CN113800994A - Method and system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction - Google Patents

Method and system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction Download PDF

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CN113800994A
CN113800994A CN202010556346.5A CN202010556346A CN113800994A CN 113800994 A CN113800994 A CN 113800994A CN 202010556346 A CN202010556346 A CN 202010556346A CN 113800994 A CN113800994 A CN 113800994A
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reaction
catalyst
methane
ethane
oxidative coupling
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武洁花
薛伟
张明森
刘东兵
白杰
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/32—Manganese, technetium or rhenium
    • C07C2523/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the field of methane oxidative coupling reaction, and discloses a method and a system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction, wherein the method is carried out in a fixed bed casing pipe reactor containing at least two layers of casing pipes, and the method comprises the following steps: introducing a reaction material I containing methane and oxygen into a tube in which the oxidative coupling reaction of methane is performed to perform the oxidative coupling reaction of methane; and introducing a reaction mass II containing ethane into a tube in which the ethane catalytic dehydrogenation reaction is carried out to carry out the ethane catalytic dehydrogenation reaction; the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction. The method provided by the invention not only can solve the problem of high reaction temperature of the oxidative coupling reaction of methane, but also can effectively prevent temperature runaway of the oxidative coupling reaction of methane at high temperature.

Description

Method and system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction
Technical Field
The invention relates to the field of methane oxidative coupling reaction, in particular to a method for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction and a system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction.
Background
Ethylene is the most important basic organic chemical raw material, and its production has long been dependent on petroleum cracking routes, and the problems of environmental pollution and the like caused by the ethylene are becoming serious. In recent years, the price of crude oil is continuously rising to cause the price of ethylene cracking raw materials to rise, and the phenomenon of short supply and short demand of the ethylene cracking raw materials is also very prominent.
Among them, if a three-step process (POM/GTM/MTO) of producing methanol from synthesis gas/methanol from synthesis gas by partial oxidation is used to produce ethylene, the reaction process has many steps, and oxygen atoms are inserted and then taken out, which is a non-atomic economic reaction.
In the research of OCM catalyst system, the supported catalyst using silicon dioxide as carrier and sodium tungstate and manganese as active components is one of the catalyst systems with the best performance, but the catalyst can react at high temperature usually, and the reaction temperature is 750-.
Therefore, there is a need for a new method for preparing ethylene by oxidative coupling of methane.
Disclosure of Invention
The invention aims to overcome the defects of high reaction temperature and high temperature runaway possibility of the oxidative coupling reaction of methane in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing ethylene by coupling an oxidative coupling reaction of methane with a catalytic dehydrogenation reaction of ethane, the method being performed in a fixed-bed shell-and-tube reactor having at least two layers of shell tubes, and the oxidative coupling reaction of methane being performed in at least one tube of the shell tubes and the catalytic dehydrogenation reaction of ethane being performed in at least another adjacent tube, wherein a catalyst I for the oxidative coupling reaction of methane and a catalyst II for the oxidative coupling reaction of methane are sequentially filled in the tubes in which the oxidative coupling reaction of methane is performed, in a direction in which reaction materials flow, wherein a reaction temperature of the catalyst I is not higher than 600 ℃, and a reaction temperature of the catalyst II is not lower than 700 ℃; filling a tube in which the ethane catalytic dehydrogenation reaction is carried out with a catalyst III for the ethane catalytic dehydrogenation reaction, the catalyst III being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the method comprises the following steps: in the fixed-bed double-pipe reactor, introducing a reaction material I containing methane and oxygen into a pipe in which the oxidative coupling reaction of methane is carried out to carry out the oxidative coupling reaction of methane; and introducing a reaction mass II containing ethane into a tube in which the ethane catalytic dehydrogenation reaction is carried out to carry out the ethane catalytic dehydrogenation reaction;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
The second aspect of the invention provides a system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction, which comprises a fixed bed sleeve reactor comprising at least two layers of sleeves, wherein at least one of the sleeves can perform the methane oxidative coupling reaction, and at least another adjacent sleeve can perform the ethane catalytic dehydrogenation reaction, and a catalyst I for the methane oxidative coupling reaction and a catalyst II for the methane oxidative coupling reaction are sequentially filled in the tubes for performing the methane oxidative coupling reaction according to the flowing direction of reaction materials, wherein the reaction temperature of the catalyst I is not higher than 600 ℃, and the reaction temperature of the catalyst II is not lower than 700 ℃; filling a pipe for carrying out the ethane catalytic dehydrogenation reaction with a catalyst III for the ethane catalytic dehydrogenation reaction, wherein the catalyst III is selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
Compared with the prior art, the method provided by the invention at least has the following advantages:
the method provided by the invention can effectively solve the problem of high reaction temperature required by the oxidative coupling reaction of methane, reduce the operation cost and realize low-temperature activation and high-temperature reaction; in addition, the invention can also remove the heat generated in the high-temperature reaction of the methane oxidative coupling reaction, effectively prevent temperature runaway in the high-temperature reaction and ensure the progress of the methane oxidative coupling reaction.
In addition, the method provided by the invention also solves the problem of high heating temperature required by the ethane catalytic dehydrogenation reaction, reduces the energy consumption of the ethane catalytic dehydrogenation reaction, realizes the optimized utilization of energy and has wide application prospect.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
Detailed Description
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.
In the present invention, the reaction temperature refers to a temperature at which the catalyst can play a catalytic role to promote the reaction, and is generally within an interval range. Thus, the reaction temperature of the catalyst as defined herein is within a temperature range such as T1-T2, and means that the temperature at which the catalyst catalyzes to promote reaction is within the temperature range T1-T2, which may be any small range within the range T1-T2, or T1-T2.
As described above, the first aspect of the present invention provides a method for preparing ethylene by coupling an oxidative coupling reaction of methane with a catalytic dehydrogenation reaction of ethane, the method being performed in a fixed-bed shell-and-tube reactor having at least two layers of shell tubes, and the oxidative coupling reaction of methane being performed in at least one tube of the shell tubes and the catalytic dehydrogenation reaction of ethane being performed in at least another adjacent tube, wherein a catalyst I for the oxidative coupling reaction of methane and a catalyst II for the oxidative coupling reaction of methane are sequentially charged in a flow direction of a reaction material in the tube in which the oxidative coupling reaction of methane is performed, wherein a reaction temperature of the catalyst I is not higher than 600 ℃, and a reaction temperature of the catalyst II is not lower than 700 ℃; filling a tube in which the ethane catalytic dehydrogenation reaction is carried out with a catalyst III for the ethane catalytic dehydrogenation reaction, the catalyst III being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the method comprises the following steps: in the fixed-bed double-pipe reactor, introducing a reaction material I containing methane and oxygen into a pipe in which the oxidative coupling reaction of methane is carried out to carry out the oxidative coupling reaction of methane; and introducing a reaction mass II containing ethane into a tube in which the ethane catalytic dehydrogenation reaction is carried out to carry out the ethane catalytic dehydrogenation reaction;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
Under the action of the catalyst I (low-temperature active catalyst), the reaction materials can start to react when heated to low temperature, and the reaction materials in the reactor can reach the active temperature of the catalyst II (high-temperature active catalyst) along with the temperature rise of the reaction without external heating, so that the methane oxidative coupling reaction is smoothly carried out, the reaction temperature of the methane oxidative coupling reaction is reduced, and the reaction energy consumption is reduced; meanwhile, heat released by methane oxidation coupling under the high-temperature condition is absorbed through ethane catalytic dehydrogenation reaction, so that the reaction heat under the high-temperature condition is effectively removed, and temperature runaway under the high temperature is prevented.
Meanwhile, the method provided by the invention supplies the heat of the methane oxidative coupling reaction to the ethane catalytic dehydrogenation reaction without continuously supplying heat to the ethane catalytic dehydrogenation reaction and then supplying heat externally, so that the energy consumption of the ethane catalytic dehydrogenation reaction is reduced, the heat released by the methane oxidative coupling reaction is effectively utilized, the optimized utilization of energy is realized, and the method has a wide application prospect.
In the invention, the content of active components in the catalyst III is 0.1-5 wt% in terms of elements by taking the total weight of the catalyst III as a reference.
Preferably, the reaction material II further comprises at least one of hydrogen, nitrogen and an inert gas, and according to a preferred embodiment of the present invention, the reaction material II comprises ethane and nitrogen, wherein the molar ratio of the ethane to the nitrogen is 1: 0.1-10.
In the present invention, the catalyst I is all low-temperature activated catalysts which can be used for catalyzing the methane oxidative coupling reaction and can catalyze the reaction at a temperature of not higher than 600 ℃, but preferably, the reaction temperature of the catalyst I is 400-600 ℃, more preferably 440-600 ℃, so that the energy consumption of the reaction is lower in the methane oxidative coupling reaction.
In the invention, the catalyst II is all high-temperature activating catalysts which can be used for catalyzing the methane oxidative coupling reaction and can perform the catalytic reaction at the temperature of not less than 700 ℃, and preferably, the reaction temperature of the catalyst II is 720-900 ℃, so that the energy consumption of the reaction is lower in the methane oxidative coupling reaction.
Preferably, the reaction temperature of the catalyst III is 500-750 ℃, more preferably 500-650 ℃.
According to a preferred embodiment of the present invention, In order to obtain a higher olefin selectivity, the catalyst III is Pt-In/SiO2Or Pt-Sn/Mg (Al) O, wherein in the catalyst Pt-Sn/Mg (Al) O, the content molar ratio of Sn element to Pt element is 0.8-2: 1.
according to another preferred embodiment of the invention, the catalyst I is selected from the group consisting of lanthanum oxide, cerium oxide, zirconium oxide, titanium oxide, strontium oxide, barium oxide, lithium hydroxide, Fex1Oy1、V2O5、MoO3、CO3O4、Pt-Rh、Ag-Au、Au/CO3O4MgO, ZnO, strontium oxide/lanthanum oxide, barium oxide/lanthanum oxide, cerium oxide/lanthanum oxide, manganese oxide/lanthanum oxide, titanium oxide/lanthanum oxide, zinc oxide/lanthanum oxide, tin oxide/lanthanum oxide, bismuth oxide/lanthanum oxide, Pt/lanthanum oxide, Mo/lanthanum oxide, Fe/lanthanum oxide, Co/lanthanum oxide, Ni/lanthanum oxide, Cr/lanthanum oxide, Cd/lanthanum oxide, Sr/lanthanum oxide, Ce/lanthanum oxide, Yb/lanthanum oxide, Sr/lanthanum oxide1.0Ce0.9Yb0.1Sm0.2Ox2、La50Nd30Sr20、Sr1.0La0.9Ox3Wherein, Fex1Oy1X1 in (a) is 0.1 to 1; y1 is 0.1-1.5; sr1.0Ce0.9Yb0.1Sm0.2Ox2X2 in (a) is 1.5 to 2.5; sr1.0La0.9Ox3X3 in (1) is 1.5-3.
More preferably, the catalyst I is selected from lanthanum oxide, cerium oxide, strontium oxide/lanthanum oxide, barium oxide/lanthanum oxide, cerium oxide/lanthanum oxide, SrCeYb, Sr1.0Ce0.9Yb0.1Sm0.2Ox2、La50Nd30Sr20、Sr1.0La0.9Ox3Wherein, Sr is1.0Ce0.9Yb0.1Sm0.2Ox2X2 in (a) is 2 to 2.5; sr1.0La0.9Ox3X3 in (1.8-2.5).
Preferably, the particles of the catalyst I are nanoparticles, and the morphology of the catalyst I is selected from at least one of a nanorod, a nanosheet, a nanoflower and a nanocavity.
According to a further preferred embodiment of the present invention, the catalyst II comprises a carrier and an active component supported on the carrier, wherein the active component comprises a manganese element, a tungsten element, an alkali metal element and optionally an alkaline earth metal element.
Preferably, based on the total weight of the catalyst II, the content of the manganese element is 1-20 wt%, the content of the tungsten element is 2-15 wt%, the content of the alkali metal element is 0.5-8 wt%, and the content of the alkaline earth metal element is 0-4 wt%.
When the content of the alkaline earth metal element is 0, it means that the alkaline earth metal element is not contained in the catalyst II.
More preferably, in the catalyst II, the active component includes manganese element, tungsten element, and sodium element; the carrier is selected from at least one of silica, alumina, barium titanate, molecular sieve, cristobalite and cordierite.
Even more preferably, the catalyst II is modified or unmodified Na2WO4-Mn/SiO2A catalyst.
In the present invention, the modified Na2WO4-Mn/SiO2The catalyst refers to the catalyst modified by element doping, wherein each doping element is at least one of alkaline earth metal elements, alkali metal elements and rare earth metal elements, and the modified Na is2WO4-Mn/SiO2The content of the doping element is 0.01-4 wt% calculated by the total weight of the catalyst.
In the present invention, the catalyst I, the catalyst II and the catalyst III may be obtained commercially or may be obtained by self-preparation according to a method disclosed in a known literature.
Preferably, the loading weight ratio of the catalyst I to the catalyst II is 0.01-100: 1, more preferably 0.02 to 50: 1, more preferably 0.1 to 10: 1, whereby said catalyst I and said catalyst II cooperate, the conversion of methane and ethane is higher.
Preferably, the ratio of the total loading weight of the catalyst I and the catalyst II to the loading weight of the catalyst III is from 0.1 to 10: 1; more preferably 0.02 to 5: 1; more preferably 0.3 to 3: 1, thus, the energy consumption of the reaction is smaller, and the selectivity of the hydrocarbon is higher.
In the invention, the bed filling heights of the catalyst I, the catalyst II and the catalyst III can be reasonably adjusted according to the actual application requirements.
According to a particularly preferred embodiment, the fixed-bed double-shell tube reactor is a fixed-bed double-shell tube reactor, and the oxidative coupling of methane reaction is carried out in the outer tube of the fixed-bed double-shell tube reactor, and the catalytic dehydrogenation of ethane is carried out in the inner tube of the fixed-bed double-shell tube reactor.
Preferably, in the oxidative coupling reaction of methane, the space velocity of the oxidative coupling reaction of methane is 0.1-10 ten thousand mL-g based on the methane contained in the reaction material I-1·h-1(ii) a More preferably 0.2 to 8 ten thousand mL g-1·h-1。
Preferably, in the methane oxidative coupling reaction, the molar ratio of the methane and the oxygen in the reaction material I is 1-10: 1, more preferably 3 to 10: 1.
preferably, in the catalytic dehydrogenation reaction of ethane, the space velocity of the catalytic dehydrogenation of ethane is 0.1 ten thousand to 10 ten thousand mL-g based on ethane contained in the reaction material II-1·h-1More preferably 0.5 to 8 ten thousand mL g-1·h-1。
Preferably, in the fixed bed jacketed pipe reactor, the reaction material I and the reaction material II run in countercurrent.
In the present invention, the reaction material I and the reaction material II may be introduced into the fixed-bed shell-and-tube reactor at the same time or at intervals, and preferably, the reaction material II is introduced when the reaction material I is introduced for 0.5 to 3min, whereby heat can be more effectively utilized and costs can be saved.
The specific type of material of the fixed-bed shell-and-tube reactor is not particularly required in the present invention, as long as the heat transfer can be carried out to realize the heat transfer between the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction, and the material can be quartz, metal stainless steel, metal inconel, etc., for example.
In the invention, the reaction materials and reaction products of the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction are respectively carried out in two reaction channels of the fixed bed-in-tube reactor in the whole reaction process, and the reaction products are respectively measured by a gas chromatograph.
As described above, the second aspect of the present invention provides a system for preparing ethylene by coupling an oxidative coupling reaction of methane with a catalytic dehydrogenation reaction of ethane, the system comprising a fixed-bed shell-and-tube reactor having at least two layers of shell-and-tube, and the oxidative coupling reaction of methane being carried out in at least one of the tubes of the shell-and-tube reactor and the catalytic dehydrogenation reaction of ethane being carried out in at least another of the adjacent tubes, wherein the oxidative coupling reaction of methane is carried out in accordance with the flow of the reaction materials in the tubes in which the oxidative coupling reaction of methane is carried outSequentially filling a catalyst I for the methane oxidative coupling reaction and a catalyst II for the methane oxidative coupling reaction, wherein the reaction temperature of the catalyst I is not higher than 600 ℃, and the reaction temperature of the catalyst II is not lower than 700 ℃; filling a tube in which the ethane catalytic dehydrogenation reaction is carried out with a catalyst III for the ethane catalytic dehydrogenation reaction, the catalyst III being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
In the second aspect of the present invention, the types and the amounts of the catalyst I, the catalyst II and the catalyst III are the same as those of the catalyst I, the catalyst II and the catalyst III described in the first aspect, and the description of the present invention is omitted, and a person skilled in the art should not be construed as limiting the present invention.
In a second aspect of the present invention, according to a preferred embodiment of the present invention, the fixed-bed double-shell tube reactor is a fixed-bed double-shell tube reactor, and the oxidative coupling reaction of methane is performed in an outer tube of the fixed-bed double-shell tube reactor, and the catalytic dehydrogenation reaction of ethane is performed in an inner tube of the fixed-bed double-shell tube reactor.
The system provided by the invention can couple the methane oxidation reaction with the ethane catalytic dehydrogenation reaction, and not only can effectively solve the problem of high reaction temperature required by the methane oxidation coupling reaction; in addition, the invention can also remove the heat generated in the high-temperature reaction of the methane oxidative coupling reaction, effectively prevent temperature runaway in the high-temperature reaction and ensure the progress of the methane oxidative coupling reaction.
Meanwhile, the problem of high heating temperature required by the ethane catalytic dehydrogenation reaction can be solved, the energy consumption of the ethane catalytic dehydrogenation reaction is reduced, and the optimized utilization of energy is realized.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
Catalyst I: lanthanum oxide is purchased from national chemical reagent limited and is of high-grade purity;
catalyst II: na (Na)2WO4-Mn/SiO2The catalyst Na was obtained by preparing the catalyst according to the method of CN111203283A and adjusting the kinds and amounts of the raw materials as required2WO4-Mn/SiO2In the composition, Mn content is 2 wt%, and Na2WO4The content of (b) is 5 wt%;
catalyst III: Pt-In/SiO2Reference is made to the literature (WEGENER E C, WU Z, TSENG H-T, et al. Structure and reactivity of Pt-In interactive nanoparticles: high hly selective catalysts for ethane dehydrogenation [ J]The catalyst Pt-In/SiO 153) is prepared by the method In Catalysis Today,2018(299):146-2In the catalyst, the content of Pt element was 0.2 wt% and the content of In element was 0.3 wt% based on the total weight of the catalyst.
In the following examples, the reaction products of the oxidative coupling of methane reaction and the catalytic dehydrogenation of ethane were determined by means of an Agilent gas chromatograph, model 7890A, manufactured by Agilent.
In the following examples, the fixed-bed double-layered reactors were all made of Inconel metal.
In the following examples, reaction Mass I
Methane conversion ═ molar amount of methane consumed by the reaction/initial molar amount of methane × 100%
Ethylene selectivity-the molar amount of methane consumed to form ethylene/the molar amount of methane consumed for the reaction x 100%
Ethane selectivity-the molar amount of methane consumed for ethane formation/the molar amount of methane consumed for reaction x 100%
Selectivity to carbo-carb-ol ethane + ethylene selectivity
In the following examples, reaction Mass II
Ethane conversion rate ═ molar amount of ethane consumed by reaction/initial molar amount of ethane × 100%
Ethylene selectivity ═ moles of ethane consumed to form ethylene/moles of ethane consumed in the reaction x 100%
In the following examples, both reaction mass I and reaction mass II were run in countercurrent, unless otherwise specified.
Example 1
In the outer tube of the fixed bed double-tube reactor, 0.2g of lanthanum oxide (catalyst I) and 0.4g of Na were sequentially charged in the flow direction of the reaction materials2WO4-Mn/SiO2(catalyst II) In the inner tube of the fixed-bed double-tube reactor, 0.5g of Pt-In/SiO was charged2(catalyst III); introducing methane and oxygen (reaction material I) into an outer pipe of a fixed bed double-pipe reactor, wherein the space velocity of the methane is 2 ten thousand mL-g-1·h-1The molar ratio of methane to oxygen is 4: 1; after methane was fed for 0.5min, ethane and nitrogen (reaction material II) were fed into the inner tube of the fixed-bed double-tube reactor at an ethane space velocity of 6 kallmage g-1·h-1Ethane to nitrogen molar ratio of 1: 1;
heating a reaction material I to 550 ℃, wherein the reaction material I firstly contacts a catalyst I to start a methane oxidative coupling reaction, and as the reaction is an exothermic reaction, the temperature of the reaction material I rises to 750 ℃ along with the progress of the reaction, and then the reaction is continued through a catalyst II; and simultaneously, when the temperature of a bed layer of the catalyst III in the reactor rises to 600 ℃, the ethane catalytic dehydrogenation reaction in the inner pipe of the jacketed pipe reactor starts to be carried out, and the methane conversion rate and the carbon dioxide hydrocarbon selectivity of the methane oxidative coupling reaction in the outer pipe and the ethane conversion rate and the ethylene selectivity of the ethane catalytic dehydrogenation reaction in the inner pipe are respectively measured through Agilent 7890A gas chromatography.
As a result: methane conversion was 40.1%, and carbo-dehyd selectivity was 52.3%; the ethane conversion was 18% and the ethylene selectivity was 78%.
In this example, the initial heating temperature for the reaction was 550 ℃ and the hot spot temperature of the bed for the oxidative coupling of methane during the reaction was 832 ℃.
Example 2
A similar procedure was followed as in example 1, except that in this example:
the space velocity of methane is 1 ten thousand mL g-1·h-1The molar ratio of methane to oxygen is 6: 1; the space velocity of ethane is 1 ten thousand mL g-1·h-1(ii) a Heating the reaction material I to 450 ℃ to start reaction, and the rest is the same as the example 1;
as a result: methane conversion 28.2%, and carbo-diimide selectivity 60.2%; the ethane conversion was 17.9% and the ethylene selectivity was 78%.
In this example, the initial heating temperature for the reaction was 450 ℃ and the hot spot temperature of the bed for the oxidative coupling of methane during the reaction was 850 ℃.
Example 3
A similar procedure was followed as in example 1, except that in this example:
the space velocity of methane is 5 ten thousand mL g-1·h-1The molar ratio of methane to oxygen is 3: 1; the space velocity of ethane is 8 ten thousand mL g-1·h-1(ii) a Heating the reaction material I to 465 ℃ to start reaction, and the rest is the same as the example 1;
as a result: methane conversion was 43% and carbo-diimide selectivity was 45.5%; the ethane conversion was 26% and the ethylene selectivity was 82.1%.
In this example, the initial heating temperature for the reaction was 465 ℃ and the hot spot temperature of the bed for the oxidative coupling of methane during the reaction was 842 ℃.
Example 4
In a similar manner to example 1, except that in this example:
the amounts of catalyst I and catalyst II used were different from those in example 1, but the kind of catalyst I and the kind of catalyst II in this example were the same as those in example 1, respectively.
Specifically, the loading of catalyst I was 0.04g and the loading of catalyst II was 0.56 g.
As a result: methane conversion was 38.1%, and carbo-diimide selectivity was 51.1%; ethane conversion was 16% and ethylene selectivity was 74%.
In this example, the initial heating temperature for the reaction was 550 ℃ and the hot spot temperature of the bed for the oxidative coupling of methane during the reaction was 850 ℃.
Example 5
In a similar manner to example 1, except that in this example:
the loading of catalyst III was different from that in example 1, but the kind of catalyst III in this example was the same as that in example 1.
Specifically, the loading of catalyst III was 3 g.
As a result: methane conversion was 41.5%, and carbo-diimide selectivity was 46.3%; the ethane conversion was 13.8% and the ethylene selectivity was 76.5%.
In this example, the initial heating temperature for the reaction was 550 ℃ and the hot spot temperature of the bed for the oxidative coupling of methane during the reaction was 842 ℃.
Comparative example 1
A similar procedure was followed as in example 1, except that in this comparative example no coupling of the ethane-catalyzed dehydrogenation reaction was carried out and the catalyst for carrying out the oxidative coupling of methane was catalyst II only.
Specifically, 0.6g of Na was added2WO4-Mn/SiO2The catalyst is filled in the outer pipe of the fixed bed double-layer sleeve pipe reactor; introducing methane and oxygen into an outer pipe of the fixed bed double-pipe reactor, wherein the space velocity of the methane is 2 ten thousand ml/gh, and the molar ratio of the methane to the oxygen is 4: 1; heating the reaction mass to 750 ℃, carrying out methane oxidation coupling reaction, and measuring CH in the outer tube of the reactor by Agilent 7890A gas chromatography4Conversion and carbo-carburisation selectivity.
As a result: methane conversion was 34.2%, and carbo-diimide selectivity was 53.4%;
in this comparative example, the initial heating temperature for the reaction was 750 ℃ and the hot spot temperature of the bed for the oxidative coupling reaction of methane during the reaction was 985 ℃.
From the above results, it can be seen that the method of the present invention not only can activate reaction at low temperature and reduce reaction temperature, but also can reduce the hot spot temperature of the reaction bed layer by coupling with the ethane catalytic dehydrogenation reaction, effectively remove the reaction heat under high temperature condition, and prevent temperature runaway at high temperature.
In conclusion, under the action of the low-temperature activation catalyst, the reaction materials can start to react when heated to the low temperature of 450 ℃, and the reaction materials in the reactor can reach the reaction temperature of the high-temperature catalyst along with the temperature rise of the reaction without external heating, so that the methane oxidation coupling reaction is smoothly carried out, and the low-temperature activation is realized; meanwhile, heat released by the methane oxidation coupling reaction under the high-temperature condition is absorbed through the ethane catalytic dehydrogenation reaction, so that the effective removal of reaction heat under the high-temperature condition is effectively realized, the temperature runaway under the high temperature is prevented, and the methane oxidation coupling reaction is ensured.
In addition, the method provided by the invention also has the advantage of reducing the energy consumption of the ethane catalytic dehydrogenation reaction, does not need to continuously supply heat to the ethane catalytic dehydrogenation reaction, realizes the optimized utilization of energy, and has wide application prospect.
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 (11)

1. A process for the preparation of ethylene by oxidative coupling of methane with catalytic dehydrogenation of ethane, characterized in that it is carried out in a fixed-bed tubular reactor comprising at least two sleeves, and in that the oxidative coupling of methane is carried out in at least one of the sleeves and the catalytic dehydrogenation of ethane is carried out in at least one other adjacent sleeve, while the oxidative coupling of methane is carried outSequentially filling a catalyst I for the methane oxidative coupling reaction and a catalyst II for the methane oxidative coupling reaction in a coupling reaction pipe according to the flowing direction of reaction materials, wherein the reaction temperature of the catalyst I is not higher than 600 ℃, and the reaction temperature of the catalyst II is not lower than 700 ℃; filling a tube in which the ethane catalytic dehydrogenation reaction is carried out with a catalyst III for the ethane catalytic dehydrogenation reaction, the catalyst III being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the method comprises the following steps: in the fixed-bed double-pipe reactor, introducing a reaction material I containing methane and oxygen into a pipe in which the oxidative coupling reaction of methane is carried out to carry out the oxidative coupling reaction of methane; and introducing an ethane-containing reaction material II into a tube in which the ethane catalytic dehydrogenation reaction is performed to perform the ethane catalytic dehydrogenation reaction;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
2. The method as claimed in claim 1, wherein the reaction temperature of the catalyst I is 400-600 ℃;
preferably, the reaction temperature of the catalyst II is 720-900 ℃;
preferably, the reaction temperature of the catalyst III is 500-750 ℃.
3. The process according to claim 1 or 2, wherein the catalyst I is selected from lanthanum oxide, cerium oxide, zirconium oxide, titanium oxide, strontium oxide, barium oxide, lithium hydroxide, Fex1Oy1、V2O5、MoO3、CO3O4、Pt-Rh、Ag-Au、Au/CO3O4MgO, ZnO, strontium oxide/lanthanum oxide, barium oxide/lanthanum oxideCerium oxide/lanthanum oxide, manganese oxide/lanthanum oxide, titanium oxide/lanthanum oxide, zinc oxide/lanthanum oxide, tin oxide/lanthanum oxide, bismuth oxide/lanthanum oxide, Pt/lanthanum oxide, Mo/lanthanum oxide, Fe/lanthanum oxide, Co/lanthanum oxide, Ni/lanthanum oxide, Cr/lanthanum oxide, Cd/lanthanum oxide, Sr/lanthanum oxide, Ce/lanthanum oxide, Yb/lanthanum oxide, Sr/lanthanum oxide1.0Ce0.9Yb0.1Sm0.2Ox2、La50Nd30Sr20、Sr1.0La0.9Ox3Wherein, Fex1Oy1X1 in (a) is 0.1 to 1; y1 is 0.1-1.5; sr1.0Ce0.9Yb0.1Sm0.2Ox2X2 in (a) is 1.5 to 2.5; sr1.0La0.9Ox3X3 in (1.5-3);
more preferably, the catalyst I is selected from lanthanum oxide, cerium oxide, strontium oxide/lanthanum oxide, barium oxide/lanthanum oxide, cerium oxide/lanthanum oxide, SrCeYb, Sr1.0Ce0.9Yb0.1Sm0.2Ox2、La50Nd30Sr20、Sr1.0La0.9Ox3Wherein, Sr is1.0Ce0.9Yb0.1Sm0.2Ox2X2 in (a) is 2 to 2.5; sr1.0La0.9Ox3X3 in (a) is 1.8 to 2.5;
preferably, the particles of the catalyst I are nanoparticles, and the morphology of the catalyst I is selected from at least one of a nanorod, a nanosheet, a nanoflower and a nanocavity.
4. The method according to any one of claims 1 to 3, wherein the catalyst II comprises a carrier and an active component loaded on the carrier, wherein the active component comprises a manganese element, a tungsten element and an alkali metal element, and the active component optionally further comprises an alkaline earth metal element;
preferably, based on the total weight of the catalyst II, the content of the manganese element is 1-20 wt%, the content of the tungsten element is 2-15 wt%, the content of the alkali metal element is 0.5-8 wt%, and the content of the alkaline earth metal element is 0-4 wt%;
preferably, in the catalyst II, the active component includes manganese element, tungsten element, and sodium element; the carrier is selected from at least one of silica, alumina, barium titanate, molecular sieve, cristobalite, and cordierite.
5. The process according to any one of claims 1 to 3, wherein the loading weight ratio of catalyst I and catalyst II is from 0.01 to 100: 1, preferably 0.02 to 50: 1, more preferably 0.1 to 10: 1.
6. the process of any of claims 1-5, wherein the ratio of the total loading weight of catalyst I and catalyst II to the loading weight of catalyst III is from 0.1 to 10: 1; preferably 0.02 to 5: 1; more preferably 0.3 to 3: 1.
7. the process according to any one of claims 1 to 6, wherein the fixed-bed double-shell tube reactor is a fixed-bed double-shell tube reactor, and the oxidative coupling reaction of methane is carried out in an outer tube of the fixed-bed double-shell tube reactor, and the catalytic dehydrogenation reaction of ethane is carried out in an inner tube of the fixed-bed double-shell tube reactor.
8. The process according to any one of claims 1 to 7, wherein in the oxidative coupling of methane, the space velocity of the oxidative coupling of methane is from 0.1 to 10 ten thousand mL-g, based on the methane contained in the reaction material I-1·h-1(ii) a Preferably 0.2 to 8-ten thousand mL g-1·h-1；
Preferably, in the methane oxidative coupling reaction, the molar ratio of the methane and the oxygen in the reaction material I is 1-10: 1, preferably 3 to 10: 1.
9. the process of any one of claims 1 to 8, wherein in the catalytic dehydrogenation reaction of ethane, the reaction mass II comprisesThe space velocity of the catalytic dehydrogenation of the ethane is 0.1-10 ten thousand mL-g by counting the ethane-1·h-1Preferably 0.5 to 8 ten thousand mL g-1·h-1。
10. The process according to any one of claims 1-9, wherein in the fixed-bed shell-and-tube reactor the reaction mass I and the reaction mass II are run in countercurrent.
11. A system for preparing ethylene by coupling methane oxidative coupling reaction and ethane catalytic dehydrogenation reaction is characterized in that the system comprises a fixed bed sleeve reactor comprising at least two layers of sleeves, at least one of the sleeves can carry out the methane oxidative coupling reaction, and at least another adjacent sleeve can carry out the ethane catalytic dehydrogenation reaction, and a catalyst I for the methane oxidative coupling reaction and a catalyst II for the methane oxidative coupling reaction are sequentially filled in the tubes for carrying out the methane oxidative coupling reaction according to the flowing direction of reaction materials, wherein the reaction temperature of the catalyst I is not higher than 600 ℃, and the reaction temperature of the catalyst II is not lower than 700 ℃; filling a tube in which the ethane catalytic dehydrogenation reaction is carried out with a catalyst III for the ethane catalytic dehydrogenation reaction, the catalyst III being selected from Pt/SiO2、Pt-In/SiO2、Pt/Mg(Al)O、Pt-Sn/Mg(Al)O、Pt-Ir/Mg(Al)O、Pt-Sn/Mg(Ga)(Al)O、Pt-Zn/ETS-2、Cr/BaZrO3、Cr/BaCeO3、Cr/MCM-41、Ga/HZSM-5、P-Mo/ZSM-5、Pd-In/SiO2At least one of;
the fixed bed shell and tube reactor is made of a material which enables heat transfer between tubes for performing the methane oxidative coupling reaction and the ethane catalytic dehydrogenation reaction.
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