CN106831291A - The method of Catalyst for Oxidative Coupling of Methane - Google Patents

The method of Catalyst for Oxidative Coupling of Methane Download PDF

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CN106831291A
CN106831291A CN201710006746.7A CN201710006746A CN106831291A CN 106831291 A CN106831291 A CN 106831291A CN 201710006746 A CN201710006746 A CN 201710006746A CN 106831291 A CN106831291 A CN 106831291A
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reaction
reactor
ice chest
temperature
catalyst
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CN106831291B (en
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堵祖荫
吴曦
唐绮颖
徐尔玲
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Sinopec Engineering Group Co Ltd
Sinopec Shanghai Engineering Co Ltd
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Sinopec Engineering Group Co Ltd
Sinopec Shanghai Engineering Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219—Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • 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
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0238—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 2 carbon atoms or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0242—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 3 carbon atoms or more
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
    • F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/12—Refinery or petrochemical off-gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/62—Ethane or ethylene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/12—External refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/60—Closed external refrigeration cycle with single component refrigerant [SCR], e.g. C1-, C2- or C3-hydrocarbons

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention relates to a kind of method of Catalyst for Oxidative Coupling of Methane, the methane oxidation coupling method production ethene that shorter mention is arrived in the prior art is mainly solved the problems, such as.The present invention is by using a kind of method of Catalyst for Oxidative Coupling of Methane, by using multi-stage fixed-bed adiabatic thin bed reactor, it is intersegmental that quencher and temperature control system are set, by reactor bed and its outlet temperature control in certain limit, intermediate reaction gas is quickly cooled to 700~800 DEG C after being exchanged heat through the corresponding rapid-cooling heat exchanger of each section of fixed bed, the whole total methane conversion of course of reaction ensures that more than 24% C2 selectivity is more than 73%；Above mentioned problem is preferably solved by the technical scheme that many energy saving means reducing energy consumptions such as technology are highly thermally integrated between multiply charging, expanding machine, rectifying column and ice chest and refrigerator, be can be used in Catalyst for Oxidative Coupling of Methane.

Description

The method of Catalyst for Oxidative Coupling of Methane
Technical field
The present invention relates to a kind of method of Catalyst for Oxidative Coupling of Methane.
Background technology
Whole world ethylene production raw materials used 70% is naphtha at present, and 25% is natural gas, and 5% is coal.Due to stone brain Oily raw material is limited by oil supply limitation, and coal utilization process environmental issue is than more prominent, and natural gas resource especially shale The unconventional gas resources such as gas, gas hydrates not only abundance, and clean environment firendly, in the long term natural gas second Alkene has bright market prospects.It is relative with reserves with the extensive discovery and exploitation of following whole world unconventional gas resource Abundant and cheap substitute gas Petroleum Production ethene and its downstream product seem more and more important, are worth causing in the industry Attention.
Compared to natural gas indirect reformer method, methane oxidation coupling (OCM) ethene processed (natural gas direct translation method) only needs one Methane can be changed into ethene by step reaction, very attractive with theory value and economic worth very high.From 1982 Nian Qi, successively carries out the trial-production of OCM catalyst and reaction process research both at home and abroad, has studied catalyst up to more than 2000 kinds.Closely Nian Lai, domestic and international research and development institution is constantly improved to catalyst, and optimizes reactor and reaction condition, to realize with high selection Property obtain low-carbon alkene purpose.The research and development of external methane oxidation coupling (OCM) technology are public with U.S. Xi Luliya technologies Department typical case the most.Nano-wire catalyst, the proprietary methane oxygen of Xi Luliya technology companys are accurately synthesized by using biological template Change coupling (OCM) technology can high-performance ground catalyzed conversion turns into ethene at a lower temperature by methane.China since the eighties, Many research units have carried out developmental research, wherein Chinese Academy of Sciences Lanzhou Chemical Physics to the catalyst and reaction technology of OCM technologies The Na of Research Institute2WO3-Mn/SiO2Catalyst Conversion and C2 selectivity are high, and good stability is preceding with good application Scape.
The product of oxidative coupling of methane is a multiple gases mixture based on the lighter hydrocarbons such as methane, ethene, is needed , to remove other components, the reaction cycle material such as ethylene product and methane, ethane is obtained by separation process.
CN102093157A discloses the process integration process of a kind of methane direct conversion ethene and synthesis gas, there is provided by Ethene is converted into containing methane feed, while producing the combined technique of synthesis gas.The invention is overcome over by methane The direct limitation with single product as target of ethene processed, be outside ethene in methane high yield conversion, it is also contemplated that entering for methane One step is utilized, i.e., high yield conversion is synthesis gas.The method needs special ethene adsorbent, and second is separated using pressure swing adsorption method Alkene product.
US2015/0368167A1 discloses the technical process for producing and separating ethane and ethene, methane oxidation coupling (OCM) contain ethane and ethene in reaction gas, by two rectifying columns of separative element, obtain rich in C2, rich in methane and richness Containing N2Three bursts of logistics.The method flow is complicated, and especially the tower top temperature of the second knockout tower reaches -210 DEG C, it is desirable to provide extremely low The cryogen of potential temperature, device fabrication high cost, realize that industrialization has larger difficulty.
The content of the invention
The technical problems to be solved by the invention are the methane oxidation coupling method production that shorter mention is arrived in the prior art A kind of problem of ethene, there is provided method of new Catalyst for Oxidative Coupling of Methane.The method has that Recovery rate of ethylene is higher, energy consumption Relatively low advantage.
To solve the above problems, the technical solution adopted by the present invention is as follows：A kind of method of Catalyst for Oxidative Coupling of Methane, Comprise the following steps：
A () in OCM reaction members, natural gas passes through anti-after mixing with methane, ethane that oxygen and separative element are returned Integrated heat exchange system is answered, is exchanged heat with product gas, reach the reaction temperature of regulation, into OCM reaction systems, in catalysis Under agent effect, methane is converted into including ethene, ethane, CO, CO2、H2The product gas of O, alkynes, product gas passes through The system cooling of reaction integrated heat exchange, the solidifying solidifying water treatment system of water feeding technique of reaction process, other reaction streams feeding separates single Unit, then by compression, removing CO2, compression, drying steps, obtain remove CO2、H2OCM product after O；The OCM is anti- The reaction process for answering unit to use includes at least two sections of the thin bed fixed bed reactors of methane oxidation coupling, by following optional Any one means realize Catalyst for Oxidative Coupling of Methane reaction process：(1) when reactor uses vertical arranged in series, every section It is directly connected to using rapid-cooling heat exchanger between reactor, every section of catalytic bed of reactor is made up of 1~2 bed, two beds It is different catalyst, is adequately mixed and is preheated to the methane after 600~900 DEG C, oxygen mixture feeding first paragraph and fix Bed reactor is reacted, and reaction pressure is 0.2~0.8MPaG, and catalyst bed layer height is 15~100mm, and volume space velocity is 50000~150000h-1, 100~300 DEG C of reaction gas limit of temperature rise, the reaction gas of reactor outlet is passed through rapid-cooling heat exchanger tube side 700~1000 DEG C are exchanged heat and be quickly cooled to shell side boiler feedwater, are re-fed into next section of fixed bed reactors and are proceeded Reaction, final stage reactor outlet is directly connected to rapid-cooling heat exchanger, and end reaction gas is by final stage rapid-cooling heat exchanger Temperature needed for down stream train is cooled to after tube side is simultaneously sent out；Each quencher shell is with corresponding HP steam drum by rising Pipe is connected with down-comer, forms boiler feedwater and the circulation of steam, constitutes Steam drum heat-exchange system；(2) reactor is used Horizontal arranged in series, every section of reactor and exports rapid-cooling heat exchanger and Steam drum heat-exchange system and (1st) of connection therewith Kind of realization rate is identical, but reactor is using horizontal arranged in series, rapid-cooling heat exchanger outlet be by one section of bend pipe with next section Reactor inlet is connected, and multiple rapid-cooling heat exchangers share a Steam drum；(3) planted (1st) or (2nd) plants realization rate On the basis of, rapid-cooling heat exchanger part is to employ the board-like quenching boiler of the light wall pipe with central tube, in quenching boiler central tube Exit, is provided with adjusting means, the reaction gas flow speed size flowed through from central tube is adjusted by adjusting means, so as to influence shell The flow velocity of reaction gas, plays the work of quick regulation quenching boiler thermic load in heat exchanger tube around formula quenching boiler inner central tube With, in the case of reactor outlet temperature fluctuation, the catalyst measured by the temperature element set in fixed bed reactors The feedback regulation of bed temperature, the heat exchange amount of quick adjustment quenching boiler, to ensure that the reaction gas that quenching boiler tube side is exported exists The temperature of regulation, it is ensured that is reacted in lower first stage reactor is steadily carried out；
B () described OCM product is formed at least by after ice chest A, ice chest B, ice chest C, which part lighter hydrocarbons are condensed Three feeding streams enter domethanizing column；
C () demethanizer column overhead distillate is by after ice chest D, ice chest E cooling, which part lighter hydrocarbons are condensed, and are formed extremely Few two strands enter lightness-removing column；
D () lightness-removing column overhead includes H2, CO and part CH4, sequentially pass through ice chest D, ice chest C, ice chest B, ice chest A Exchanged heat with OCM product；
E () lightness-removing column tower reactor distillate is liquid CH4, refrigeration is depressured by expanding machine after first evaporation recovery cold and is passed through again After ice chest E, ice chest C, ice chest B, the heat exchange of ice chest A and OCM product, OCM reaction members are returned；
F () domethanizing column reactor distillate removes C by dethanizer3 +Component, tower top C2 +Component enters ethene after acetylene removal After rectifying column, tower top obtains high-purity ethylene product.
In above-mentioned technical proposal, it is preferable that catalyst is Na2WO3-Mn/SiO2Catalyst；The thin bed of methane oxidation coupling The hop count of fixed bed reactors is 2~6 sections；In realization rate (1), reactor sets the temperature control system matched with charging System；Other section of reactor in addition to first paragraph reactor, is provided with gas inlet and distributor, anti-near reactor inlet Answer it is intersegmental be passed through oxygen and/or natural gas, be every section reaction supplemental oxygen and/or natural gas, with adjust every section reaction alcoxyl ratio, Alcoxyl is 4~10 than scope, to control the temperature rise of beds and reaction gas；Or water vapour or inert gas are passed through as dilute Outgassing controls the temperature rise of beds and reaction gas；In realization rate (2), risen in the bend pipe of rapid-cooling heat exchanger outlet connection Air inlet is provided with beginning, oxygen, natural gas, carrier gas or water are passed through during the course of the reaction, realized in bend pipe and reaction gas Be sufficiently mixed, regulation is passed through the amount of oxygen and/or natural gas, to adjust every section of alcoxyl ratio of reaction, by inject carrier gas or Water, is sufficiently mixed and exchanges heat in bend pipe with reaction gas, the temperature rise of control beds and reaction gas；Realization rate (1) or (2) in, when beds produce temperature runaway, by cutting off the oxygen in reaction mixture gas and each section of reactor before the oxygen that is passed through Gas come stop reaction, while continuing to be passed through temperature of the methane gas to take away beds, whole reactor is cooled to safety Temperature；In realization rate (1) or (2), rapid-cooling heat exchanger selects any one in linear bushing type, bushing type boiler, often Section rapid-cooling heat exchanger is connected with corresponding HP steam drum by tedge and down-comer, and the high steam produced in HP steam drum leads to Pipeline above crossing is sent out, and pressure-regulating valve is set on pipeline, is measured according to the temperature element set in fixed bed reactors Reaction bed temperature, or rapid-cooling heat exchanger tube side exports the temperature of the temperature control component feedback of reaction gas, is adjusted by this Valve action adjusts the pressure of high steam, so as to adjust the heat exchange amount of rapid-cooling heat exchanger so that the reactor under different operating modes When outlet temperature is different, the reaction gas temperature of rapid-cooling heat exchanger outlet is maintained at the temperature of regulation, it is ensured that in lower first stage reactor The steady of reaction is carried out；100~200 DEG C of reaction gas limit of temperature rise, the reaction gas of reactor outlet is passed through rapid-cooling heat exchanger tube side 700~800 DEG C are exchanged heat and are quickly cooled to shell side boiler feedwater.
In above-mentioned technical proposal, it is preferable that the removing CO2Step is using hydramine method come the CO in elimination reaction product2, Adding 3% with 15%~20%MEA or 35%~50%MDEA~5% piperazine is absorbent, in CO2With product in absorption tower Contact, removes CO therein2, obtain CO2Product of the content less than 1~100ppm.
In above-mentioned technical proposal, it is preferable that OCM product is cooled down in ice chest A, ice chest B, ice chest C, is exchanged heat therewith Cold logistics is lightness-removing column overhead, lightness-removing column tower reactor distillate, C2Cryogen and C3Cryogen.
In above-mentioned technical proposal, it is preferable that the operating pressure of domethanizing column is 2.5~3.5MPaG, tower top temperature is -120 ~-80 DEG C.
In above-mentioned technical proposal, it is preferable that demethanizer column overhead distillate is cooled down in ice chest D, ice chest E, is exchanged heat therewith Cold logistics be through throttling cooling lightness-removing column tower reactor distillate, expanded machine step-down refrigeration lightness-removing column tower reactor distillate.
In above-mentioned technical proposal, it is preferable that the operating pressure of lightness-removing column is 2.0~3.0MPaG, tower top temperature is -150 ~-120 DEG C.
In above-mentioned technical proposal, it is preferable that the outlet pressure of expanding machine is 0.2~1.0MPaG, the outlet streams of expanding machine Temperature is -150~-120 DEG C.
In above-mentioned technical proposal, it is preferable that the OCM product by after ice chest A, ice chest B, ice chest C, 30~ 70wt% lighter hydrocarbons are condensed；Demethanizer column overhead distillate is by after ice chest D, ice chest E cooling, 50~90wt% lighter hydrocarbons are cold It is solidifying.
In above-mentioned technical proposal, it is preferable that acetylene removal step uses catalytic hydrogenation method, and catalyst is Pd/Al2O3Type catalyst, Acetylene hydrogenation generation ethane and the ethene in fixed bed reactors, obtains product of the acetylene content less than 2ppm.
It is an object of the invention to provide the technique of Catalyst for Oxidative Coupling of Methane, the technical process is fixed by using multistage The adiabatic thin bed reactor of bed, intersegmental setting quencher and temperature control system, by reactor bed and its outlet temperature control System is maintained at 100~200 DEG C in a range of technological means, the temperature rise for realizing bed reaction gas, and intermediate reaction gas is through each At 700~800 DEG C, the whole total methane conversion of course of reaction ensures temperature after the corresponding rapid-cooling heat exchanger heat exchange of section fixed bed More than 24%, C2 selectivity are more than 73%；By height between multiply charging, expanding machine, rectifying column and ice chest and refrigerator Be thermally integrated many energy saving means such as technology, can not only the reaction cycle material such as isolated ethylene product and methane, ethane, and Energy consumption is low, be easily achieved industrialization.The present invention is by oxidative coupling of methane product by compression, hydramine method, drying, deep cooling essence The operation such as evaporate to separate component one by one, while using height heat between multiply charging, expanding machine, rectifying column and ice chest and refrigerator Many energy saving means reducing energy consumptions such as integrated technology, the ethylene product purity for obtaining reaches 99.95%, and Recovery rate of ethylene reaches More than 99%, with compared with scale light hydrocarbon cracking ethene flow, unit ethene energy consumption can reduce by more than 30%, achieve preferably Technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 be natural gas, 2 be pure oxygen or it is oxygen-enriched, 41 for preheating after reaction mixture gas, 42 be product gas, 43 For the solidifying water of reaction process, 3 are reaction gas, 4 for the reaction gas after compression, 5 are removing CO2Rear reaction gas, 6 are for again after compression Reaction gas, 7 be reaction gas after drying and dehydrating, 8 be reaction gas after being cooled down through ice chest A, 9 be point flow container A gas phases, 10 be a point liquid Tank A liquid phases, 11 are to divide a flow container B gas phases, 13 for a point flow container B liquid phases, 14- are through ice chest through the reaction gas after ice chest B coolings, 12 Reaction gas after C coolings, 15 is demethanizer column overhead distillate (H2、N2、CH4Etc. component), 16 be demethanizer reactor distillate (C2 +~C3 +Component), 17 be demethanizer column overhead distillate after being cooled down through ice chest D, 18 be point flow container C gas phases, 19 be a point liquid Tank C liquid phases, 20 are for lightness-removing column overhead (is rich in H through the demethanizer column overhead distillate after ice chest E coolings, 212、CO And N2), 22 be lightness-removing column tower reactor distillate (be rich in CH4), 23 be through pressure-reducing valve throttling cooling after lightness-removing column tower reactor distillate, 24 is for the lightness-removing column tower reactor distillate after the cooling of expanded machine, 26 are through the lightness-removing column tower reactor distillate after ice chest D heating, 25 Lightness-removing column tower reactor distillate after being heated through ice chest E, 27 be lightness-removing column tower reactor distillate after being heated through ice chest C, 28 be through cold Lightness-removing column tower reactor distillate after case B heating, 29 be lightness-removing column tower reactor distillate after being heated through ice chest A, 30 be through ice chest C Lightness-removing column overhead after heating, 31 be lightness-removing column overhead after being heated through ice chest B, 32 be to be heated through ice chest A Lightness-removing column overhead afterwards, 33 is deethanizer overhead distillate (C2 +Component), 34 be dethanizer tower reactor distillate (C3 +Component), 35 be ethylene rectifying column charging (ethene, ethane), 36 be ethylene rectifying column overhead (ethylene product), 37 be Ethylene rectifying column tower reactor distillate (ethane), 38 are CO2。
Fig. 2 OCM reaction process is vertically arranged schematic diagram.
Fig. 3 OCM reaction process lateral arrangement schematic diagrames.
Shell-and-tube quenching boiler schematic diagram with central tube in Fig. 4 OCM reaction process.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
【Embodiment 1】
Using the technical process shown in accompanying drawing 1, enter equipped with Na after natural gas and oxygen mix2WO3-Mn/SiO2Catalyst Oxidative coupling of methane device.As shown in figs 2-4.
Fig. 2 is vertically arranged schematic diagram for OCM reaction process.Natural gas, oxygen mixture after being adequately mixed and preheating (121) feeding first paragraph oxidative coupling of methane device (101) is reacted, and the reaction of the high temperature containing ethene of reactor outlet is produced The tube side that thing gas enters the first paragraph rapid-cooling heat exchanger (102) being directly connected to first paragraph reactor is cooled rapidly, then send Enter second segment oxidative coupling of methane device (105) to be reacted, the high-temperature reaction product gas of reactor outlet enters and the The tube side of the second segment rapid-cooling heat exchanger (106) that second stage reactor is directly connected to is cooled rapidly, cold through final stage quencher But the reaction product gas (123) after are re-fed into downstream separation flow or next section of oxidative coupling of methane device；It is oxygen, natural Gas, carrier gas or vapor (122) can from second stage reactor (105) or afterwards each section of reactor air inlet feeding reaction In device, mixed with reaction gas after distributor is distributed；High pressure boiler water supply (126) or (130) through with from first paragraph The high-temperature boiler feedwater of rapid-cooling heat exchanger (102) or second segment rapid-cooling heat exchanger (106), vapour mixture (125) or (129) vapour After liquid equilibrium separation, aqueous water (124) or (128) with HTHP are from Steam drum hydrostatic column H1 or H2 One section of HP steam drum (103) or the bottom of second segment HP steam drum (107), be respectively fed to first paragraph rapid-cooling heat exchanger (102) or The shell side of second segment rapid-cooling heat exchanger (106) is quickly exchanged heat with high-temperature reaction product gas, the high-temperature boiler feedwater of generation, Vapour mixture (125) or (129) return to first paragraph HP steam drum (103) respectively or second segment HP steam drum (107) enters promoting the circulation of qi Liquid is separated, and adjusted valve (104) or (108) are sent out respectively for the high temperature and high pressure steam (127) of generation or (131).
Fig. 3 is OCM reaction process lateral arrangement schematic diagrames.Natural gas, oxygen mixture after being adequately mixed and preheating (221) feeding first paragraph oxidative coupling of methane device (201) is reacted, and the reaction of the high temperature containing ethene of reactor outlet is produced The tube side that thing gas enters the first paragraph rapid-cooling heat exchanger (202) being directly connected to first paragraph reactor is cooled rapidly, then leads to Cross one section of bend pipe (203) feeding second segment oxidative coupling of methane device (204) to be reacted, the pyroreaction of reactor outlet The tube side that product gas enter the second segment rapid-cooling heat exchanger (205) being directly connected to second segment reactor is cooled rapidly, and passes through Reaction product gas (223) after the cooling of final stage quencher are re-fed into downstream separation flow or next section of methane oxidation coupling Reactor；Oxygen, natural gas, carrier gas or water (222) can entering from (203) section start of the bend pipe after each section of rapid-cooling heat exchanger In gas port feeding reactor, first stage reactor under being sent into after being mixed with reaction gas in bend pipe；High pressure boiler water supply (228) Through with from first paragraph rapid-cooling heat exchanger (202) and second segment rapid-cooling heat exchanger (205) high-temperature boiler feedwater, vapour mixture (225) after being separated with (227) VLE, aqueous water (224) and (226) with HTHP are from quiet with Steam drum The bottom of the HP steam drum (206) of fluid column H21, is respectively fed to first paragraph rapid-cooling heat exchanger (202) and second segment rapid-cooling heat exchanger (205) shell side is quickly exchanged heat with high-temperature reaction product gas, the high-temperature boiler feedwater of generation, vapour mixture (225) (227) returning to HP steam drum (206) respectively carries out gas-liquid separation, high temperature and high pressure steam (229) adjusted valve (207) of generation Send out.
Fig. 4 is the shell-and-tube quenching boiler schematic diagram with central tube in OCM reaction process.The pyroreaction of reactor outlet Product gas (321) enter the tube side of the board-like quenching boiler of the light wall pipe with central tube being directly connected to reactor by fast quickly cooling But, high pressure boiler water supply (323) enters the shell of quenching boiler and high-temperature reaction product gas (321) and carries out directly from the bottom mouth of pipe Heat exchange is connect, the high-temperature boiler feedwater of generation, vapour mixture (324) return to high pressure vapour from the shell top mouth of pipe of quenching boiler Bag；Adjusting means (303) is provided with the exit of the central tube (301) of quenching boiler, can be by adjusting adjusting means (303) Aperture, adjustment by reaction product gas (321) uninterrupted for being flowed through from central tube (301), so as to influence shell-and-tube urgency The flow rate of reaction product gas (321), plays quick regulation quenching boiler in heat exchanger tube (302) around cold boiler inner central tube The effect of heat exchange amount.
To Fig. 2~Fig. 4, reaction gas leaves each section of bed temperature for 850~900 DEG C.Especially, for Tu3Zhong Dai centers Adjusting means aperture in the board-like quenching boiler of light wall pipe of pipe is controllable to 80~40%, the stream that reaction gas passes through surrounding heat exchanger tube Speed is controlled to 71~93m/s.
It is 1000 tons/year of OCM reaction units of ethene for unit scale, reactor is single bed, is used The W-Mn/SiO of the excellent performance disclosed in CN1187118C2Catalyst, bed is divided into four sections, and every section of catalyst bed layer height is 20~40mm, CH in every section of bed charging4/O2Mol ratio is 5~9, and each section of bed volume air speed is 80000~140000h-1, A diameter of 0.3~the 0.5m of bed, the temperature after the mixture of feed preheating being adequately mixed is 750 DEG C, and bed reaction pressure is 0.5MPaG, bed reaction temperature is 750~950 DEG C, and intermediate reaction gas temperature after each section of correspondence rapid-cooling heat exchanger heat cooling is 750℃.4th section of rapid-cooling heat exchanger outlet temperature is 800 DEG C, 0.3MPaG.Stop of the reaction gas in each section of rapid-cooling heat exchanger Time is 0.03~0.08s.Each section of rapid-cooling heat exchanger vaporization rate is controlled to 10~20%, Steam drum hydrostatic column H1~H4, H11 is highly 2~4m.By adjusting HP steam drum steam (vapor) outlet governor valve control pressure, can produce high-pressure saturated steam 8~ 13MPaG。
Reactor outlet composition is shown in Table 1.
Table 1
The reaction stream of OCM reaction members outlet is separated using flow as shown in Figure 1.Reaction gas is through compressor pressure It is reduced to 1.5~2.5MPaG；Subsequently into CO2Absorption tower, it is absorbent to use 35%MDEA plus 3% piperazine, the reaction after absorption CO in product2Content is reduced to 1~10ppm (mol%)；Go successively to compressor and be pressurized to 3.0~3.5MPaG, and enter dry Dry device removes moisture, water content is reduced to 1~10ppm；Product after dehydration is distillated into ice chest A with lightness-removing column tower top Thing, lightness-removing column tower reactor distillate, (- 40~-35 DEG C) heat exchange of C3 cryogens, are cooled to -37~-32 DEG C, after being separated through undue flow container, Condensate liquid enters domethanizing column, do not coagulate gas go successively to ice chest B and lightness-removing column overhead, lightness-removing column tower reactor distillate, (- 81~-76 DEG C) heat exchange of C2 cryogens, are cooled to -78~-73 DEG C, and after being separated through undue flow container, condensate liquid enters domethanizing column, Gas is not coagulated goes successively to ice chest C and lightness-removing column overhead, lightness-removing column tower reactor distillate, C2 cryogens (- 101~-96 DEG C) Heat exchange, domethanizing column is fully entered after being cooled to -98~-93 DEG C；Demethanizer column overhead 2.9~3.2MPaG of operating pressure, tower top Condensation temperature -98~-93 DEG C, tower top obtains distillate key component H2、N2、CO、CH4, tower reactor distillate key component C2H4、 C2H6、C3H6；Demethanizer column overhead distillate enters ice chest D and is exchanged heat with lightness-removing column overhead, is cooled to -102~-105 DEG C, after being separated through undue flow container, condensate liquid enters lightness-removing column, gas is not coagulated and goes successively to ice chest E and lightness-removing column tower reactor distillate With (- 140~-130 DEG C) heat exchange of C1 cryogens, lightness-removing column is fully entered after being cooled to -125~135 DEG C；Lightness-removing column tower top operation pressure 2.2~2.5MPaG of power, -128~-135 DEG C of overhead condensation temperature, overhead key component H2、N2, CO, tower reactor distillate It is CH4Cycle stock, CH4Content reaches more than 98%；CH4After expanding machine is depressurized to 0.5~0.8MPaG, temperature reaches cycle stock To -148~-140 DEG C, by returning to OCM reaction members after ice chest E, ice chest C, ice chest B, ice chest A heating；Lightness-removing column tower top evaporates Go out thing to be used as fuel gas by after ice chest ice chest D, ice chest C, ice chest B, ice chest A heat exchange；Demethanizer reactor distillate enters Enter dethanizer, tower reactor distillate is C3+Component, overhead enters acetylene reactor, and it is anti-that acetylene therein occurs hydrogenation Ethene and ethane should be changed into, acetylene content is reduced to 1~5ppm (mol%)；Material after acetylene removal enters ethylene rectifying column, Tower reactor distillate is ethane, returns to OCM reaction members, and overhead is ethylene product.Ethylene product composition is shown in Table 2.
Table 2.
Component Carbon dioxide Methane Acetylene Ethene Ethane
Composition mol% ＜ 1ppm ＜ 300ppm ＜ 2ppm ≥99.95 ＜ 200ppm
Ethylene product purity reaches polymer grade ethylene specification, and Recovery rate of ethylene reaches 99%.
It is that 540kg marks oil/ton ethene, Catalyst for Oxidative Coupling of Methane synthesis energy with scale cracking ethylene device comprehensive energy consumption Consume for 360kg marks oil/ton ethene, more than 30% is reduced compared with cracking ethylene technology.
【Comparative example】
Patent US2015/0368167A1 discloses a kind of process of Catalyst for Oxidative Coupling of Methane, the methane oxidation of use Coupling reaction catalyst is nano-wire catalyst (methane oxidative coupling catalyst of Siluria companies exploitation), and reaction temperature is 260~950 DEG C, reaction pressure is 0.345~1.38Mpa, and the product that reaction is obtained mainly is constituted and is shown in Table 3.
Table 3
Product separation process is provided with the first knockout tower and the second knockout tower, and be divided into for product by the first knockout tower Rich in C2 logistics and rich in CH4And N2Logistics, first knockout tower 205~900kPa of operating pressure, operation temperature -162~-134 ℃.Expanding machine is set on the first knockout tower wherein one feed stream carries out decompression cooling.Second knockout tower will be enriched in CH4、N2 Logistics is divided into rich in CH4Logistics and rich in N2Logistics, second knockout tower 275~585kPa of operating pressure, operation temperature -168~- 210℃.The patent is different from the oxidative coupling of methane product composition that this patent is generated, and reacts and separation operation condition Differ.

Claims (10)

1. a kind of method of Catalyst for Oxidative Coupling of Methane, comprises the following steps：
A () in OCM reaction members, natural gas is collected after mixing with oxygen and the methane of separative element return, ethane by reaction Into heat-exchange system, exchanged heat with product gas, reached the reaction temperature of regulation, into OCM reaction systems, made in catalyst Under, methane is converted into including ethene, ethane, CO, CO2、H2The product gas of O, alkynes, product gas is by reaction Integrated heat exchange system is cooled down, the solidifying solidifying water treatment system of water feeding technique of reaction process, other reaction streams feeding separative element, so Afterwards by compression, removing CO2, compression, drying steps, obtain remove CO2、H2OCM product after O；The OCM reactions are single The reaction process that unit uses includes at least two sections of the thin bed fixed bed reactors of methane oxidation coupling, by following optional A kind of means of anticipating realize Catalyst for Oxidative Coupling of Methane reaction process：(1) when reactor uses vertical arranged in series, every section of reaction It is directly connected to using rapid-cooling heat exchanger between device, every section of catalytic bed of reactor is made up of 1~2 bed, two beds are not for With catalyst, be adequately mixed and be preheated to methane after 600~900 DEG C, oxygen mixture feeding first paragraph fixed bed anti- Device is answered to be reacted, reaction pressure is 0.2~0.8MPaG, catalyst bed layer height is 15~100mm, and volume space velocity is 50000 ~150000h-1, 100~300 DEG C of reaction gas limit of temperature rise, the reaction gas of reactor outlet is passed through rapid-cooling heat exchanger tube side and shell Journey boiler feedwater exchanges heat and is quickly cooled to 700~1000 DEG C, is re-fed into next section of fixed bed reactors and proceeds reaction, Final stage reactor outlet is directly connected to rapid-cooling heat exchanger, and end reaction gas is by after final stage rapid-cooling heat exchanger tube side Temperature needed for being cooled to down stream train is simultaneously sent out；Each quencher shell and corresponding HP steam drum by tedge and under Drop pipe is connected, and forms boiler feedwater and the circulation of steam, constitutes Steam drum heat-exchange system；(2) reactor is using laterally string Townhouse is arranged, and every section of reactor and is exported the rapid-cooling heat exchanger and Steam drum heat-exchange system of connection therewith and is planted realization with (1st) Means are identical, but reactor, using horizontal arranged in series, rapid-cooling heat exchanger outlet is by one section of bend pipe and lower first stage reactor Entrance is connected, and multiple rapid-cooling heat exchangers share a Steam drum；(3) basis of realization rate is planted in (1st) kind or (2nd) On, rapid-cooling heat exchanger part is to employ the board-like quenching boiler of the light wall pipe with central tube, in the exit of quenching boiler central tube, Adjusting means is provided with, the reaction gas flow speed size flowed through from central tube is adjusted by adjusting means, so as to influence shell-and-tube chilling The flow velocity of reaction gas in heat exchanger tube around boiler inner central tube, plays a part of quick regulation quenching boiler thermic load, anti- In the case of answering device outlet temperature to fluctuate, the reaction bed temperature measured by the temperature element set in fixed bed reactors Feedback regulation, the heat exchange amount of quick adjustment quenching boiler, to ensure the temperature of reaction gas that quenching boiler tube side exports in regulation Degree, it is ensured that is reacted in lower first stage reactor is steadily carried out；
B () described OCM product forms at least three strands by after ice chest A, ice chest B, ice chest C, which part lighter hydrocarbons are condensed Enter domethanizing column；
C () demethanizer column overhead distillate is by after ice chest D, ice chest E cooling, which part lighter hydrocarbons are condensed, and form at least two Stock enters lightness-removing column；
D () lightness-removing column overhead includes H2, CO and part CH4, sequentially pass through ice chest D, ice chest C, ice chest B, ice chest A and OCM Product exchanges heat；
E () lightness-removing column tower reactor distillate is liquid CH4, refrigeration is depressured again by ice chest by expanding machine after first evaporation recovery cold After E, ice chest C, ice chest B, the heat exchange of ice chest A and OCM product, OCM reaction members are returned；
F () domethanizing column reactor distillate removes C by dethanizer3 +Component, tower top C2 +Component enters ethylene distillation after acetylene removal After tower, tower top obtains high-purity ethylene product.
2. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that catalyst is Na2WO3-Mn/ SiO2Catalyst；The hop count of the thin bed fixed bed reactors of methane oxidation coupling is 2~6 sections；In realization rate (1), reactor The temperature control system matched with charging is set；Other section of reactor in addition to first paragraph reactor, it is attached in reactor inlet Closely be provided with gas inlet and distributor, react it is intersegmental be passed through oxygen and/or natural gas, be every section reaction supplemental oxygen and/or Natural gas, to adjust every section of alcoxyl ratio of reaction, alcoxyl is 4~10 than scope, to control the temperature of beds and reaction gas Rise；Or it is passed through water vapour or inert gas and is controlled as carrier gas the temperature rise of beds and reaction gas；Realization rate (2) In, air inlet is provided with the bend pipe section start of rapid-cooling heat exchanger outlet connection, oxygen, natural gas, dilute is passed through during the course of the reaction Outgassing or water, realize being sufficiently mixed with reaction gas in bend pipe, the amount for being passed through oxygen and/or natural gas are adjusted, adjusting every section The alcoxyl ratio of reaction, by injecting carrier gas or water, is sufficiently mixed and exchanges heat in bend pipe with reaction gas, controls beds With the temperature rise of reaction gas；In realization rate (1) or (2), when beds produce temperature runaway, by cutting off reaction mixture gas in Oxygen and each section of reactor before the oxygen that is passed through stop reaction, while continuing to be passed through methane gas to take away beds Temperature, safe temperature is cooled to by whole reactor；In realization rate (1) or (2), rapid-cooling heat exchanger selects linear sleeve pipe Any one in formula, bushing type boiler, every section of rapid-cooling heat exchanger passes through tedge and down-comer phase with corresponding HP steam drum Even, the high steam for being produced in HP steam drum is sent out by the pipeline of top, pressure-regulating valve is set on pipeline, according to fixed bed The reaction bed temperature that the temperature element set in reactor is measured, or rapid-cooling heat exchanger tube side exports the temperature control of reaction gas The temperature of cell feeds back processed, adjusts valve action to adjust the pressure of high steam, so as to adjust changing for rapid-cooling heat exchanger by this Heat so that when reactor outlet temperature is different under different operating modes, the reaction gas temperature of rapid-cooling heat exchanger outlet is maintained at rule Fixed temperature, it is ensured that is reacted in lower first stage reactor is steadily carried out；100~200 DEG C of reaction gas limit of temperature rise, reactor outlet Reaction gas be passed through rapid-cooling heat exchanger tube side and shell side boiler feedwater and exchange heat and be quickly cooled to 700~800 DEG C.
3. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that the removing CO2Step is used The CO that hydramine method is come in elimination reaction product2, adding 3% with 15%~20%MEA or 35%~50%MDEA~5% piperazine is suction Agent is received, in CO2Contacted with product in absorption tower, remove CO therein2, obtain CO2Reaction of the content less than 1~100ppm Product.
4. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that OCM product ice chest A, Cooled down in ice chest B, ice chest C, the cold logistics for exchanging heat therewith is lightness-removing column overhead, lightness-removing column tower reactor distillate, C2Cryogen And C3Cryogen.
5. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that the operating pressure of domethanizing column It is 2.5~3.5MPaG, tower top temperature is -120~-80 DEG C.
6. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that demethanizer column overhead distillate Cooled down in ice chest D, ice chest E, the cold logistics for exchanging heat therewith is lightness-removing column tower reactor distillate, the expanded machine drop through throttling cooling The cold lightness-removing column tower reactor distillate of compacting.
7. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that the operating pressure of lightness-removing column is 2.0~3.0MPaG, tower top temperature is -150~-120 DEG C.
8. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that the outlet pressure of expanding machine is 0.2~1.0MPaG, the outlet streams temperature of expanding machine is -150~-120 DEG C.
9. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that the OCM product is passed through After ice chest A, ice chest B, ice chest C, 30~70wt% lighter hydrocarbons are condensed；Demethanizer column overhead distillate is cold by ice chest D, ice chest E But after, 50~90wt% lighter hydrocarbons are condensed.
10. the method for Catalyst for Oxidative Coupling of Methane according to claim 1, it is characterised in that the acetylene removal step is using urging Change hydrogenation method, catalyst is Pd/Al2O3Type catalyst, acetylene hydrogenation generation ethane and ethene, obtains in fixed bed reactors Product of the acetylene content less than 2ppm.
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CN113557401A (en) * 2019-03-11 2021-10-26 环球油品有限责任公司 Hydrocarbon gas processing
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CN111747821A (en) * 2019-03-27 2020-10-09 中国石油化工股份有限公司 Process for preparing olefin by oxidative coupling of methane
CN111747820A (en) * 2019-03-27 2020-10-09 中国石油化工股份有限公司 Method for producing hydrocarbons
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CN111747815B (en) * 2019-03-27 2023-04-11 中国石油化工股份有限公司 Separation method of product gas of oxidative coupling reaction of methane
CN114736095A (en) * 2022-05-12 2022-07-12 中海石油气电集团有限责任公司 Method for preparing hydrogen and olefin by catalytic oxidation of natural gas
CN115046326A (en) * 2022-05-31 2022-09-13 连云港石化有限公司 Binary refrigeration start system and method for light hydrocarbon cracking device
CN115046326B (en) * 2022-05-31 2024-06-18 连云港石化有限公司 Binary refrigeration driving system and method for light hydrocarbon cracking device

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