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WO2018124791A1 - Réacteur à microcanaux à échange de chaleur pour couplage oxydant de méthane - Google Patents

Réacteur à microcanaux à échange de chaleur pour couplage oxydant de méthane Download PDF

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WO2018124791A1
WO2018124791A1 PCT/KR2017/015693 KR2017015693W WO2018124791A1 WO 2018124791 A1 WO2018124791 A1 WO 2018124791A1 KR 2017015693 W KR2017015693 W KR 2017015693W WO 2018124791 A1 WO2018124791 A1 WO 2018124791A1
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reaction
methane
flow path
endothermic
catalyst
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PCT/KR2017/015693
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English (en)
Korean (ko)
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이윤조
박선주
김석기
곽근재
전기원
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한국화학연구원
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Priority claimed from KR1020160181386A external-priority patent/KR102079036B1/ko
Priority claimed from KR1020170169774A external-priority patent/KR102032482B1/ko
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2018124791A1 publication Critical patent/WO2018124791A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • 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
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/04—Methane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
    • C07C9/06—Ethane

Definitions

  • the methane oxidative dimerization reaction channel and the endothermic reaction flow path of the exothermic reaction are alternately provided, and the temperature (T 1 ) of the exothermic reaction flow path is higher than the temperature (T 2 ) of the endothermic reaction flow path from the exothermic reaction path to the endothermic reaction flow path.
  • Heat exchange microchannel reactor for heat transfer; And to converting methane in the heat exchange microchannel reactor to produce a gas product.
  • the present invention also relates to a method for more efficiently converting methane by combining an oxidative dimerization reaction of methane which is an exothermic reaction and a steam reforming reaction of methane which is an endothermic reaction.
  • Methane the main component of natural gas, is mainly used for power generation or domestic heat sources, but some are used as raw materials for producing liquid fuels or chemicals. Methane conversion reaction for this is mostly through the reforming reaction of methane, a synthesis gas manufacturing process. These syngases are used as raw materials for methanol synthesis, hydrogen production, ammonia production or synthetic oil production by Fischer-Tropsch reaction.
  • the oxidative coupling of methane has a merit as a reaction that is directly converted to ethylene and ethane by the reaction of methane and oxygen on the catalyst, but accompanied by various side reactions.
  • Methane and oxygen react to form ethylene or ethane according to the forward reaction as in Scheme 1) or Scheme 2). In this process, very strong exothermic reaction may occur with side reactions such as Scheme 3) and Scheme 4). .
  • the reaction temperature is not easy to control the reaction heat of the reaction forward, the reaction proceeds further with CO and CO 2 to reduce the yield of the desired C 2 hydrocarbon compound. Therefore, control of the heat of reaction in the oxidative dimerization of methane is important for the stability of the reaction process as well as the yield of the product.
  • methane reforming reaction is a strong endothermic reaction, as shown in the following reaction scheme, unlike methane oxidative dimerization reaction. That is, a lot of heat must be supplied from the outside in order for methane reforming to occur.
  • methane may react with water vapor as in Scheme 5), carbon dioxide may be used instead of water vapor as in Scheme 6), and steam and carbon dioxide may be used at the same time as in Scheme 7).
  • Methane is a very stable compound, and when it is converted to another compound, there is a problem that thermal efficiency is lowered because it involves a very strong endothermic reaction or exothermic reaction.
  • thermal efficiency is lowered because it involves a very strong endothermic reaction or exothermic reaction.
  • a microchannel reactor has a plate stacked structure, in which a catalyst layer has a cooling layer above and below, and a catalyst layer has a thickness of several millimeters.
  • the microchannel reactor has attracted attention as a strong exothermic or endothermic reactor because of its excellent heat exchange performance since the heat transfer area is 10 to 100 times larger than the conventional tube-type fixed bed catalytic reactor.
  • Microchannel reactors are currently being commercialized as compact reactors of the Fischer-Tropsch reaction, a highly exothermic reaction.
  • the inventors of the present invention implement reactions in which the entire reaction is thermally neutralized using a reactor having excellent heat exchange in one reactor, and the products of these reactions are recycled to each reaction of the unreacted product through a secondary reaction. It was confirmed that the efficiency of the and completed the present invention. Therefore, the present invention is to improve the thermal efficiency of the reaction by performing the reaction in the thermal neutral conditions when the conversion from methane to other compounds, and to provide a high efficiency methane conversion method through integration with the secondary reaction.
  • the present invention also provides a microchannel reactor in which a strong exothermic reaction layer and a strong endothermic reaction catalyst layer are separated from each other and alternately stacked, and easily control heat of reaction and have high thermal efficiency in a reaction process.
  • the first aspect of the present invention is provided with an exothermic reaction flow path and an endothermic reaction flow path, wherein the temperature (T 1 ) of the exothermic reaction flow path where the oxidative dimerization reaction of methane is performed is performed in the endothermic reaction flow path where the steam reforming reaction of methane is performed.
  • T 1 the temperature of the exothermic reaction flow path where the oxidative dimerization reaction of methane is performed
  • the first step of performing oxidative dimerization of methane in the exothermic reaction passage and performing steam reforming reaction of methane in the endothermic reaction passage It provides a method of converting methane characterized in that it comprises a.
  • ethylene and / or ethane are formed as a product as C2 hydrocarbons by the oxidative dimerization reaction of methane in a first step, and a synthesis gas is formed as a product by steam reforming of methane, optionally, formed in the first step.
  • the second aspect of the present invention includes one or more exothermic reaction passages and two or more endothermic reaction passages, wherein the temperature (T 1 ) of the exothermic reaction passage is higher than the temperature (T 2 ) of the endothermic reaction passage and endothermic from the exothermic reaction passage.
  • T 1 the temperature of the exothermic reaction passage
  • T 2 the temperature of the endothermic reaction passage and endothermic from the exothermic reaction passage.
  • Heat exchange microchannel reactor characterized in that the reaction temperature in the exothermic reaction passage is controlled within the range of 800 °C ⁇ 50 °C, the reaction temperature in the endothermic reaction passage through the heat exchange with the exothermic reaction passage is controlled within the range of 750 °C ⁇ 50 °C To provide.
  • the third aspect of the present invention includes one or more exothermic reaction passages and two or more endothermic reaction passages, wherein the temperature T 1 of the exothermic reaction passage is higher than the temperature T 2 of the endothermic reaction passage and endothermic from the exothermic reaction passage.
  • a heat exchange microchannel reactor in which heat is transferred to a reaction passage, an exothermic reaction passage is filled with a catalyst for oxidative dimerization reaction of methane, an endothermic reaction passage is filled with a catalyst for endothermic reaction, and the calorific value of the exothermic reaction passage can be controlled.
  • the thickness of a catalyst bed in an exothermic reaction flow path located between two adjacent endothermic flow paths is controlled within a range of 1 to 5 mm.
  • the thickness of the catalyst bed in the endothermic reaction flow path may be adjusted within 0.1 to 2 times the thickness of the catalyst layer in the exothermic reaction flow path so as to remove the calorific value downstream in the exothermic reaction flow path.
  • the fourth aspect of the present invention includes one or more exothermic reaction passages and two or more endothermic reaction passages, and the temperature (T 1 ) of the exothermic reaction passage is higher than the temperature (T 2 ) of the endothermic reaction passage and endothermic from the exothermic reaction passage.
  • a heat exchange microchannel reactor in which heat is transferred to a reaction flow path, an exothermic reaction flow path is filled with a catalyst for oxidative dimerization reaction of methane, an endothermic reaction flow path is filled with a catalyst for reforming reaction of methane, and
  • the reforming reaction provides a heat exchange microchannel reactor characterized by controlling the conversion of methane to 95% or less of equilibrium conversion under reaction conditions by controlling catalytic activity.
  • the fifth aspect of the present invention includes one or more exothermic reaction passages and two or more endothermic reaction passages, wherein the temperature T 1 of the exothermic reaction passage is higher than the temperature T 2 of the endothermic reaction passage and endothermic from the exothermic reaction passage.
  • an exothermic reaction flow path is filled with a catalyst for oxidative dimerization reaction of methane
  • an endothermic reaction flow path is filled with a catalyst for reforming reaction of methane, and upstream of the exothermic reaction flow path.
  • the methane conversion rate is 60% to 95% in the reforming reaction of methane in the endothermic passage to lower the rate of oxidative dimerization of the methane to suppress rapid temperature increase and to remove the calorific value of the oxidative dimerization reaction of methane downstream in the exothermic passage. It provides a heat exchange microchannel reactor characterized by being controlled in a range.
  • the sixth aspect of the present invention provides a method for producing a gas product by converting methane or ethane in the heat exchange microchannel reactor of the second to fifth aspects.
  • the catalyst packed in the endothermic flow path may be a catalyst for reforming the methane, and the synthesis gas may be prepared by reforming the methane in the endothermic flow path.
  • the catalyst packed in the endothermic flow path may be a catalyst for dehydrogenation of ethane, and ethylene may be prepared through pyrolysis of ethane without additional catalyst filling. have.
  • the present invention achieves the thermal neutral reaction conditions by performing heat exchange reaction of methane which is exothermic reaction and steam reforming reaction of methane which is endothermic at the same time to improve the thermal efficiency of the process, and through integration with the rear end reaction It can provide a high efficiency whole integrated process.
  • the present invention provides a means for effectively controlling the heat of reaction by exchanging and receiving the heat of reaction by simultaneously carrying out the oxidative dimerization reaction and endothermic reaction of methane exothermic reaction using a heat exchange microchannel reactor, thereby selecting a high C2 product It is possible to provide a way to more efficiently convert methane by improving the thermal efficiency of the process by obtaining a diagram and achieving thermal neutral reaction conditions.
  • 1 is a schematic of a process for preparing a liquid hydrocarbon or compound in methane.
  • FIG. 2 is a process schematic diagram illustrating the conversion process of the methane-containing gas in more detail.
  • FIG. 3 is a schematic diagram (a) of a microchannel reactor in which methane oxidative dimerization (OCM) and steam reforming (SMR) of methane occurs, in-channel exothermic and endothermic reactions, and heat exchange between channels;
  • OCM methane oxidative dimerization
  • SMR steam reforming
  • Figure 4 shows the parallel conversion rate according to the reaction temperature of the methane reforming reaction under various reaction conditions
  • the methane conversion method of the present invention is characterized in that the thermal neutral reaction is performed by exchanging heat of reaction by performing oxidative dimerization reaction of methane and steam reforming reaction of methane in one reactor.
  • the methane conversion method of the present invention comprises the exothermic reaction flow path and the endothermic reaction flow path of the oxidative dimerization reaction of methane and the steam reforming reaction of methane, and the temperature of the exothermic reaction flow path where the oxidative dimerization reaction of methane is performed (T 1 ) is higher than the temperature (T 2 ) of the endothermic reaction flow path where the steam reforming reaction of methane is being performed, characterized in that it is carried out in a heat exchange reactor in which heat transfer from the exothermic reaction flow path to the endothermic reaction flow path.
  • the heat exchange reactor may be a microchannel reactor, and each channel of the microchannel reactor may be filled with a catalyst for oxidative dimerization of methane or a catalyst for steam reforming of methane.
  • the methane conversion method according to the first aspect of the present invention is characterized in that in the heat exchange reactor, a oxidative dimerization reaction of methane is carried out in an exothermic passage and a steam reforming reaction of methane is carried out in an endothermic reaction passage. It is done. At this time, each reaction occurs while passing through the catalyst layer in the channel of the heat exchange reactor.
  • the reactant injected into the heat exchange reactor of the first stage does not need to be 100% methane, which contains methane as a main component, and may be derived from natural gas or petrochemical by-products, and furthermore, a small amount of ethane, propane or nitrogen or carbon dioxide. It may include.
  • Another steam reforming reaction of the methane of the first step is a reaction of reacting methane with steam, carbon dioxide, or a mixture thereof to generate syngas (CO + H 2 ).
  • Steam reforming of methane occurs at 700–900 ° C., a reaction temperature similar to that of methane oxidative dimerization, but a strong endothermic reaction occurs.
  • the steam reforming reaction of methane is preferably carried out at a reaction pressure of 1 to 30 bar and a molar ratio of water vapor / methane of 1 to 4. Since the ratio of H 2 / CO of syngas obtained in steam reforming of methane is higher than 3, in the present invention, subsequent reactions utilizing these syngases are either methanol synthesis or Fischer-Tropsch reactions. In order to lower the H 2 / CO ratio H 2 O / CH 4 ratio was lowered and carbon dioxide was added to some reactions.
  • CH 4: H 2 O: CO 2 molar ratio is 1: 1.5 ⁇ 2.0: 0.4 ⁇ 0.8 when a is the reaction temperature is 800 ⁇ 850 °C, the H 2 / CO molar ratio of 2.0 ⁇ 2.5 degree methanol synthesis or Syngas suitable for Fischer-Tropsch reactions can be obtained.
  • the oxidative dimerization reaction of methane and the steam reforming reaction of methane are important for the transfer of reaction heat in close contact with each other in the same reactor, and it is preferable to use a microchannel reactor for this purpose.
  • the microchannel reactor may be suitable for a reaction having a large heat transfer area relative to the volume of the reactor.
  • the heat exchanging microchannel reactor includes one or more exothermic reaction passages and two or more endothermic reaction passages, and the exothermic reaction passage temperature T 1 is higher than the temperature of the endothermic reaction passage T 2 .
  • Heat is transferred from the reaction passage to the endothermic reaction passage, the exothermic reaction passage is filled with a catalyst for oxidative dimerization reaction of methane, and the endothermic reaction passage is filled with a catalyst for endothermic reaction.
  • the exothermic reaction flow path and / or the endothermic reaction flow path may be charged with a particulate catalyst to form a catalyst layer.
  • a catalyst-free reaction eg, a catalyst cracking / pyrolysis reaction of ethane
  • the endothermic reaction can absorb the heat of the exothermic reaction so that the endothermic reaction can be carried out.
  • the endothermic reaction can absorb the heat of the exothermic reaction so that the endothermic reaction can be carried out.
  • the endothermic reaction is not particularly limited, but when the exothermic reaction is oxidative dimerization of methane, the endothermic reaction may be a reforming reaction of methane and / or a dehydrogenation or pyrolysis reaction of ethane.
  • the optimum reaction temperature for the oxidative dimerization reaction of methane is around 800 °C, which is somewhat different depending on the catalyst, but the yield of C 2 hydrocarbon compound is maximized near 800 °C, and below 750 °C, most of the methane oxidative dimerization catalyst There is little activity, and the selectivity of the C 2 product is greatly reduced above 900 ° C.
  • Methane reforming is a reaction in which methane is reacted with steam, carbon dioxide, or a mixture thereof to produce syngas (CO + H 2 ).
  • the reforming reaction of methane occurs at 600 ⁇ 900 °C, which is similar to the oxidative dimerization reaction of methane, but a strong endothermic reaction occurs.
  • the methane reforming reaction can achieve high methane conversion around 700-800 degrees.
  • the reforming reaction of methane is a reversible reaction and the equilibrium conversion increases with increasing reaction temperature. As shown in FIG.
  • reaction temperature of methane reforming reaction is around 700 °C
  • reaction temperature of oxidative dimerization reaction of methane is 800 °C
  • the heat exchange microchannel reactor capable of heat transfer to the endothermic reaction passage is controlled in the exothermic reaction passage through heat exchange with the endothermic reaction passage in the reaction temperature within the range of 800 ° C. ⁇ 50 ° C.
  • the reaction temperature in the endothermic reaction passage through heat exchange with the reaction passage is characterized in that it is controlled within the range of 750 °C ⁇ 50 °C.
  • the oxidation dimerization reaction of methane is 700 ⁇ 900 °C, preferably 800 °C ⁇ 50 °C, the reaction pressure 1 ⁇ 10 bar, methane / oxygen molar ratio is 2 ⁇ 10, space velocity is 1000 ⁇ 50000 h -1 .
  • Temperature control of the oxidative dimerization reaction layer of methane in the microchannel reactor according to the present invention may be achieved by controlling the injection amount of the reactant of the steam reforming reaction of methane compared to the oxidative dimerization reactant. As the reactants of the steam reforming reaction of methane increases, the endothermic reaction may increase and the temperature of the oxidative dimerization reaction of methane may drop.
  • Combining the oxidative dimerization reaction of methane and the steam reforming reaction of methane as in the present invention has the advantage that the waste heat of the oxidative dimerization reaction of methane can be utilized as the reaction heat of the methane reforming reaction, the reaction heat of the oxidative dimerization reaction of methane There is an easier advantage to solve the problem of the prior art, which requires the use of much more high temperature steam in order to control the exothermic amount of the high temperature reaction.
  • the plates are stacked vertically at regular intervals, each reaction is alternately made in the channel consisting of plates
  • Each channel used a microchannel reactor filled with a catalyst (see FIG. 3 (b)).
  • the catalytic reaction layer of each channel may be an exothermic reaction flow path or an endothermic reaction flow path.
  • the present invention was adjusted so that the reaction conditions of the endothermic reactions performed adjacent to the reaction heat of the exothermic reaction correspond to the conditions of the exothermic reaction.
  • the reactor structure, the catalytic performance control, and the reaction condition control in the endothermic reaction are necessary for the exothermic reaction heat control.
  • the present invention proposes a reaction heat control method of the exothermic reaction in the heat exchange microchannel reactor.
  • the first method relates to the structure of a microchannel reactor, in which the contact time of the reactants of the methane reforming reaction layer is controlled by controlling the thickness of the methane reforming catalyst layer relative to the thickness of the catalytic reaction layer of the oxidative dimerization reaction of methane. It is a way.
  • the thickness of the oxidation dimerization catalyst layer of methane is suitably 1 to 5 mm. When the thickness of the catalyst layer is too thin, the amount of catalyst charged in the reactor is small, so economic efficiency is low, and when the thickness is too thick, it is difficult to control the amount of heat generated, so the above range is preferable.
  • the thickness of the reforming catalyst layer of methane depends on the thickness of the oxidative dimerization catalyst layer of methane, and preferably 0.1 to 2 relative to the thickness of the oxidative dimerization catalyst layer of methane. If the thickness of the methane reforming catalyst layer is less than the ratio of 0.1, the contact time of the reactants is too short, the conversion rate of methane in the methane reforming reaction is too low, it may be difficult to effectively remove the heat of the oxidative dimerization reaction of methane, the ratio If it is larger than 2, the contact time is increased in the methane reforming reaction, so that the conversion of the methane reforming reaction may occur only at the upper portion of the catalyst, and thus, it may be difficult to control the heat of reaction of the oxidative dimerization reaction of the middle and lower methane. Therefore, the catalyst layer thickness ratio is suitable for controlling the heat of reaction of the oxidative dimerization reaction of methane.
  • the second method of controlling the heat of reaction of the oxidative dimerization reaction of methane is a method of artificially reducing the activity of the catalyst in the catalyst of the methane reforming reaction.
  • the reforming catalyst of methane may be one in which catalytically active metal components such as Ni, Pt, Rh, Co and the like are supported on various catalyst supports.
  • Methods of lowering the artificial catalyst activity include a catalyst sintering method at a high temperature (> 1000 ° C.), supporting an alkali metal such as K, and catalyst poisoning by a component such as S, and the like, but the present invention is not particularly limited thereto. .
  • the catalytic activity of the methane reforming reaction is lowered to achieve an optimum temperature similar to that of the methane reforming reaction.
  • the third method is to control the conversion of methane by adjusting the reaction conditions of the methane reforming reaction.
  • the reforming reaction of methane can control the rate of methane conversion with temperature by the ratio of water vapor or carbon dioxide or a mixture thereof or the reaction pressure. As shown in FIG. 2, the conversion rate of methane is lower as the molar ratio of H 2 O / CH 4 or CO 2 / CH 4 or (H 2 O + CO 2 ) / CH 4 decreases, and as the reaction pressure increases.
  • the reaction conditions were adjusted to prevent excessive conversion in the upper stage of the catalyst layer of the methane reforming reaction. The proper methane conversion of methane reforming is thus 60% to 95%.
  • the conversion rate is lower than 60% may cause a problem that the efficiency of the after-stage reaction of the produced synthesis gas is lowered, and if the conversion rate is higher than 95%, the temperature in the bottom catalyst layer of the oxidative dimerization reaction of methane may be too high. This occurs because almost no endothermic reaction occurs at the bottom of the methane reforming reaction.
  • the reaction heat control method of the oxidative dimerization reaction of methane can be used without limitation to the type of endothermic reaction.
  • the dehydrogenation or pyrolysis reaction of ethane is also endothermic and is preferred as endothermic because the reaction can be carried out at temperature conditions similar to the oxidative dimerization of methane.
  • non-limiting examples of endothermic reactions include methane reforming as well as ethane cracking.
  • an exothermic reaction passage filled with a catalyst for oxidative dimerization reaction of methane and an endothermic reaction passage filled with an endothermic catalyst are alternately provided, and the temperature (T 1 ) of the exothermic reaction passage is endothermic.
  • the heat exchange microchannel reactor which is heat transfer from the exothermic reaction flow path to the endothermic reaction flow path higher than the temperature T 2 of the flow path, is characterized by satisfying each of the following four requirements or a combination thereof:
  • reaction temperature in the exothermic reaction passage through heat exchange with the endothermic reaction passage is controlled within the range of 800 ° C. ⁇ 50 ° C., and the reaction temperature in the endothermic reaction passage through the heat exchange with the exothermic reaction passage ranges from 750 ° C. ⁇ 50 ° C. Controlling within;
  • the thickness of the catalytic bed in the exothermic reaction flow path located between two adjacent endothermic reaction flow paths (ie, the two endothermic reaction flow paths) so as to enable control of the calorific value in the exothermic reaction flow path without lowering the product yield.
  • the thickness of the catalytic bed in the endothermic reaction flow path is adjusted to within the range of 1 to 5 mm and / or to remove the calorific value downstream in the exothermic flow path. Adjusting within a range of 0.1 to 2 times the thickness of the catalyst layer in the flow path;
  • the fluid flow in the exothermic reaction flow path and the fluid flow in the endothermic reaction flow path are preferably in the same direction.
  • the fluid flow of the oxidative dimerization reaction of methane and the flow of the reforming reaction of methane are reversed, the product yield is lowered due to the high temperature in the upper catalyst layer of the oxidative dimerization reaction of methane (Comparative Example 6).
  • the heat exchange microchannel reactor according to the present invention can be used in a methane conversion process.
  • the methane conversion method of the present invention may perform the oxidative dimerization of methane in the exothermic flow passage in the heat exchange microchannel reactor, and / or the reforming reaction of methane in the endothermic flow passage. At this time, each reaction occurs while passing through the catalyst layer in the channel of the heat exchange reactor.
  • one aspect of the present invention provides a method for producing a gas product by converting methane in the heat exchange microchannel reactor of the various aspects of the present invention.
  • synthesis gas may be prepared from methane-containing gas by reforming the methane in the endothermic reaction flow path, or ethylene may be produced from the ethane by carrying out dehydrogenation of ethane or cracking of ethane in the endothermic flow path.
  • the reaction temperature is controlled within the range of 800 °C ⁇ 50 °C
  • the reaction temperature in the endothermic reaction passage is controlled within the range of 750 °C ⁇ 50 °C
  • methane in the exothermic reaction passage The ethane-containing gas formed through the oxidative dimerization reaction may be introduced as a reactant into the endothermic reaction path that performs dehydrogenation of ethane or cracking reaction of ethane, and at this time, the preheating of the reactants may be omitted during the endothermic reaction. Can be.
  • the products of the oxidative dimerization of methane may include ethane, ethylene, CO, CO 2 , H 2 , H 2 O, traces of C 3+ hydrocarbons and unreacted methane.
  • ethylene and / or ethane can be formed as the product as C 2 hydrocarbons by oxidative dimerization of methane.
  • the production rate of ethane and ethylene is similar, but as the reaction temperature increases, the production rate of ethylene tends to increase.
  • the oxidative dimerization of methane is a strong exothermic reaction. If the heat of reaction is not well controlled, the production of CO or CO 2 increases and the yield of C2 + hydrocarbons decreases. Therefore, it is important to keep the reaction temperature within a certain temperature range.
  • the temperature (T 1 ) of the exothermic reaction passage in which the oxidative dimerization reaction of methane is performed while the exothermic reaction passage and the endothermic reaction passage are alternately arranged adjacent to each other is the temperature of the endothermic reaction passage (T 2 ).
  • the heat exchanging microchannel reactor may further meet the characteristics of various combinations of (i) to (iv).
  • the heat exchange microchannel reactor according to the present invention can perform the methane conversion process through the reforming reaction of methane in the endothermic reaction passage.
  • the reactants of the methane reforming reaction are methane; And water vapor, carbon dioxide or mixtures thereof.
  • a portion of the product containing the unreacted methane of the oxidative dimerization of methane may be recycled to the reactant in the endothermic flow path for performing the methane reforming reaction.
  • By-products of methane oxidative dimerization include CO, H 2 , H 2 O and CO 2 , which are products or reactants of methane reforming, and it is advantageous to recycle them to methane reforming rather than oxidative dimerization. Do.
  • the amount and composition of the by-products in the oxidative dimerization of methane depends on the reaction conditions, but it is advantageous in terms of the efficiency of the overall process to recycle the remaining by-products to the oxidative dimerization reaction of methane.
  • the oxidative dimerization reaction of methane and the reforming reaction of methane are important for the transfer of reaction heat in close contact with each other in the same reactor.
  • a microchannel reactor is used as the heat exchange reactor, and each channel of the microchannel reactor may be filled with a catalyst for oxidative dimerization of methane or a catalyst for reforming of methane.
  • Methane conversion rate in methane reforming in the endothermic flow path to lower the rate of oxidative dimerization of methane upstream in the exothermic flow path to suppress rapid temperature increase and to remove the calorific value of the oxidative dimerization reaction of methane downstream in the exothermic flow path.
  • the reforming reaction of methane may control the conversion of methane by controlling the molar ratio of water vapor / methane, the molar ratio of carbon dioxide / methane or the molar ratio of (water vapor + carbon dioxide) / methane in the endothermic reaction channel.
  • the reforming reaction of methane is preferably adjusted to a molar ratio of (water vapor + carbon dioxide) / methane to 0.8 to 2 in order to control the methane conversion to 60 to 95%.
  • the reforming reaction of methane is preferably carried out at a reaction pressure of 1 ⁇ 10bar, a molar ratio of (water vapor + carbon dioxide) / methane of 0.8 ⁇ 2, the space velocity of 1000 ⁇ 50000 h -1 .
  • the conversion of methane to the equilibrium conversion in the reaction conditions can be adjusted to 95% or less.
  • Subsequent reactions utilizing syngas obtained for the reforming of methane may be methanol synthesis or Fischer-Tropsch reactions.
  • the reactant composition of the methane reforming reaction can be adjusted to match the composition of the syngas suitable for each subsequent reaction.
  • the product of the oxidative dimerization reaction of methane prepared in the heat exchange microchannel reactor according to the present invention is a high temperature of 700 ° C or more, it has to be rapidly cooled below a certain level. This is because a highly reactive ethylene product can undergo a secondary reaction if it is maintained at a high temperature for a long time. Cooling of the hot product can be accomplished by cooling water or steam. The high pressure or high temperature steam generated in this process can be utilized as utility steam in the process. The cooled reaction product is further secondary cooled and then fed to a gas-liquid separator to separate the gas-liquid separation to recover the liquid product, water, and the gas product is fed to the olefin oligomerization reactor, which is a subsequent reactor after being preheated. Can be.
  • all of the products of the oxidative dimerization reaction of methane may be introduced into a subsequent olefin oligomerization reactor without performing the secondary cooling and gas-liquid separation separately.
  • the temperature of the product flow after the primary cooling may be adjusted in the range of 250 °C to 500 °C temperature of the ethylene oligomerization reaction.
  • a second step of preparing a synthetic oil by methanol synthesis, hydrogen production, ammonia production, or a Fischer-Tropsch reaction is carried out from the synthesis gas formed in the first step. It may further include.
  • the first aspect of the present invention may further include a third step of preparing a liquid hydrocarbon product by ethylene oligomerization reaction from the C 2 hydrocarbon formed in the first step after the second step.
  • the composition discharged through the reactor of the third stage may include CO, CO 2 , H 2 O, hydrogen, methane, C 2 hydrocarbons, C 3 ⁇ C 4 hydrocarbons, C 5 + hydrocarbons, aromatics (aromatic) and the like.
  • the C 2 hydrocarbons discharged through the reactor of the third stage may include ethane and ethylene.
  • a complicated process such as a multi-stage distillation column is required, resulting in high operating and investment costs. It may take a lot, so it is necessary to increase the conversion of ethylene to exclude this. Therefore, the present invention was to identify the optimum reaction conditions and catalysts that can maximize the conversion of ethylene in the third step reaction, it is possible to recycle to the first step without having to separate them separately.
  • the present invention may further include a fourth step of recycling the unreacted gas of the third step to the steam reforming reaction of the first step and the oxidative dimerization reaction of methane after the third step.
  • the product of the third step may be gas-liquid separated, and the gas phase of the gas-liquid separated second step product may be separated and recycled to the first step.
  • unreacted methane is the main component in the oxidative dimerization reaction of methane in the first step.
  • the recycled gaseous component to the first stage can be partitioned in oxidative dimerization of methane or steam reforming of methane, or alternatively in proportion to all of the reactions.
  • by-products of the oxidative dimerization of methane include CO, H 2 , H 2 O and CO 2 , which are products or reactants of the methane reforming reaction and recycled to the methane reforming reaction rather than the oxidative dimerization reaction of methane. It is advantageous.
  • the amount and composition of the by-products in the oxidative dimerization of methane depends on the reaction conditions, but it is advantageous in terms of the efficiency of the overall process to recycle the remaining by-products to the oxidative dimerization reaction of methane.
  • the liquid product consists of C5 + hydrocarbons containing C5 + olefins and water which is the product of the oxidative dimerization reaction of methane.
  • C5 + hydrocarbons can be obtained as gasoline by further hydrogenation processes and converted to light olefins by cracking processes.
  • the conversion rate of methane is 20 to 80%
  • the selectivity for C 2+ hydrocarbons is 40 to 80%
  • the overall yield of C 2+ hydrocarbons may be 15 to 25%.
  • Figure 2 is a process schematic showing the conversion process of the methane-containing gas in more detail, in the production of C5 + hydrocarbons and synthetic oil or methanol or hydrogen in methane, showing a process according to the invention less energy consumption, lower equipment costs and operating costs .
  • the methane-containing reaction gas is introduced into the oxidative dimerization reaction layer 2 of methane in the microchannel reactor 1 through the flow 21, where oxygen is supplied together as the oxidant of the methane.
  • the recycle stream 27 of unreacted and recovered methane is mixed with the stream 21 and fed to the oxidative dimerization reaction bed 2 of methane.
  • the product is discharged as stream 22 and quenched by cooling water, where the cooling water is heated to obtain additional high pressure steam.
  • the cooled stream 22 enters the flash column 4, which is a gas-liquid separator, and the phases are separated, and the liquid water is discharged into the stream 24.
  • the water condensed and discharged may be reused as process water after the purification process.
  • the remaining gaseous gas component is a stream 23 which is boosted or adjusted to a pressure of at least 3 atm suitable for the ethylene oligomerization reaction, and then introduced into the olefin oligomerization reactor 5 via heat exchange.
  • the product is withdrawn into stream 25 and fed to separator 6 to separate the phases.
  • the gaseous phase separated in separator 6 is recycled to microchannel reactor 1 as stream 27.
  • the methane-containing reaction gas is introduced into the reforming reaction layer 3 of methane of the microchannel reactor 1 through the stream 31, where steam or carbon dioxide or a mixture thereof is supplied together.
  • the recycle stream 27 of unreacted and recovered methane is mixed with the stream 31 and supplied to the reforming reaction layer 3 of methane.
  • the syngas is discharged as stream 32 and quenched by cooling water.
  • the cooled stream 32 is introduced into a flash column, which is a gas-liquid separator, to separate phases, and to separate unreacted liquid water.
  • the remaining gaseous gas component is boosted or adjusted to a pressure suitable for the syngas conversion reaction and then introduced into the syngas conversion device 7.
  • the product is discharged to stream 33 and fed to separator 8 to separate the product. Unreacted syngas separated in the separator 8 is recycled to the syngas converter 7 via a flow 34.
  • Inconel 600 was used as a heat resistant material of the microchannel reactor.
  • Inconel plates are stacked and each layer has a predetermined thickness and they are separated from each other.
  • the microchannel reactor consists of alternating oxidant dimerization reaction beds of methane and reforming reaction beds of methane.
  • the oxidation dimerization reaction layer is three layers
  • the methane reforming reaction layer is 4 layers
  • the plate size is 6 cm x 6 cm, the same as the catalyst layer of the oxidation dimerization reaction of methane and the reforming reaction of methane 3 mm thick.
  • Each layer is filled with the respective catalysts and the rear end has a built-in filter to prevent the catalysts from escaping.
  • (A) to (c) is a schematic diagram showing a microchannel reactor in which the oxidative dimerization reaction of methane and steam reforming reaction of methane produced as described above, and (d) of FIG. Photo of the reactor.
  • a microchannel reactor was manufactured in the same manner as in Preparation Example 1, but the thickness and the number of stacked layers of the catalyst layer were prepared as shown in Table 1.
  • silica (SiO 2 , Davisil grade 635) was used as a catalyst carrier to prepare a catalyst for oxidative dimerization of methane.
  • the aqueous solution was supported on the silica carrier by incipient impregnation.
  • the supported catalyst was dried and calcined at 800 ° C. for 5 hours to use as an oxidation dimerization catalyst of methane.
  • the composition of the prepared catalyst is 4.75 Na 2 WO 4 /2Mn/0.25La/SiO 2 , the number indicating the weight percent.
  • the catalytic activity was adjusted to prepare a catalyst for the reforming reaction of methane which is suitable for controlling the heat of reaction of the oxidative dimerization reaction of methane.
  • a catalyst for reforming methane was prepared using gamma-alumina ( ⁇ -Al 2 O 3 ) as a catalyst carrier.
  • gamma-alumina ⁇ -Al 2 O 3
  • Pt, Ni, Mg, and a K source (source) Pt (NH 3) 4 (OH) 2 ⁇ xH 2 O (Tetraammineplatinum (II) hydroxide hydrate), Ni (NO 3) 2 ⁇ 6H 2 O, Mg ( NO 3 )
  • Aqueous solution prepared by dissolving 2 ⁇ 6H 2 O and KNO 3 in distilled water was prepared by sequentially supporting the alumina carrier by incipient impregnation. The supported catalyst was dried and calcined at 1100 ° C. for 5 hours to use as a reforming catalyst for methane.
  • the composition of the prepared catalyst is 0.05Pt / 2K / 12Ni-5Mg / Al 2 O 3 , the number of which indicates wt%.
  • a catalyst for reforming methane having general catalytic activity was prepared. It was prepared in a similar manner to Preparation Example 2, except that it did not carry K and was fired at a lower temperature.
  • a catalyst for reforming methane was prepared using gamma-alumina ( ⁇ -Al 2 O 3 ) as a catalyst carrier.
  • Pt, Ni and a Mg source of Pt (NH 3) 4 (OH ) 2 ⁇ xH 2 O, Ni (NO 3) 2 ⁇ 6H 2 O, and Mg (NO 3) 2 ⁇ dissolved 6H 2 O in distilled water The prepared aqueous solution was prepared by sequentially supporting the alumina carrier by the initial wet impregnation method.
  • the supported catalyst was dried and calcined at 900 ° C. for 5 hours to use as a reforming catalyst for methane.
  • the composition of the prepared catalyst is 0.05Pt / 12Ni-5Mg / Al 2 O 3 , the number of which indicates wt%.
  • Iron-based Fischer-Tropsch catalysts having a composition of 2.5K / 100Fe / 4Cu / 10Mn / 20Al 2 O 3 molar ratio were prepared using mixed-coprecipitation and extrusion-molding.
  • a methanol synthesis catalyst having a composition of 0.75Cu / 1Zn / 0.26Al oxide molar ratio was prepared using mixed-coprecipitation and extrusion-molding.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 3 above were mounted in the microchannel reactor prepared in Preparation Example 1, and the exothermic and endothermic reactions were thermally neutralized by heat exchange. It was.
  • the volume of the catalyst mounted in the oxidative dimerization reaction layer of methane was 23 cc
  • the volume of the catalyst mounted in the reforming reaction layer of methane was 28 cc.
  • the microchannel reactor equipped with the catalyst was heated to 780 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300cc / min. When the temperature outside the reactor rose to 780 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the amount of gas in the normal reforming reaction is methane 700cc / min, nitrogen 500cc / min (GC standard gas), water 1.4cc / min, and the reaction inlet pressure is 0.4 bar.
  • the amount of gas in the oxidative dimerization reaction of methane was 1500 cc / min of methane, 3000 cc / min of nitrogen (GC standard gas and diluent gas), and 600 cc / min of oxygen, where the reaction inlet pressure was 1.8 bar.
  • the temperature inside the oxidative dimerization reaction layer of methane was 795 ° C., and the temperature inside the reforming reaction layer of methane was 723 ° C.
  • An oxidation dimerization catalyst of methane was prepared in the same manner as in Preparation Example 1, but a 3Na 2 WO 4 /2Mn/0.5La/SiO 2 catalyst was prepared, and a reforming catalyst of methane was used in the same catalyst as in Preparation Example 2.
  • the gas content of the normal reforming reaction is methane 700cc / min, nitrogen 500cc / min (GC standard gas), water 1.4cc / min, and the reaction inlet pressure is 0.4 bar.
  • the amount of gas in the oxidative dimerization reaction of methane is methane 1300cc / min, nitrogen 2600cc / min (GC standard gas and diluent gas), oxygen 520cc / min, except that the reaction inlet pressure is 1.8 bar and It was done in the same way.
  • the temperature in the oxidative dimerization reaction layer of methane was 818 ° C, and the temperature in the reforming reaction layer of methane was 710 ° C.
  • an oxidation dimerization catalyst of methane and a reforming catalyst of methane were used.
  • the volume of the catalyst mounted on the methane oxidative dimerization reaction bed is 20 cc
  • the volume of the catalyst mounted on the methane reforming reaction bed is 28 cc.
  • 1.6cc / min of water where the reaction inlet pressure is 0.5bar.
  • the amount of gas in the oxidative dimerization reaction of methane is methane 1100cc / min, nitrogen 1833cc / min (GC standard gas and diluent gas), oxygen 436cc / min, except that the reaction inlet pressure is 1.1 bar and It was done in the same way.
  • the temperature inside the oxidative dimerization reaction layer of methane was 782 ° C., and the temperature inside the reforming reaction layer of methane was 778 ° C.
  • Example 2 The same oxidation dimerization catalyst (3Na 2 WO 4 / 2Mn / 0.5La / SiO 2 ) of methane was used as in Example 2 .
  • the catalyst was mounted in an Inconel tube (1/2 inch outer diameter) reactor to conduct oxidative dimerization of methane. Unlike Examples 1 to 3, only the oxidation dimerization reaction of methane was carried out using a single tube.
  • the weight of the catalyst mounted in the oxidative dimerization reaction of methane was 0.2 g.
  • the reactor equipped with the catalyst was heated to 800 ° C. by an electric furnace.
  • the amount of gas in the oxidative dimerization reaction of methane was methane 166cc / min, nitrogen 139cc / min (GC standard gas and diluent gas), oxygen 55cc / min, and the reaction inlet pressure was 0.2 bar.
  • the temperature inside the oxidative dimerization reaction layer of methane was 850 ° C., but the internal temperature increased due to the exothermic reaction of the oxidative dimerization reaction of methane.
  • the reaction heat is easily controlled even when the reactor scale is increased, and the exothermic reaction is divergent.
  • heat can be effectively used as a heat source of the endothermic reaction.
  • the temperature of the reactor could be kept constant.
  • the temperature inside the oxidative dimerization reaction layer of methane was 920 ° C., and the internal temperature greatly increased due to the exothermic reaction of the oxidative dimerization reaction of methane.
  • the reaction was carried out in a fixed bed reactor packed with catalyst, and the reactants used in the reaction were simulated gas having a composition similar to that of the product of oxidative dimerization of methane (composition gas composition: nitrogen 5.0%, methane 60.5%).
  • the reaction temperature was 400 ° C.
  • the reaction pressure was 5 bar
  • the space velocity (GHSV) was performed at 4,000 h ⁇ 1 to convert ethylene into C5 + hydrocarbon.
  • Ethylene conversion was calculated based on the internal standard nitrogen.
  • Selectivity of the hydrocarbon product was calculated on the basis of ethylene.
  • the product distribution of the ethylene oligomerization reaction is shown in Table 4 (product distribution of the ethylene oligomerization reaction).
  • the olefin (ethylene) oligomerization reaction was carried out to convert ethylene into C5 + olefins. The results are shown in Table 4 below.
  • the iron-based Fischer-Tropsch catalyst prepared in Preparation Example 6 was crushed and classified into a size of about 1 mm, 1 g of the catalyst was charged, and charged into a one-stage fixed bed reactor, and activated under a hydrogen atmosphere at atmospheric pressure at 450 ° C. for 12 hours. Reduced. Reaction temperature 280 °C, reaction pressure 10 kg / cm 2 , The molar ratio of reactants carbon monoxide: hydrogen: carbon dioxide: argon (internal standard) at a space velocity of 3600 L / kg cat / hr was fixed at a ratio of 18.0: 60.5: 16.0: 5.5 and injected into the reactor. Fischer Tropsch reaction was performed, and the results of measuring the activity of the catalyst after the reaction time of 40 hours are shown in Table 5 below.
  • the methanol synthesis catalyst prepared in Preparation Example 7 was crushed and classified into a size of about 1 mm, 1 g of the catalyst was charged, and charged in a one-stage fixed bed reactor, and reduced by performing an activation process in a hydrogen atmosphere at atmospheric pressure at 280 ° C. for 5 hours.
  • Reaction temperature 250 °C, reaction pressure 60 kg / cm 2 The composition of gas composition suitable for methanol synthesis reaction is fixed by fixing the molar ratio of carbon monoxide: hydrogen: carbon dioxide: argon (internal standard) as reactants at the space velocity of 4000 L / kg cat / hr at the ratio of 19.0: 66.5: 9.5: 5.0.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 above were mounted in the microchannel reactor prepared in Preparation Example 1, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is methane 300 cc / min, hydrogen 300 cc / min, nitrogen 400 cc / min (GC standard gas), water 0.24 cc / min, and the reaction inlet pressure is 0.5 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 1300 cc / min of methane, 2000 cc / min of nitrogen (GC standard gas and diluent gas), and 520 cc / min of oxygen, where the reaction inlet pressure was 1.4 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 815 ° C.
  • Table 6 The results of the oxidative dimerization reaction of methane and the reforming reaction of methane obtained above are shown in Table 6 below.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 2, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is methane 700 cc / min, hydrogen 600 cc / min, nitrogen 700 cc / min (GC standard gas), water 0.56 cc / min, and the reaction inlet pressure is 0.8 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 2500 cc / min of methane, 3000 cc / min of nitrogen (GC standard gas and diluent gas), and 1000 cc / min of oxygen, with a reaction inlet pressure of 1.74 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 829 ° C.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 3, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is 200 cc / min of methane, 200 cc / min of hydrogen, 300 cc / min of nitrogen (GC standard gas), and 0.16 cc / min of water, where the reaction inlet pressure is 0.3 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 600 cc / min of methane, 700 cc / min of nitrogen (GC standard gas and diluent gas), and 240 cc / min of oxygen, and the reaction inlet pressure was 0.9 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 813 ° C.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 4, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is methane 350 cc / min, hydrogen 300 cc / min, nitrogen 400 cc / min (GC standard gas), carbon dioxide 180 cc / min, water 0.18 cc / min, and the reaction inlet pressure is 0.5 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 1500 cc / min of methane, 2500 cc / min of nitrogen (GC standard gas and diluent gas), and 600 cc / min of oxygen, and the reaction inlet pressure was 0.9 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 822 ° C.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 5, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is methane 300 cc / min, hydrogen 300 cc / min, nitrogen 300 cc / min (GC standard gas), water 0.24 cc / min, and the reaction inlet pressure is 0.4 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was methane 1400 cc / min, nitrogen 1800 cc / min (GC standard gas and diluent gas), oxygen 560 cc / min, and the reaction inlet pressure was 0.9 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 829 ° C.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 2, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas reforming rate is 800 cc / min for methane, 600 cc / min for hydrogen, 700 cc / min for nitrogen (GC standard gas), and 0.64 cc / min for water.
  • the reaction was carried out by raising the pressure to 2.1 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 2500 cc / min of methane, 3000 cc / min of nitrogen (GC standard gas and diluent gas), and 1000 cc / min of oxygen, where the reaction inlet pressure was 1.7 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 833.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 6, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is methane 900 cc / min, hydrogen 600 cc / min, nitrogen 700 cc / min (GC standard gas), water 0.72 cc / min, and the reaction inlet pressure is 0.7 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was methane 2700 cc / min, nitrogen 3300 cc / min (GC standard gas and diluent gas), oxygen 1080 cc / min, and the reaction inlet pressure was 1.8 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 835 ° C.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 2 were mounted in the microchannel reactor prepared in Preparation Example 2, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is 700 cc / min of methane, 700 cc / min of nitrogen (GC standard gas), and 1.69 cc / min of water, where the reaction inlet pressure is 0.95 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 2500 cc / min of methane, 3000 cc / min of nitrogen (GC standard gas and diluent gas), and 1000 cc / min of oxygen, where the reaction inlet pressure was 1.7 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 830 ° C.
  • the methane oxidative dimerization catalyst and the methane reforming catalyst prepared in Preparation Examples 1 and 3 above were mounted in the microchannel reactor manufactured in Preparation Example 2, and the exothermic and endothermic reactions were thermally neutralized by heat exchange.
  • the flow of reactants is in the same direction.
  • the microchannel reactor equipped with the catalyst was heated to 760 ° C by an electric furnace. At this time, the inside of the reactor was allowed to flow at 300 cc / min. When the temperature outside the reactor rose to 760 ° C, the gas composition and flow rate of the reforming reaction layer were gradually changed.
  • the gas content of the normal reforming reaction is 700 cc / min of methane, 700 cc / min of nitrogen (GC standard gas), and 1.13 cc / min of water, where the reaction inlet pressure is 0.75 barg.
  • the amount of gas in the oxidative dimerization reaction of methane was 2500 cc / min of methane, 3000 cc / min of nitrogen (GC standard gas and diluent gas), and 1000 cc / min of oxygen, where the reaction inlet pressure was 1.7 barg.
  • the temperature inside the oxidative dimerization reaction layer of methane was 825 ° C.
  • Example 10 was carried out in the same manner as in Example 10, except that the fluid flow of the reactants of the methane oxidative dimerization reaction and the methane reforming reaction was reversed.
  • the catalyst layer thickness of the oxidative dimerization reaction of methane is in an appropriate range, or a catalyst having a low catalytic activity in the reforming reaction of methane is used, and the molar ratio of (water vapor + carbon dioxide) / methane Lowering to near 1 prevents the methane conversion of the methane reforming reaction from being rapidly converted at low temperatures, which is more effective in controlling the heat of reaction of the oxidative dimerization reaction of methane by endothermic reaction, which is advantageous for obtaining a high product, and more easily in the reactor.
  • the catalyst layer thickness of the oxidative dimerization reaction of methane is in an appropriate range, or a catalyst having a low catalytic activity in the reforming reaction of methane is used, and the molar ratio of (water vapor + carbon dioxide) / methane Lowering to near 1 prevents the methane conversion of the methane reforming reaction from being rapidly converted at low temperatures, which is more effective in controlling the heat of reaction of the oxidative

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Abstract

La présente invention concerne un procédé qui : fournit un moyen capable de réguler efficacement la chaleur de réaction à l'aide d'un réacteur à microcanaux d'échange de chaleur de façon à réaliser simultanément une réaction exothermique, de couplage oxydant de méthane, et une réaction endothermique, ce qui permet d'obtenir et de recevoir la chaleur de réaction, et peut ainsi obtenir une sélectivité de produit C2 élevée ; et améliore l'efficacité thermique d'un processus en obtenant des conditions de réaction thermiquement neutres, et ainsi convertir plus efficacement le méthane.
PCT/KR2017/015693 2016-12-28 2017-12-28 Réacteur à microcanaux à échange de chaleur pour couplage oxydant de méthane WO2018124791A1 (fr)

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KR1020170169774A KR102032482B1 (ko) 2017-12-11 2017-12-11 메탄의 산화이량화 반응용 열교환 마이크로채널 반응기
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JP2014131804A (ja) * 2001-02-16 2014-07-17 Battelle Memorial Inst 一体型反応器、その製造方法並びに、発熱反応及び吸熱反応を同時に実施する方法
KR20140133077A (ko) * 2013-05-09 2014-11-19 한국에너지기술연구원 Gtl 공정에서 메탄의 수증기/co2 복합 개질 방법
KR101568859B1 (ko) * 2013-08-01 2015-11-13 한국화학연구원 경질 알칸으로부터 액체탄화수소를 제조하는 방법
WO2016050583A1 (fr) * 2014-09-29 2016-04-07 Haldor Topsøe A/S Déshydrogénation d'alcanes en alcènes

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