and drying and roasting are sequentially carried out. Specifically, in the solution a, the weight concentration of magnesium element is: 1-3wt% of lanthanum element, wherein the weight concentration of lanthanum element is as follows: 1-6wt%; in the solution B, the weight concentration of the carbon element is as follows: 1-3wt%; in a mixed system formed after the solution A and the solution B are completely added, the weight concentration of magnesium element is as follows: 0.5 to 1.1 weight percent, and the weight concentration of lanthanum element is as follows: 0.4-2wt% of carbon element, the weight concentration of which is: 0.5-1.2wt%.
In the present invention, the solvent may be water, preferably, deionized water.
In the present invention, the precipitant may be a substance whose solution after hydrolysis is alkaline (preferably pH 9 to 13), preferably, the precipitant is an alkali metal carbonate and/or an alkali metal bicarbonate. The alkali metal carbonate is an alkali metal water-soluble carbonate, more preferably sodium carbonate and/or potassium carbonate; and/or the alkali metal bicarbonate is an alkali metal water-soluble bicarbonate, more preferably sodium bicarbonate and/or potassium bicarbonate. Further preferably, the precipitant may contain a water-soluble base to ensure the alkaline environment required for the co-precipitation reaction, still further preferably, the water-soluble base is sodium hydroxide and/or potassium hydroxide.
In the present invention, preferably, the magnesium precursor is a water-soluble magnesium salt, more preferably at least one selected from magnesium nitrate, magnesium chloride and magnesium chlorate, and still more preferably magnesium nitrate; and/or the lanthanum precursor is water-soluble lanthanum salt, more preferably lanthanum nitrate and/or lanthanum acetate, and further preferably lanthanum nitrate.
In the present invention, preferably, the molar ratio of the magnesium precursor in Mg to the lanthanum precursor in La is 1:0.01-1, more preferably 1:0.2-0.4.
In the present invention, the magnesium precursor is preferably used in an amount of 0.1 to 50g, preferably 1 to 20g, more preferably 1 to 5g, in terms of Mg per 100g of the mixed system.
In the invention, in order to promote the coprecipitation reaction, the aging temperature is 50-70 ℃; the aging time is 10 to 50 hours, preferably 12 to 36 hours.
In the present invention, preferably, the precipitant is used in an amount such that the precipitant provides carbonate and/or bicarbonate in a molar ratio to the magnesium precursor in terms of Mg of 1 to 5:1.
In the invention, in order to promote the generation of the magnesium-lanthanum composite oxide, the roasting temperature is preferably 500-750 ℃, more preferably 550-600 ℃; the calcination time is preferably 2 to 10 hours, more preferably 2 to 8 hours, still more preferably 2 to 5 hours.
In the present invention, the drying method is not particularly limited, and a method of naturally drying or drying in a drying apparatus may be employed.
In the present invention, the method may further comprise a step of washing. There is no particular limitation on the manner of washing, and washing with water (preferably deionized water) may be performed 2 to 5 times.
In the invention, in order to further reduce the catalytic activation reaction temperature and improve the conversion rate of methane, the method further comprises loading other metal elements on the roasting product, wherein the other metal elements are at least one selected from Li, na, ca, cs, ce, W, mn, ru, rh, ni and Pt. The method of supporting other metals on the above magnesium lanthanum composite oxide is not particularly limited in the present invention, and those skilled in the art can use methods in the prior art, for example: mixing, precipitation/co-precipitation, impregnation, sol-gel, template/surface derived metal oxide synthesis, solid state synthesis of mixed metal oxides, microemulsion technology, solvothermal synthesis, sonochemical synthesis, combustion synthesis, etc., to achieve doping of other metals.
According to a preferred embodiment of the invention, doping of other elements is performed by adopting a dipping mode, and after the dipping is completed, the magnesium-lanthanum composite oxide is obtained by drying and roasting in sequence, wherein the drying temperature is 80-120 ℃ and the time is 10-25 hours. The roasting temperature is 500-750 ℃ and the roasting time is 3-5h.
The amount of the other metal element used in the present invention is not limited as long as it is capable of making the weight percentage of the other metal element in the magnesium lanthanum composite oxide 0.01 to 50wt%, for example, 0.01wt%, 1wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or any value between the above values; more preferably 0.1 to 20wt%, for example, 0.1wt%, 0.5wt%, 1wt%, 5wt%, 8wt%, 10wt%, 15wt%, 20wt% or any value between the above values; further preferably 1 to 5wt%, for example, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% or any value between the above values.
In the present invention, the method may further include a step of molding the obtained magnesium lanthanum composite oxide. The molding method is not limited, and a conventional extrusion molding may be employed, and the shape of the resulting molded composite carrier may be cylindrical, honeycomb or sheet. And then crushing and sieving the formed composite carrier, wherein the particle size of the obtained composite carrier is 40-60 meshes.
In a third aspect of the invention, there is provided a method as hereinbefore described.
In a fourth aspect of the invention, there is provided a process for producing more than two carbon hydrocarbons from methane, the process comprising: in the presence of oxygen, contacting methane with the magnesium-lanthanum composite oxide to perform catalytic reaction; or preparing the magnesium-lanthanum composite oxide according to the method, and then contacting methane with the obtained magnesium-lanthanum composite oxide in the presence of oxygen to perform catalytic reaction.
In the present invention, the catalytic reaction 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 magnesium lanthanum composite oxide 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 the invention, in order to promote the catalytic reaction and improve the conversion rate of methane, the molar ratio of the methane to the oxygen is 2-10:1, preferably 3-8:1.
In the present invention, the conditions of the catalytic reaction are not particularly limited and may be selected conventionally in the art, and preferably the reaction initiation temperature of the catalytic reaction is 400 to 450 ℃. The time of the catalytic reaction is 1-500h. The pressure of the catalytic reaction is 0.004-0.02MPa. The space velocity of methane is 1000-80000 mL/(g.h), preferably 10000-50000 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.
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. Room temperature refers to "25 ℃ and" pressure "both refer to gauge pressure. The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A. The muffle furnace is manufactured by CARBOLITE company and is model CWF1100. The pH value during the experiment was measured using Metler S220.
Example 1
26.05G of Mg (NO 3)2·6H2 O and 14.66g of La (NO 3)3·6H2 O) are dissolved in 95g of deionized water and recorded as solution (A), K 2CO3 (40.3 g) and NaOH (11.7 g) are dissolved in deionized water (180 g) and recorded as solution (B). 60g of deionized water is added to the flask, then solution (B) is added dropwise to deionized water until the pH of the solution reaches 13, at this time, dropwise addition of solution (A) is started until the pH of the solution reaches 10. The flow rates of (A) and (B) are controlled to keep the pH of the solution at 10.+ -. 0.5 until all metal ion solutions (A) are added, the obtained slurry/mixture is aged for 12 hours at 65 ℃, then precipitate is separated by filtration and washed 3 times with 70 ℃ deionized water (volume=1.5L). The obtained solid is dried in an oven at 80 ℃ for 24 hours at 500 ℃ for 5 hours, and after cooling to room temperature, tabletting is carried out, crushing and sieving is carried out to obtain a 40-60 mesh magnesium lanthanum composite oxide.
Example 2
42.7G of MgCl 2·6H2 O and 2.21g of La (CH 3COO)3) were dissolved in 100g of deionized water, denoted as solution (A), KHCO 3 (50 g) and NaOH (10.1 g) were dissolved in deionized water (200 g), denoted as solution (B). 40g of deionized water was added to the flask, then solution (B) was added dropwise to deionized water until the pH of the solution reached 12, at which point dropwise addition of solution (A) was started until the pH of the solution reached 9.5. The flow rates of (A) and (B) were controlled to maintain the pH of the solution at 10.5.+ -. 0.5 until all metal ion solutions (A) were added were completed. The resulting slurry/mixture was aged at 50℃for 24 hours, then the precipitate was isolated by filtration and washed 3 times with 70℃deionized water (volume=1.5L). The resulting solid was dried in an oven at 80℃for 24 hours. Calcination in air at 600℃for 2 hours, and after cooling to room temperature, the crushing, sieving was carried out to obtain a magnesium lanthanum composite oxide.
Example 3
Magnesium lanthanum composite oxide was prepared in the same manner as in example 1 except that Mg (NO 3)2·6H2 O mass 26.05g and La (NO 3)3·6H2 O mass 43.3 g) was used.
Example 4
Magnesium lanthanum composite oxide was prepared in the same manner as in example 1 except that Mg (NO 3)2·6H2 O mass 26.05g and La (NO 3)3·6H2 O mass 4.5 g) was used.
Example 5
Magnesium lanthanum composite oxide was prepared according to the method of example 1, except that 2g of the solid was added to cerium nitrate solution after calcination, the solution composition was cerium nitrate 0.062g was dissolved in 50g of deionized water, cerium was loaded by impregnation, stirred in a water bath at 80 ℃ until water volatilized, dried at 120 ℃ for 24 hours, and then placed in a muffle furnace for calcination at 550 ℃ for 4 hours. And cooling to room temperature, tabletting, crushing, screening and taking 40-60 mesh part to obtain the magnesium-lanthanum composite oxide.
Example 6
Magnesium lanthanum composite oxide was prepared according to the method of example 1, except that 2g of the solid was added to a strontium nitrate solution after calcination, the solution composition was such that 0.060g of strontium nitrate was dissolved in 50g of deionized water, strontium was loaded by dipping, stirred in a water bath at 80 ℃ until the water volatilized, dried at 120 ℃ for 12 hours, and then placed in a muffle furnace for calcination at 550 ℃ for 4 hours. And cooling to room temperature, tabletting, crushing, screening and taking 40-60 mesh part to obtain the magnesium-lanthanum composite oxide.
Example 7
A magnesium lanthanum composite oxide was prepared according to the method of example 2, except that the firing temperature during the preparation was 750 ℃ and the firing time was 8 hours.
Comparative example 1
Magnesium lanthanum composite oxide was prepared according to the method of example 1, except that the mixing process of the solutions was not controlled by pH value during the preparation, but the two solutions were directly mixed.
Comparative example 2
Magnesium lanthanum composite oxide was prepared according to the method of example 1, except that Mg (NO 3)2·6H2 O was replaced with equimolar Ba (NO 3)2, la (NO 3)3·6H2 O was replaced with equimolar Ce (NO 3)3·6H2 O).
Test example 1
The nitrogen adsorption and desorption experiments of the composite oxide samples obtained in the examples and comparative examples were performed on an ASAP2020M+C fully automatic physico-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 2
0.2G of the composite oxides obtained in the examples and comparative examples were respectively charged into a fixed bed quartz reactor to perform oxidative coupling of methane to prepare ethylene-ethane, the reaction pressure was 0.004MPa, methane: the molar ratio of oxygen is 5:1, the contact time is 100h, the space velocity of methane is 20000 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%
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%
Hydrocarbon over two carbon number selectivity = ethane selectivity + ethylene selectivity + propylene selectivity + propane selectivity hydrocarbon over two carbon number yield = methane conversion x hydrocarbon over two carbon number selectivity
The results obtained are shown in Table 1.
Test example 3
The composite oxides obtained in examples and comparative examples were subjected to X-ray powder diffractometer testing using a copper target on a Bruker D8 Adti diffractometer, the copper target being characterized by its spectral wavelength The XRD patterns of the magnesium lanthanum composite oxides obtained in examples 1 to 7 have characteristic peaks at 23.05、25.83、26.01、27.45、31.02、33.74、43.26、45.02、46.3、47.75、50.86、56.3、57.75、58.01、64.1、8.0、71.5、3.2、76 in 2. Theta. The X-ray diffraction pattern obtained in example 1 is shown in FIG. 1.
Test example 4
The magnesium lanthanum composite oxide obtained in the example was subjected to a transmission electron microscope test using a test instrument model JEOL 2100F-FEG with an acceleration voltage of 200kV. The test result shows that the magnesium lanthanum composite oxide obtained in the example is of a layered nano structure. The TEM image of the transmission electron microscope obtained in example 1 is shown in FIG. 2.
Test example 5
The reaction initiation temperature is the temperature at which the reaction of the oxidative coupling of the alkane begins, that is, the temperature of the catalyst bed when the formation of any hydrocarbon of more than two carbons in the reaction product is detected. The reaction activation temperature of the composite oxide of examples and comparative examples was measured by thermocouple monitoring the temperature of the site where the reaction mass and the bed were in contact, and the reaction products were detected at a series of temperatures of ,350℃、360℃、370℃、380℃、386℃、400℃、410℃、413℃、415℃、418℃、420℃、425℃、430℃、433℃、435℃、438℃、440℃、442℃、444℃、446℃、448℃、450℃、452℃、455℃ and 480 c, respectively, with the other conditions being the same as in test example 2.
Test example 6
The elemental content of the composite oxides in examples and comparative examples was determined by inductively coupled plasma atomic emission spectroscopy (ICP-OES), instrument model FISHER ICAP 6500 analyzer, test results are shown in table 1.
TABLE 1
As can be seen from Table 1, when the composite oxides obtained in examples 1-7 and comparative examples 1-2 were used in the oxidative coupling reaction of methane, the reaction starting temperatures of examples 1-7 were all below 450 ℃ and after 100 hours of reaction, higher methane conversion and selectivity of hydrocarbons with more than two carbons could still be maintained; the reaction activation temperatures of comparative examples 1-2 are 650 ℃ and 700 ℃ respectively, and after 100 hours of reaction, the methane conversion rate, the carbon dioxide selectivity and the carbon dioxide yield are reduced relative to those of examples 1-7, which indicates that the magnesium lanthanum composite oxide has lower reaction activation temperature, excellent stability and is beneficial to industrial scale-up production. Further, the catalytic effects of examples 1 and 4, in which the molar ratio of Mg and La falls within the preferred range of the present invention, are more excellent than those of examples 2 and 3, indicating that the control of the molar ratio of Mg and La can obtain more excellent technical effects within the preferred range.
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 (31)

1. The magnesium-lanthanum composite oxide is characterized in that the molar ratio of Mg to La in the magnesium-lanthanum composite oxide is 1:0.05-0.1; wherein the XRD pattern of the magnesium lanthanum composite oxide has a characteristic peak at a position of 23.05±0.3、25.83±0.3、26.01±0.3、27.45±0.3、31.02±0.3、33.74±0.3、43.26±0.3、45.02±0.3、46.3±0.3、47.75±0.3、50.86±0.3、56.3±0.3、57.75±0.3、58.01±0.3、64.1±0.3、68±0.3、71.5±0.3、73.2±0.3、76±0.3 of 2 theta;
Wherein the magnesium lanthanum composite oxide is of a layered nano structure; wherein the specific surface area of the magnesium lanthanum composite oxide is 40-500m 2/g; wherein the pore volume of the magnesium lanthanum composite oxide is 0.1-0.5cm 3/g; wherein the average pore diameter of the magnesium lanthanum composite oxide is 8-20nm.
2. The magnesium lanthanum composite oxide according to claim 1, wherein the specific surface area of the magnesium lanthanum composite oxide is 50-200m 2/g;
and/or the pore volume of the magnesium lanthanum composite oxide is 0.2-0.4cm 3/g;
And/or the average pore diameter of the magnesium lanthanum composite oxide is 10-15nm.
3. The magnesium lanthanum composite oxide according to claim 1 or 2, further comprising other metal elements selected from Ce or Sr.
4. A magnesium lanthanum composite oxide according to claim 3, wherein the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.01 to 50wt%.
5. A magnesium lanthanum composite oxide according to claim 3, wherein the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.1 to 20wt%.
6. A magnesium lanthanum composite oxide according to claim 3, wherein the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 1 to 5wt%.
7. A method for producing the magnesium lanthanum composite oxide according to any one of claims 1 to 6, characterized in that the method comprises: in the presence of a solvent, mixing a magnesium precursor, a lanthanum precursor and a precipitant in a gradual contact manner, wherein the gradual contact manner controls the pH value of a mixed system to be 9-13, aging is carried out after the gradual contact is finished, a solid phase is separated from an aged product, and drying and roasting are sequentially carried out.
8. The method of claim 7, wherein the step-wise contacting is performed in a manner that: the precipitant solution is prepared in advance so that the pH value of the precipitant solution is 12-13, and then the magnesium precursor and the lanthanum precursor are mixed with the precipitant solution in a gradual contact manner.
9. The method according to claim 7 or 8, characterized in that the molar ratio of the magnesium precursor in Mg and the lanthanum precursor in La is 1:0.01-1.
10. The method of claim 7 or 8, wherein the magnesium precursor is a water-soluble magnesium salt;
and/or, the lanthanum precursor is water-soluble lanthanum salt;
And/or the solvent is water.
11. The method of claim 7 or 8, wherein the magnesium precursor is at least one of magnesium nitrate, magnesium chloride, and magnesium chlorate;
and/or the lanthanum precursor is lanthanum nitrate and/or lanthanum acetate;
and/or the solvent is deionized water.
12. The method according to claim 7 or 8, characterized in that the precipitant is an alkali metal carbonate and/or an alkali metal bicarbonate; the carbonate of the alkali metal is water-soluble carbonate of the alkali metal; and/or the alkali metal bicarbonate is an alkali metal water-soluble bicarbonate.
13. The method according to claim 12, characterized in that the alkali metal carbonate is sodium carbonate and/or potassium carbonate;
And/or the bicarbonate of the alkali metal is sodium bicarbonate and/or potassium bicarbonate.
14. The method according to claim 8 or 9, characterized in that the precipitant is used in an amount such that the precipitant provides a molar ratio of carbonate and/or bicarbonate to the magnesium precursor in Mg of 1-5:1.
15. The method according to claim 7 or 8, characterized in that the magnesium precursor is used in an amount of 0.1-50g in Mg per 100g of the mixed system.
16. The method according to claim 15, wherein the magnesium precursor is used in an amount of 1-20g in Mg per 100g of the mixed system.
17. The method according to claim 15, wherein the magnesium precursor is used in an amount of 1-5g in Mg per 100g of the mixed system.
18. The method according to claim 7 or 8, characterized in that the method further comprises loading other metal elements selected from Ce or Sr on the calcined product.
19. The method according to claim 18, wherein the other metal element is used in an amount such that the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.01 to 50wt%.
20. The method according to claim 18, wherein the other metal element is used in an amount such that the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 0.1 to 20wt%.
21. The method according to claim 18, wherein the other metal element is used in an amount such that the weight percentage of the other metal element in the magnesium lanthanum composite oxide is 1 to 5wt%.
22. The method according to claim 7 or 8, wherein the firing temperature is 500-750 ℃; the roasting time is 2-10h.
23. The method of claim 22, wherein the firing temperature is 550-600 ℃.
24. The method of claim 22, wherein the firing time is 2-8 hours.
25. The method of claim 22, wherein the firing time is 2-5 hours.
26. The method according to claim 7 or 8, wherein the temperature of aging is 50-70 ℃; the time is 10-50 hours.
27. The method of claim 26, wherein the aging is for a period of 12-36 hours.
28. A magnesium lanthanum composite oxide, characterized in that the magnesium lanthanum composite oxide is prepared by the method of any one of claims 7 to 27.
29. A process for producing more than two hydrocarbons from methane, the process comprising: contacting methane with the magnesium lanthanum composite oxide according to any one of claims 1 to 6 and claim 28 in the presence of oxygen to perform a catalytic reaction;
Or preparing the magnesium-lanthanum composite oxide according to the method of any one of claims 7 to 27, and then contacting methane with the obtained magnesium-lanthanum composite oxide in the presence of oxygen to perform a catalytic reaction.
30. The method of claim 29, wherein the molar ratio of methane to oxygen is from 2 to 10:1, a step of;
and/or, the reaction initiation temperature of the catalytic reaction is 400-450 ℃; the time of the catalytic reaction is 1-500h; the pressure of the catalytic reaction is 0.004-0.02MPa, and the airspeed of methane is 1000-80000 mL/(g.h).
31. The method of claim 30, wherein the molar ratio of methane to oxygen is 3-8:1;
and/or, the space velocity of methane is 10000-50000 mL/(g.h).
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