CN105399604B - A kind of energy-saving ultra-large methane synthesizing method and device producing different brackets steam - Google Patents

A kind of energy-saving ultra-large methane synthesizing method and device producing different brackets steam Download PDF

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CN105399604B
CN105399604B CN201510658690.4A CN201510658690A CN105399604B CN 105399604 B CN105399604 B CN 105399604B CN 201510658690 A CN201510658690 A CN 201510658690A CN 105399604 B CN105399604 B CN 105399604B
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methanol
gas
outlet
steam
liquid
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CN105399604A (en
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杨震东
王彪
李丹
董红军
张守亮
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Shanghai International Engineering Consulting Co
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SHANGHAI INTERNATIONAL CONSTRUCTION ENGINEERING CONSULTING CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The energy-saving ultra-large methane synthesizing method of production different brackets steam disclosed by the invention, it is that virgin gas is mixed to form gaseous mixture with circulating air after overcompression, gaseous mixture carries out methanol synthesis reaction after heating and forms the complete synthesis gas and methanol steam mixture of unreacted in synchronous two the first methanol reactors for entering parallel connection, the complete synthesis gas of unreacted and methanol steam mixture continue methanol synthesis reaction into the second methanol reactor after cooling and obtain end product, end product passes through refrigerated separation, the portion gas isolated is as the circulating air, liquid crude carbinol enters downstream rectification cell.The invention also discloses the devices for realizing this method.The heat-exchange network that the present invention passes through reasonable disposition, conversion per pass and reactor outlet methanol concentration are improved to greatest extent, recycle ratio and energy consumption are reduced, different grades of steam can be produced, low-pressure steam can satisfy the demand for low pressure steam of downstream methanol rectifier unit.

Description

A kind of energy-saving ultra-large methane synthesizing method producing different brackets steam and Device
Technical field
The present invention relates to preparing methanol technical field by the synthesis gas comprising hydrogen and oxycarbide, in particular to a kind of life Produce the energy-saving ultra-large methane synthesizing method and device of different brackets steam.
Background technique
It is known to those skilled in the art by by (H2-CO2)/(CO+CO2) value be 2.0~2.1 or so synthesis gas be catalyzed The method and technique of reaction production methanol.
Current methanol-fueled CLC process units is towards scale enlargement, and conversion per pass is high, and energy regenerating is reasonable, catalyst bed The directions such as the temperature difference is small, and synthesis reactor pressure drop is small, and structure is simple, stable operation reliably facilitates are developed.
For the method and system of large scale preparation methanol as described by CN102171171A, virgin gas is first after mixing with circulating air It is introduced into the first pipe-type water-cooling reactor and methanol synthesis reaction occurs, the mixture of synthesis gas and methanol steam after then reacting It is again introduced into air cooling reactor, using the reaction heat of the cooling air cooling reactor of the gaseous mixture of virgin gas and circulating air, after reaction Mixture is after supercooling, and into gas-liquid separator, one gas isolated recycles again.Make in this methanol synthesis loop With air cooling reactor, it is lower that there is heat transfer efficiencys, and bed temperature is not easily controlled, it is possible to the methanol in process gas occurs The case where catalyst bed condenses；Since capacity usage ratio is low, lead to that follow-up process is air-cooled, water cooling load increases；And due to Air cooling reactor does not have heat source, and the reaction heat of itself is few, the problems such as driving initial stage heating rate is slow, and the recovery time is long easily occurs. Patent CN1989092B description the method for gas phase reaction, refer to a kind of methanol synthesis loop of large size, it may be assumed that virgin gas and By preheating, methanol synthesis reaction, synthesis occur synthesis gas for the methanol reactor for initially entering the radial generation steam of First For gas with methanol steam mixture after supercooling and separating methanol, gas enters second radial direction after recompression and preheating Methanol synthesis reaction occurs for the methanol reactor for generating steam.Final unreacted synthesis gas and methanol steam, after supercooling Into gas-liquid separator, isolated gas is recycled again.In above-mentioned extensive methanol synthesis loop, methanol synthesis reaction Device upper catalyst bed layer is constantly in overtemperature state, and hot(test)-spot temperature reaches as high as 309 DEG C, and when load adjustment is well over 309 DEG C, there are hidden danger when leading to system heavy-duty service；Appearance system wax deposition is serious, and by-product increases, and internal circulating load is big, compresses function Consume the problems such as high.
Summary of the invention
The first technical problem to be solved by the present invention is in the presence of existing large scale preparation methanol technics Above-mentioned technical problem and a kind of energy-saving ultra-large methane synthesizing method for producing different brackets steam is provided.
The second technical problem to be solved by the present invention, which is to provide, realizes the energy-saving of above-mentioned production different brackets steam The device of ultra-large methane synthesizing method.
The energy-saving ultra-large methane synthesizing method of production different brackets steam as first aspect present invention, it is special Sign is that virgin gas is mixed to form the first gaseous mixture after overcompression with circulating air, and the first gaseous mixture is synchronous after heating to be entered simultaneously Methanol synthesis reaction is carried out in two the first methanol reactors of connection generates the complete synthesis gas and methanol steam mixture of unreacted, The complete synthesis gas of the unreacted and methanol steam mixture are laggard after cooling or by condensing and separating portion of product between section Entering the second methanol reactor and continue methanol synthesis reaction to obtain end product, the end product passes through refrigerated separation, point The portion gas separated out enters downstream rectification cell as the circulating air, liquid crude carbinol.
In a preferred embodiment of the invention, first methanol reactor is water cooling methanol reactor.
In a preferred embodiment of the invention, several reaction tubes are configured in the water cooling methanol reactor, Copper-based catalysts are configured in the reaction tube, first gaseous mixture enters in the reaction tube, in the reaction tube Copper-based catalysts catalytic action under occur methanol synthesis reaction, methanol reaction is removed by boiled water outside the reaction tube and is produced Raw heat.
In a preferred embodiment of the invention, second methanol reactor is urging for CN203227477U description Agent is loaded on the isothermal fixed bed reactors between heat exchanger tube or by catalyst loaded on the board-like synthesis of IMC isothermal on the outside of plank Tower.
In a preferred embodiment of the invention, the complete synthesis gas of unreacted and methanol steam mixture enter described On the outside of the heat exchanger tubes of isothermal fixed bed reactors or on the outside of the plank of the board-like synthetic tower of IMC isothermal, on the outside of heat exchanger tube or plank Methanol synthesis reaction occurs under the copper-based catalysts catalytic action in outside, is moved on the inside of heat exchanger tube or on the inside of plank by boiled water Except methanol reacts generated heat.
In a preferred embodiment of the invention, in second methanol reactor, the flow direction of reaction gas is axis To or it is radial.
In a preferred embodiment of the invention, the copper-based catalysts and the second methanol in first methanol reactor Copper-based catalysts in reactor are identical, are high/low temperature activity copper-based catalysts.
In a preferred embodiment of the invention, the copper-based catalysts in first methanol reactor are high temperature active Copper-based catalysts, the copper-based catalysts in second methanol reactor are low temperature active copper-based catalysts.
In a preferred embodiment of the invention, the virgin gas is 7.4~8.1MPag by compressed pressure.
In a preferred embodiment of the invention, first gaseous mixture enters the first methanol in parallel after heating The temperature of reactor is 210 DEG C~230 DEG C.
In a preferred embodiment of the invention, each component content of first gaseous mixture after heating is H2For 40~70mol%；CO is 5~25mol%；CO2For 1~10mol%.
In a preferred embodiment of the invention, first methanol reactor is anti-using boiled water removal methanol-fueled CLC The heat that should be released.
In a preferred embodiment of the invention, first methanol reactor sends out the first liquid-vapor mixture, described First liquid-vapor mixture generates the middle pressure steam that a pressure is 2.2MPag~2.7MPag after carrying out vapor-liquid separation.
In a preferred embodiment of the invention, the reaction forms the complete synthesis gas of unreacted and methanol steam mixing The temperature of object is 240 DEG C~260 DEG C.
In a preferred embodiment of the invention, the complete synthesis gas of the unreacted and methanol steam mixture are by drop Temperature after temperature is 210 DEG C~220 DEG C.
In a preferred embodiment of the invention, the complete synthesis gas of the unreacted and methanol steam mixture with it is described First gaseous mixture exchanges heat.
In a preferred embodiment of the invention, the complete synthesis gas of the unreacted and methanol steam mixture with it is described After first gaseous mixture is exchanged heat, enter after condensing and separating portion of product between section, then after being exchanged heat with end product Second methanol reactor continues methanol synthesis reaction and obtains end product.
In a preferred embodiment of the invention, the complete synthesis gas of the unreacted and methanol steam mixture with it is described Circulating air exchanges heat.
In a preferred embodiment of the invention, second methanol reactor is anti-using boiled water removal methanol-fueled CLC The heat that should be released.
In a preferred embodiment of the invention, second methanol reactor sends out the second liquid-vapor mixture, described Second liquid-vapor mixture generates the low-pressure steam that a pressure is 1.1MPag~1.7MPag after carrying out steam-water separation.
In a preferred embodiment of the invention, the end product is 30 DEG C~45 DEG C by temperature after cooling.
In a preferred embodiment of the invention, it is carried out in the end product cooling procedure with first gaseous mixture Heat exchange.
In a preferred embodiment of the invention, the alcohol net value in the end product is 18~21mol%.
The energy-saving ultra-large methanol-fueled CLC side of above-mentioned production different brackets steam as a second aspect of the invention The device of method, comprising:
First cooling device, first cooling device have the first gaseous mixture entrance, the first mixed gas outlet, first most Afterwards product inlet, the first end product outlet, wherein the first gaseous mixture entrance connect a fresh letter shoot one end and One end of first circulation letter shoot, the fresh letter shoot send virgin gas, and the first circulation letter shoot, which is sent, to follow Ring gas；
The top of two the first methanol reactors, every one first methanol reactor is configured with the second gaseous mixture entrance, top It is exported configured with the first liquid-vapor mixture, configured with the first separation water refluxing opening, bottom is complete configured with the first unreacted for lower part Synthesis gas and methanol steam mixture outlet, wherein every one second gaseous mixture entrance by one first mixed gas pipeline with it is described The first mixed gas outlet connection in first cooling device；
One first vapour liquid separator, first vapour liquid separator at least configure there are two the first liquid-vapor mixture entrance, Two first separation water outs and the outlet of middle pressure steam, two of them the first liquid-vapor mixture entrance pass through two pieces the respectively One liquid-vapor mixture delivery pipe is exported with first liquid-vapor mixture on a corresponding methanol reactor top and is connected, and two first Separation water out passes through two first separation water delivery pipes respectively and separates water reflux with the first of corresponding methanol reactor lower part Mouth connection；Medium pressure steam (vapor) outlet sends out middle pressure steam；
One second methanol reactor, the synthesis complete configured with first unreacted of the top of second methanol reactor Gas and methanol steam mixture inlet and two the second liquid-vapor mixture outlets, bottom is configured with the first end product outlet With two second separation water refluxing openings, the complete synthesis gas of first unreacted and methanol steam mixture inlet pass through first not First unreacted of reacted synthesis gas and methanol steam mixture delivery pipe and two the first methanol reactor bottoms is complete Synthesis gas is connected with methanol steam mixture outlet；The first end product outlet passes through the first end product delivery pipe and institute State the first end product entrance connection in the first cooling device；
One second vapour liquid separator, second vapour liquid separator at least configure there are two the second liquid-vapor mixture entrance, Two second separation water outs and a low-pressure steam outlet, two of them the second liquid-vapor mixture entrance pass through two respectively Two liquid-vapor mixture delivery pipes are exported with the second liquid-vapor mixture corresponding in second methanol reactor and are connected, and two second Separation water out passes through two second separation water delivery pipes respectively and separates water in second methanol reactor corresponding second Refluxing opening connection, the low-pressure steam outlet send out low-pressure steam；
There is the second end product entrance and the second end product to export for second cooling device, second cooling device, Second end product entrance is exported by the first end product in the second end product delivery pipe and first cooling device Connection；
There is third end product entrance and third end product to export for third cooling device, the third cooling device, Third end product entrance is exported by the second end product in third end product delivery pipe and second cooling device Connection；
There is the 4th end product entrance, first circulation gas to go out for one third gas-liquid separator, the third gas-liquid separator Mouth and separation liquid outlet, wherein the 4th end product entrance passes through the 4th end product delivery pipe and third cooling Third end product in device exports connection；On the one hand connection one speeds to put pipe for the first circulation gas outlet, on the other hand logical A recycle compressor is crossed to connect with the other end of the first circulation letter shoot；
There is a separation liquid inlet, crude carbinol outlet and flashed vapour to go out for one reduced-pressure flash tank, the reduced-pressure flash tank Mouthful, the separation liquid inlet is connected by the separation liquid outlet on separation liquid delivery tube and the third gas-liquid separator It connects, the crude carbinol outlet output crude carbinol, flashed vapour is sent out in the flashed vapour outlet.
In a preferred embodiment of the invention, first cooling device is gas-gas heat exchanger, the second cooling device For air cooler, third cooling device is water cooling heat exchanger.
It in a preferred embodiment of the invention, further include the 4th cooling device, the 4th cooling device has the The complete synthesis gas of two unreacteds and the complete synthesis gas and methanol steam mixture of methanol steam mixture inlet, the second unreacted go out Mouth, third gaseous mixture entrance or second circulation gas entrance, third mixed gas outlet or the outlet of second circulation gas, described second is not anti- The synthesis gas and methanol steam mixture inlet the answered synthesis gas and methanol steam mixture complete by second unreacted The delivery pipe synthesis gas complete with the first unreacted of two the first methanol reactor bottoms and methanol steam mixture outlet are connect, The complete synthesis gas of second unreacted and methanol steam mixture outlet are steamed by the complete synthesis gas of third unreacted and methanol First unreacted of vapour mixture delivery pipe and second methanol reactor complete synthesis gas and methanol steam mixture inlet Connection, the third gaseous mixture entrance are gone out by the second mixed gas pipeline and the first gaseous mixture in first cooling device Mouth connection or second circulation gas entrance are connect by second circulation letter shoot with the first circulation letter shoot；Described Three mixed gas outlets connect with the second gaseous mixture entrance in two the first methanol reactors by third mixed gas pipeline or The outlet of second circulation gas described in person recycles letter shoot by third and enters with the second gaseous mixture in two the first methanol reactors Mouth is connected and is connect by third mixed gas pipeline with the second gaseous mixture entrance in two the first methanol reactors.
In a preferred embodiment of the invention, it connects in the fresh letter shoot compressor.
In a preferred embodiment of the invention, first methanol reactor is water cooling methanol reactor.
In a preferred embodiment of the invention, configured with several first reactions in the water cooling methanol reactor Pipe is configured with copper-based catalysts in first reaction tube, and first gaseous mixture enters in first reaction tube, Methanol synthesis reaction occurs under copper-based catalysts catalytic action in first reaction tube, passes through boiling outside first reaction tube It is cooling to rise water.
In a preferred embodiment of the invention, second methanol reactor is urging for CN203227477U description Agent is loaded on the isothermal fixed bed reactors between heat exchanger tube or by catalyst loaded on the board-like synthesis of IMC isothermal on the outside of plank Tower.
In a preferred embodiment of the invention, the reaction gas flow direction in second methanol reactor to be axial or Radial form.
In a preferred embodiment of the invention, the copper-based catalysts and the second methanol in first methanol reactor Copper-based catalysts in reactor are identical, are high/low temperature activity copper-based catalysts.
In a preferred embodiment of the invention, the copper-based catalysts in first methanol reactor are high temperature active Copper-based catalysts, the copper-based catalysts in second methanol reactor are low temperature active copper-based catalysts.
In a preferred embodiment of the invention, first cooling device, the 4th cooling device are gas-gas heat exchanger, Second cooling device is air cooler, and third cooling device is water cooling heat exchanger.
Alternatively, the energy-saving ultra-large methanol of above-mentioned production different brackets steam as a second aspect of the invention closes At the device of method, comprising:
5th cooling device, the 5th cooling device have the 4th gaseous mixture entrance, the 4th mixed gas outlet, third not Reacted synthesis gas and the complete synthesis gas and methanol steam mixture outlet of methanol steam mixture inlet, third unreacted, Wherein the 4th gaseous mixture entrance connects one end of a fresh letter shoot and one end of first circulation letter shoot, described new Fresh letter shoot sends virgin gas, and the first circulation letter shoot sends circulating air；
The top of two the first methanol reactors, every one first methanol reactor is configured with the second gaseous mixture entrance, top It is exported configured with the first liquid-vapor mixture, configured with the first separation water refluxing opening, bottom is complete configured with the first unreacted for lower part Synthesis gas and methanol steam mixture outlet, wherein every one second gaseous mixture entrance by one first mixed gas pipeline with it is described Third mixed gas outlet connection in 5th cooling device；The complete synthesis of first unreacted of two the first methanol reactor bottoms Gas and methanol steam mixture outlet and after connecing by the 4th unreacted complete synthesis gas and methanol steam mixture delivery pipe with The synthesis gas that the third unreacted of 5th cooling device is complete is connected with methanol steam mixture inlet；
One first vapour liquid separator, first vapour liquid separator at least configure there are two the first liquid-vapor mixture entrance, Two first separation water outs and the outlet of middle pressure steam, two of them the first liquid-vapor mixture entrance pass through two pieces the respectively One liquid-vapor mixture delivery pipe is exported with first liquid-vapor mixture on a corresponding methanol reactor top and is connected, and two first Separation water out passes through two first separation water delivery pipes respectively and separates water reflux with the first of corresponding methanol reactor lower part Mouth connection；Medium pressure steam (vapor) outlet sends out middle pressure steam；
6th cooling device, the synthesis gas and methanol steam mixture that the 6th cooling device has the 4th unreacted complete Entrance, the 4th unreacted complete synthesis gas and methanol steam mixture outlet, the 4th unreacted of the 6th cooling device are complete Synthesis gas and methanol steam mixture inlet by the complete synthesis gas and methanol steam mixture delivery pipe of the 5th unreacted with The synthesis gas that the third unreacted of 5th cooling device is complete is connected with methanol steam mixture outlet；
4th gas-liquid separation device, the synthesis gas and methanol that the 4th gas-liquid separation device has the 5th unreacted complete steam Vapour mixture inlet, the complete syngas outlet of the first unreacted and the first separation liquid outlet, the 4th gas-liquid separation device The complete synthesis gas of 5th unreacted and methanol steam mixture inlet are mixed by the 6th unreacted complete synthesis gas and methanol steam Object the delivery pipe synthesis gas and methanol steam mixture outlet complete with the 4th unreacted of the 6th cooling device is closed to connect；
One second methanol reactor, the synthesis complete configured with first unreacted of the top of second methanol reactor Gas entrance and two the second liquid-vapor mixture outlets, bottom is configured with the first end product outlet and two second separation water Refluxing opening；
One second vapour liquid separator, second vapour liquid separator at least configure there are two the second liquid-vapor mixture entrance, Two second separation water outs and a low-pressure steam outlet, two of them the second liquid-vapor mixture entrance pass through two respectively Two liquid-vapor mixture delivery pipes are exported with the second liquid-vapor mixture corresponding in second methanol reactor and are connected, and two second Separation water out passes through two second separation water delivery pipes respectively and separates water in second methanol reactor corresponding second Refluxing opening connection, the low-pressure steam outlet send out low-pressure steam；
7th cooling device, the 7th cooling device have the 5th end product entrance, the outlet of the 5th end product, the The complete synthesis gas entrance of two unreacteds, the complete syngas outlet of the second unreacted, the 5th end product of the 7th cooling device enter It mouthful is exported and to be connected by the first end product of the 5th end product delivery pipe and second methanol reactor bottom, described the The complete synthesis gas entrance of second unreacted of seven cooling devices passes through the complete synthesis letter shoot of the first unreacted and the 4th gas-liquid The complete syngas outlet connection of first unreacted of separator；The complete syngas outlet of the second unreacted of 7th cooling device Entered by the complete synthesis letter shoot of the second unreacted synthesis gas complete with the first unreacted at the top of second methanol reactor Mouth connection；
There is the second end product entrance and the second end product to export for second cooling device, second cooling device, Second end product entrance is exported by the 5th end product in the 6th end product delivery pipe and the 7th cooling device Connection；
There is third end product entrance and third end product to export for third cooling device, the third cooling device, Third end product entrance is exported by the second end product in the 7th end product delivery pipe and second cooling device Connection；
There is the 4th end product entrance, first circulation gas to go out for one third gas-liquid separator, the third gas-liquid separator Mouth and the second separation liquid outlet, wherein the 4th end product entrance passes through the 8th end product delivery pipe and the third Third end product in cooling device exports connection；On the one hand connection one speeds to put pipe, another party for the first circulation gas outlet Face is connect by a recycle compressor with the other end of the first circulation letter shoot；
One reduced-pressure flash tank, the reduced-pressure flash tank have third separation liquid inlet, crude carbinol outlet and flash distillation Gas outlet, the third separation liquid inlet pass through second on the first separation liquid delivery tube and the third gas-liquid separator Liquid outlet connection is separated, the crude carbinol outlet output crude carbinol, flashed vapour is sent out in the flashed vapour outlet；
8th cooling device, the 8th cooling device have the 4th separation liquid inlet, the 4th separation liquid outlet, institute It states the 4th separation liquid inlet and liquid is separated with the first of the 4th gas-liquid separation device by the second separation liquid delivery tube 4th separation liquid outlet of outlet connection, the 8th cooling device separates liquid delivery tube and described first point by third It is connected from liquid delivery tube.
In a preferred embodiment of the invention, it connects in the fresh letter shoot compressor.
In a preferred embodiment of the invention, first methanol reactor is water cooling methanol reactor.
In a preferred embodiment of the invention, configured with several first reactions in the water cooling methanol reactor Pipe is configured with copper-based catalysts in first reaction tube, and first gaseous mixture enters in first reaction tube, Methanol synthesis reaction occurs under copper-based catalysts catalytic action in first reaction tube, passes through boiling outside first reaction tube It is cooling to rise water.
In a preferred embodiment of the invention, second methanol reactor is urging for CN203227477U description Agent is loaded on the isothermal fixed bed reactors between heat exchanger tube or by catalyst loaded on the board-like synthesis of IMC isothermal on the outside of plank Tower.
In a preferred embodiment of the invention, the reaction gas flow direction in second methanol reactor to be axial or Radial form.
In a preferred embodiment of the invention, the copper-based catalysts and the second methanol in first methanol reactor Copper-based catalysts in reactor are identical, are high/low temperature activity copper-based catalysts.
In a preferred embodiment of the invention, the copper-based catalysts in first methanol reactor are high temperature active Copper-based catalysts, the copper-based catalysts in second methanol reactor are low temperature active copper-based catalysts.
In a preferred embodiment of the invention, second cooling device is air cooler, and third cooling device is water Cold heat exchanger, the 5th cooling device is gas-gas heat exchanger, the 6th cooling device is air cooler, and the 7th cooling device is gas-gas heat exchange Device, the 8th cooling device are water cooling heat exchanger.
The problem that present invention is configured by the process of above-mentioned methanol synthesis loop, can be to avoid the prior art.And And analyzed from the chemical balance angle of methanol synthesis reaction, setting in this way can improve conversion per pass and anti-to greatest extent It answers device to export methanol concentration, reduces recycle ratio and energy consumption.
The present invention can be used for extensive methyl alcohol product installation (5500 ton/days or 1,800,000 tons/year), realize single series Ultra-large methanol production；The methanol synthesis loop of the invention patent can produce different grades of steam simultaneously, not only can be with Outer defeated middle pressure steam, and can satisfy the demand for low pressure steam of downstream methanol rectifier unit.The present invention can be maximum Conversion per pass and reactor outlet methanol concentration are improved, recycle ratio and energy consumption are reduced.
The isothermal fixed bed reactors or IMC isothermal of water cooling methanol reactor and another structure type of the invention are board-like Synthetic tower removes heat of reaction using boiled water, and heat transfer efficiency is high, and heat of reaction is rationally utilized, the low-pressure steam of generation It is used for downstream methanol rectifier unit.
Compared with prior art, the present invention having the following characteristics that
1. the present invention can be used for extensive methyl alcohol product installation, the production capacity of methanol device can achieve 5500 tons of daily output/ The ability of it or 1,800,000 tons/year.
2. the present invention is that inlet tower gas initially enters two water cooling methanol reactors in parallel, the mixture after reaction is entered back into The methanol reactor of one another structure type, continues methanol synthesis reaction, so that the alcohol of final reactor outlet is net Value is high.From the chemical balance angle of methanol synthesis reaction, in this way setting can improve to greatest extent conversion per pass and Reactor outlet methanol concentration reduces recycle ratio and energy consumption.
3. in synthesis loop of the invention, can select according to actual condition, two gas-gas heat exchanger series connection preheatings are designed； The preheating of separate unit gas-gas heat exchanger or two gas-gas heat exchangers distinguish the gaseous mixture of one circulating air and circulating air and virgin gas Preheating.The optimization design of heat-exchange network may be implemented in synthesis loop, energy rationally and efficiently uses.
4. the methanol reactor of another kind structure type of the invention, which uses, is similar to applicant's patent (grant number CN203227477U) the isothermal fixed bed reactors structure type or the skill of description being loaded on catalyst between heat exchanger tube The board-like synthetic tower structure of IMC isothermal of known Casale design in art field.Copper-based catalysts are placed on outside pipe or plank Side, synthesis gas carry out methanol synthesis reaction on the outside of reactor tube or plank.It is removed in reactor tube or plank using boiled water Reaction heat, and low-pressure steam is generated in drum.The low-pressure steam that isothermal methanol reactor of the invention generates can satisfy down Swim the demand for low pressure steam of methanol rectifying system.
5, the reaction gas flow direction that the methanol reactor of another structure type of the invention can use can be for axially It or is radial form.
6, the methanol reactor of two water-cooled reactors and another structure type can be filled and is provided simultaneously in the present invention The active copper-based catalysts of the same race of high/low temperature；High temperature active copper-based catalysts can be filled in two water-cooled reactors respectively, another A kind of copper-based catalysts of the methanol reactor dress low temperature active of outer structure type.
7. in synthesis loop of the invention, can be selected according to actual condition, design between two water-cooled reactor series blocks Condensation separator realizes that methanol is separated with unreacted synthesis gas.Unreacted synthesis gas enters an another structure type Methanol reactor continues methanol synthesis reaction.
Method and system of the invention can be used for extensive methyl alcohol product installation, production capacity reach 5500 tons of daily output/ It or 1,800,000 tons/year；Use the isothermal methanol of another structure type producing steam of water cooling methanol reactor series connection one in parallel The synthesis loop of reactor, can produce different grades of steam, and low-pressure steam can satisfy the low of downstream methanol rectifier unit Press steam demand.By the heat-exchange network of reasonable disposition, improves conversion per pass to greatest extent and reactor outlet methanol is dense Degree reduces recycle ratio and energy consumption.
Detailed description of the invention
Fig. 1 is that the energy-saving ultra-large methanol synthesizer process of the production different brackets steam of the embodiment of the present invention 1 is shown It is intended to.
Fig. 2 is that the energy-saving ultra-large methanol synthesizer process of the production different brackets steam of the embodiment of the present invention 2 is shown It is intended to.
Fig. 3 is that the energy-saving ultra-large methanol synthesizer process of the production different brackets steam of the embodiment of the present invention 3 is shown It is intended to.
Fig. 4 is that the energy-saving ultra-large methanol synthesizer process of the production different brackets steam of the embodiment of the present invention 4 is shown It is intended to.
Specific embodiment
Embodiment 1
Referring to Fig. 1, the energy-saving ultra-large methanol synthesizer of the production different brackets steam provided in figure, including two Platform water cooling methanol reactor A1, A2, the methanol reactor C of another structure type, two vapour liquid separator B, D, one Gas-liquid separator H, a compressor K, two gas-gas heat exchangers L, E, an air cooler F, a water cooling heat exchanger G, one is followed Ring compressor J, a reduced-pressure flash tank I.
Gaseous mixture entrance A11, A21 are configured at the top of water cooling methanol reactor A1, A2, top goes out configured with liquid-vapor mixture Mouth A12, A22, lower part is configured with separation water refluxing opening A13, A23, the bottom synthesis gas and methanol steam complete configured with unreacted Mixture outlet A14, A24 are also configured in the lower part water cooling methanol reactor A1, A2 and go into operation with heating device A15, A25.Water cooling It is configured with several reaction tubes in methanol reactor A1, A2, copper-based catalysts are configured in reaction tube, pass through water cooling outside reaction tube But.
The methanol reactor C of another structure type is CN203227477U description catalyst is loaded between heat exchanger tube Isothermal fixed bed reactors or by catalyst loaded on the board-like synthetic tower of IMC isothermal on the outside of plank.Lead in heat exchanger tube or plank It is cooling to cross water.In the top of the methanol reactor C of another the structure type synthesis gas and methanol complete configured with a unreacted Vapour mixture entrance C1 and two liquid-vapor mixtures export C2, C3, and bottom exports C6 and two configured with an end product Separate water refluxing opening C4, C5.
On vapour liquid separator B at least configured with two liquid-vapor mixture entrance B1, B2, two separation water out B3, B4 and One middle pressure steam exports B5.
Vapour liquid separator D is at least configured there are two liquid-vapor mixture entrance D1, D2, two separation water out D3, D4 and one A low-pressure steam outlet D5.
Gas-liquid separator H has end product entrance H1, circulating air outlet H2 and separation liquid outlet H3.
The complete synthesis of the synthesis gas and methanol steam mixture inlet L1, unreacted that gas-gas heat exchanger L has unreacted complete Gas and methanol steam mixture outlet L2, gaseous mixture entrance L3, mixed gas outlet L4.
Gas-gas heat exchanger E has gaseous mixture entrance E1, mixed gas outlet E2, end product entrance E3, end product outlet E4。
There is reduced-pressure flash tank I a separation liquid inlet I1, crude carbinol outlet I2 and flashed vapour to export I3.
Fresh letter shoot 1 after compressors in series K with circulation letter shoot 2 and the mixing after connecing with gas-gas heat exchanger E The E1 connection of gas entrance, the mixed gas outlet E2 of gas-gas heat exchanger E pass through the gaseous mixture of mixed gas pipeline 3a and gas-gas heat exchanger L The mixed gas outlet L4 of entrance L3 connection, gas-gas heat exchanger L is pushed up by mixed gas pipeline 3 and water cooling methanol reactor A1, A2 Gaseous mixture entrance A11, the A21 in portion are connected, water cooling methanol reactor A1, A2 parallel running.
Liquid-vapor mixture outlet A12, the A22 on the top water cooling methanol reactor A1, A2 are conveyed by liquid-vapor mixture respectively Two liquid-vapor mixture entrances B1, B2 on pipe 13,13a and vapour liquid separator B are connected, two separation on vapour liquid separator B Water out B3, B4 by separation water delivery pipe 14,14a and the lower part water cooling methanol reactor A1, A2 separation water refluxing opening A13, A23 connection.
The unreacted of the bottom water cooling methanol reactor A1, A2 complete synthesis gas and methanol steam mixture outlet A14, A24 Pass through the synthesis complete with unreacted of the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4 and gas-gas heat exchanger L Gas is connected with methanol steam mixture inlet L1, the synthesis gas complete with unreacted and the methanol steam mixing of gas-gas heat exchanger L Object outlet L2 is reacted by unreacted complete synthesis gas and methanol steam mixture delivery pipe 5 with the methanol of another structure type The complete synthesis gas of unreacted at the top of device C is connected with methanol steam mixture inlet C1.
The outlet of two liquid-vapor mixtures C2, C3 at the top of the methanol reactor C of another structure type pass through vapour-liquid respectively Two liquid-vapor mixture entrances D1, D2 of delivery pipe 15,15a and vapour liquid separator D are connected, two separation of vapour liquid separator D Water out D3, D4 pass through two of the bottom methanol reactor C of separation water delivery pipe 16,16a and another structure type respectively Separate water refluxing opening C4, C5 connection.
Another methanol reactor C bottom of structure type end product outlet C6 by end product delivery pipe 6 with The end product outlet E4 of the end product entrance E3 connection of gas-gas heat exchanger E, gas-gas heat exchanger E passes through end product delivery pipe 7 connect with the entrance of air cooler F, and the outlet of air cooler F is connect by end product delivery pipe 8 with the entrance of water cooling heat exchanger G, The outlet of water cooling heat exchanger G is connect by end product delivery pipe 9 with the end product entrance H1 of gas-liquid separator H.
On the one hand the circulating air outlet H2 of gas-liquid separator H is connect with the one end for speeding to put pipe 10, on the other hand press with circulation The entrance of contracting machine J connects, and the outlet of recycle compressor J is connect with the other end of circulation letter shoot 2, point of gas-liquid separator H Liquid inlet I1, reduced-pressure flash tank I are separated with the connection of reduced-pressure flash tank I by separating liquid delivery tube 17 from liquid outlet H3 Crude carbinol outlet I2 and flashed vapour outlet I3 be separately connected crude carbinol delivery pipe 11 and flashed vapour outlet 12.
Virgin gas enters compressor K, pressure rise to 7.4~8.1MPag, then and from following by fresh letter shoot 1 The circulating air of ring letter shoot 2 mixes, and mixed gas passes through gas-gas heat exchanger E, preheating mixture temperature to 180 DEG C~ 200℃.Gaseous mixture after preheating in gas-gas heat exchanger L again pre-heating temperature elevation to 210 DEG C~230 DEG C.Inlet tower gas after heating Entered in two water cooling methanol reactors A1, A2 in parallel with evenly distributing by mixed gas pipeline 3.H2 is 40 in inlet tower gas ~70mol%；CO is 5~25mol%；CO2 is 1~10mol%.
Inlet tower gas enters in the reaction tube of two water cooling methanol reactors A1, A2, and copper-based catalysts urges in reaction tube Change effect is lower to occur methanol synthesis reaction, and specific reaction equation is as follows:
Outside the pipe of the reaction tube of two water cooling methanol reactors A1, A2, methanol synthesis reaction is removed using boiled water and is put Heat out, while steam water interface enters vapour liquid separator B by liquid-vapor mixture delivery pipe 13,13a.In vapour liquid separator The separation of liquid-vapor mixture is carried out in B and the middle pressure steam for generating 2.2MPag~2.7MPag passes through on vapour liquid separator B Pressure steam (vapor) outlet B5 is sent to full factory's steam pipe network.
By separating, water delivery pipe 14, that 14a has respectively entered two water cooling methanol to the separation water of vapour liquid separator B separation is anti- It answers and is recycled in device A1, A2.
By two water cooling methanol reactor A1, A2 unreacteds in parallel complete synthesis gas and methanol steam mixture, temperature Degree is at 240 DEG C~260 DEG C.Enter gas-gas heat exchanger L by the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4, It exchanges heat in gas-gas heat exchanger L with the preheating material gas come from gas-gas heat exchanger E, after temperature is down to 220 DEG C~210 DEG C.It is cooling The complete synthesis gas of unreacted afterwards and methanol steam mixture pass through the complete synthesis gas of unreacted and the conveying of methanol steam mixture Pipe 5 enters the methanol reactor C of another structure type, and Shanghai state can be used in the methanol reactor C of the another kind structure type The isothermal of Ji Huajian engineering consulting company patent (grant number CN203227477U) description being loaded on catalyst between heat exchanger tube The board-like synthetic tower structure of IMC isothermal of known Casale design in fixed bed reactors or the technical field.Unreacted Complete synthesis gas and methanol steam mixture enters on the outside of the pipe or plank of the methanol reactor C of another structure type, and On the outside of pipe or plank under the action of copper-based catalysts, continue that methanol synthesis reaction occurs.Due to another structure type Generation drum pressure in methanol reactor C is lower, so that reaction temperature is than water cooling methanol reactor A1, A2 temperature in parallel It is low, so that the thermodynamics in synthetic reaction are analyzed, so that having in the complete synthesis gas and methanol steam mixture of unreacted The more complete of gas reaction is imitated, the methanol content of outlet is higher, and alcohol net value reaches 18~21mol%.Another structure type Methanol reactor C pipe or plank on the inside of using boiled water remove reaction heat, liquid-vapor mixture by vapour-liquid delivery pipe 15, 15a enters in vapour liquid separator D, and vapor-liquid separation is carried out in vapour liquid separator D, and generates the low pressure of 1.1MPag~1.7MPag Steam is sent out by the low-pressure steam outlet D5 of vapour liquid separator D.The temperature of end product after reaction be 210 DEG C~230 DEG C from The methanol reactor C for opening another structure type is cooled down by end product delivery pipe 6 into gas-gas heat exchanger E, and pre- Gaseous mixture in hot gas-gas heat exchanger E.The flow direction of reaction gas in methanol reactor C is axially or radially.And two simultaneously Copper-based catalysts in water cooling methanol reactor A1, A2 of connection and the copper-based catalysts in methanol reactor C are all the same, are height Low temperature active copper-based catalysts.Or the copper-based catalysts in two water cooling methanol reactor A1, A2 in parallel are high temperature active Copper-based catalysts, the copper-based catalysts in methanol reactor C are low temperature active copper-based catalysts.
End product after cooling enters air cooler F by end product delivery pipe 7, and temperature is down to 60 DEG C~80 DEG C, then Enter water cooling heat exchanger G by end product delivery pipe 8,30 DEG C~45 DEG C are cooled in water cooling heat exchanger G.It is after cooling most Product is entered in gas-liquid separator H by end product delivery pipe 9 afterwards, carries out the separation of gas-liquid mixture.Gas after separation One carries out speeding to put by speeding to put pipe 10；It is compressed in another gang of entrance recycle compressor J, then passes through circulation letter shoot 2 are reacted again with virgin gas mixing.Isolated liquid enters reduced-pressure flash tank I and carries out the crude carbinol generated after vacuum flashing Into methanol tank or it is sent into downstream methanol rectifier unit.
Embodiment 2
Referring to fig. 2, the energy-saving ultra-large methanol synthesizer of the production different brackets steam provided in figure and implementation The difference of example 1 is to eliminate gas-gas heat exchanger L, the unreacted of the bottom water cooling methanol reactor A1, A2 complete synthesis gas and first Alcohol vapour mixture outlet A14, A24 directly pass through the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4 with it is another It plants the complete synthesis gas of the unreacted at the top of the methanol reactor C of structure type to connect with methanol steam mixture inlet C1, gas gas The mixed gas outlet E2 of heat exchanger E directly passes through mixed gas pipeline 3 and enters with the gaseous mixture at the top of water cooling methanol reactor A1, A2 Mouth A11, A21 connection.
Virgin gas by fresh letter shoot 1 enter compressor K, pressure rise to 7.9MPag, then with it is defeated from circulating air The circulating air of pipe 2 is sent to mix, mixed gas passes through gas-gas heat exchanger E, preheats mixture temperature to 210 DEG C.After heating Inlet tower gas entered in parallel two water cooling methanol reactors A1, A2 with evenly distributing by mixed gas pipeline 3.Inlet tower gas Middle H2 is 40~70mol%；CO is 5~25mol%；CO2 is 1~10mol%.
Inlet tower gas enters in the reaction tube of two water cooling methanol reactors A1, A2, and copper-based catalysts urges in reaction tube Change effect is lower to occur methanol synthesis reaction, and specific reaction equation is as follows:
Outside the pipe of the reaction tube of two water cooling methanol reactors A1, A2, methanol synthesis reaction is removed using boiled water and is put Heat out, while steam water interface enters vapour liquid separator B by gas-liquid mixture delivery pipe 13,13a.In vapour liquid separator The separation of liquid-vapor mixture is carried out in B and the middle pressure steam for generating 2.5MPag passes through the middle pressure steam outlet on vapour liquid separator B B5 is sent to full factory's steam pipe network.
By separating, water delivery pipe 14, that 14a has respectively entered two water cooling methanol to the separation water of vapour liquid separator B separation is anti- It answers and is recycled in device A1, A2.
By two water cooling methanol reactor A1, A2 unreacteds in parallel complete synthesis gas and methanol steam mixture, temperature Degree is at 250 DEG C.Enter the methanol of another structure type by the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4 (the authorization of Shanghai International Construction Engineering Consultation Corp.'s patent can be used in reactor C, the methanol reactor C of the another kind structure type Number CN203227477U) description by catalyst loaded on the isothermal fixed bed reactors or the technical field between heat exchanger tube The board-like synthetic tower structure of IMC isothermal of the design of Casale known to interior.The complete synthesis gas of unreacted and methanol steam mixture Into on the outside of the pipe or plank of the methanol reactor C of another structure type, and the copper-based catalysts on the outside of pipe or plank Under the action of, continue that methanol synthesis reaction occurs.Due to the generation drum pressure in the methanol reactor C of another structure type It is lower, so that reaction temperature is lower than water cooling methanol reactor A1, A2 temperature in parallel, thus in the thermodynamics of synthetic reaction Analysis so that available gas reaction in the complete synthesis gas and methanol steam mixture of unreacted more completely, the first of outlet Alcohol content is higher, and alcohol net value reaches 19.6mol%.Make on the inside of the pipe or plank of the methanol reactor C of another structure type Reaction heat is removed with boiled water, liquid-vapor mixture is entered in vapour liquid separator D by vapour-liquid delivery pipe 15,15a, in vapor-liquid separation Vapor-liquid separation is carried out in device D, and the low-pressure steam for generating 1.45MPag is sent out by the low-pressure steam outlet D5 of vapour liquid separator D. The temperature of end product after reaction is that 223 DEG C of methanol reactor C for leaving another structure type are conveyed by end product Pipe 6 is cooled down into gas-gas heat exchanger E, and preheats the gaseous mixture in gas-gas heat exchanger E.Reaction gas in methanol reactor C The flow direction of body is axially or radially.And copper-based catalysts in two water cooling methanol reactor A1, A2 in parallel and methanol are anti- It answers the copper-based catalysts in device C all the same, is high/low temperature activity copper-based catalysts.Or two water cooling methanol reactions in parallel Copper-based catalysts in device A1, A2 are high temperature active copper-based catalysts, and the copper-based catalysts in methanol reactor C are low temperature active Copper-based catalysts.
End product after cooling enters air cooler F by end product delivery pipe 7, and temperature is down to 70 DEG C, then by most Product delivery pipe 8 enters water cooling heat exchanger G afterwards, and 40 DEG C are cooled in water cooling heat exchanger G.End product after cooling is by most Product delivery pipe 9 enters in gas-liquid separator H afterwards, carries out the separation of gas-liquid mixture.Gas after separation one by speeding to put Pipe 10 carries out speeding to put；Another strand enters in recycle compressor J and is compressed, then mixed by circulation letter shoot 2 and virgin gas It closes and carries out secondary response again.Isolated liquid enters the crude carbinol that reduced-pressure flash tank I generate after vacuum flashing and enters methanol storage Tank is sent into downstream methanol rectifier unit.
Embodiment 3
Referring to Fig. 3, the energy-saving ultra-large methanol synthesizer of the production different brackets steam provided in figure and implementation The synthesis gas and methanol steam mixture inlet L1, unreacted that the difference of example 1 is that gas-gas heat exchanger L has unreacted complete are complete Synthesis gas and methanol steam mixture outlet L2, circulating air entrance L3 ', circulating air export L4 ', and circulation letter shoot 2 also passes through One circulation letter shoot 2a is connect with the circulating air entrance L3 ' of gas-gas heat exchanger L, and the circulating air outlet L4 ' of gas-gas heat exchanger L is logical It crosses mixed gas pipeline 3 ' to connect with gaseous mixture entrance A11, A21 at the top of water cooling methanol reactor A1, A2, gas-gas heat exchanger E Mixed gas outlet E2 connect with mixed gas pipeline 3 ' by mixed gas pipeline 3 ".
Virgin gas by fresh letter shoot 1 enter compressor K, pressure rise to 7.9MPag, then with it is defeated from circulating air One circulating air of pipe 2 is sent to mix, mixed gas passes through gas-gas heat exchanger E, preheats mixture temperature to 205 DEG C.It follows Another stock of ring gas enters gas-gas heat exchanger L by recycling letter shoot 2a, and the temperature after preheating rises to 240 DEG C, following after preheating Gaseous mixture after ring gas and preheating mixes again, and temperature is down to 212 DEG C, and mixed inlet tower gas is equal by mixed gas pipeline 3 ' It is even distributively to enter in two water cooling methanol reactors A1, A2 in parallel.H2 is 40~70mol% in inlet tower gas；CO be 5~ 25mol%；CO2 is 1~10mol%.
Inlet tower gas enters in the reaction tube of two water cooling methanol reactors A1, A2, and copper-based catalysts urges in reaction tube Change effect is lower to occur methanol synthesis reaction, and specific reaction equation is as follows:
Outside the pipe of the reaction tube of two water cooling methanol reactors A1, A2, methanol synthesis reaction is removed using boiled water and is put Heat out, while steam water interface enters vapour liquid separator B by liquid-vapor mixture delivery pipe 13,13a.In vapour liquid separator The separation of gas-liquid mixture is carried out in B and the middle pressure steam for generating 2.2MPag~2.7MPag passes through on vapour liquid separator B Pressure steam (vapor) outlet B5 is sent to full factory's steam pipe network.
By separating, water delivery pipe 14, that 14a has respectively entered two water cooling methanol to the separation water of vapour liquid separator B separation is anti- It answers and is recycled in device A1, A2.
By two water cooling methanol reactor A1, A2 unreacteds in parallel complete synthesis gas and methanol steam mixture, temperature Degree is at 240 DEG C~260 DEG C.Enter gas-gas heat exchanger L by the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4, It exchanges heat in gas-gas heat exchanger L with the circulating air brought from circulation letter shoot 2a, after temperature is down to 205 DEG C.It is after cooling The complete synthesis gas of unreacted and methanol steam mixture by unreacted complete synthesis gas and methanol steam mixture delivery pipe 5 into Enter the methanol reactor C of another structure type, Shanghai internationalization can be used to build for the methanol reactor C of the another kind structure type The isothermal fixed bed of engineering consulting company's patent (grant number CN203227477U) description being loaded on catalyst between heat exchanger tube The board-like synthetic tower structure of IMC isothermal of known Casale design in reactor or the technical field.The complete conjunction of unreacted Enter on the outside of the pipe or plank of the methanol reactor C of another structure type at gas and methanol steam mixture, and in pipe Or on the outside of plank under the action of copper-based catalysts, continue that methanol synthesis reaction occurs.Since the methanol of another structure type is anti- Answer the generation drum pressure in device C lower, so that reaction temperature is lower than water cooling methanol reactor A1, A2 temperature in parallel, thus It is analyzed in the thermodynamics of synthetic reaction, so that the available gas in the complete synthesis gas and methanol steam mixture of unreacted is anti- That answers is more complete, and the methanol content of outlet is higher, and alcohol net value reaches 20.3mol%.The methanol of another structure type reacts Reaction heat is removed using boiled water on the inside of the pipe or plank of device C, liquid-vapor mixture enters vapour by vapour-liquid delivery pipe 15,15a In liquid/gas separator D, vapor-liquid separation is carried out in vapour liquid separator D, and generates the low-pressure steam of 1.29MPag by vapour liquid separator D Low-pressure steam outlet D5 send out.The temperature of end product after reaction is that 215 DEG C of methanol for leaving another structure type are anti- It answers device C to be cooled down by end product delivery pipe 6 into gas-gas heat exchanger E, and preheats the gaseous mixture in gas-gas heat exchanger E. The flow direction of reaction gas in methanol reactor C is axially or radially.And in two water cooling methanol reactor A1, A2 in parallel Copper-based catalysts and the copper-based catalysts in methanol reactor C it is all the same, be high/low temperature activity copper-based catalysts.Or two Copper-based catalysts in water cooling methanol reactor A1, A2 of platform parallel connection are high temperature active copper-based catalysts, in methanol reactor C Copper-based catalysts are low temperature active copper-based catalysts.
End product after cooling enters air cooler F by end product delivery pipe 7, and temperature is down to 70 DEG C, then by most Product delivery pipe 8 enters water cooling heat exchanger G afterwards, and 40 DEG C are cooled in water cooling heat exchanger G.End product after cooling is by most Product delivery pipe 9 enters in gas-liquid separator H afterwards, carries out the separation of gas-liquid mixture.Gas after separation one by speeding to put Pipe 10 carries out speeding to put；Another strand enters in recycle compressor J and is compressed, then mixed by circulation letter shoot 2 and virgin gas It closes and carries out secondary response again.Isolated liquid enters the crude carbinol that reduced-pressure flash tank I generate after vacuum flashing and enters methanol storage Tank is sent into downstream methanol rectifier unit.
Embodiment 4
Referring to fig. 4, the energy-saving ultra-large methanol synthesizer of the production different brackets steam provided in figure, including two Platform water cooling methanol reactor A1, A2, the methanol reactor C of another structure type, two vapour liquid separator B, D, one Gas-liquid separator H, a compressor K, two gas-gas heat exchanger L ', E ', an air cooler F, a water cooling heat exchanger G, one Recycle compressor J, reduced-pressure flash tank an I, air cooler a M, gas-liquid separator a N, a water cooler P.
Gaseous mixture entrance A11, A21 are configured at the top of water cooling methanol reactor A1, A2, top goes out configured with liquid-vapor mixture Mouth A12, A22, lower part is configured with separation water refluxing opening A13, A23, the bottom synthesis gas and methanol steam complete configured with unreacted Mixture outlet A14, A24 are also configured in the lower part water cooling methanol reactor A1, A2 and go into operation with heating device A15, A25.Water cooling It is configured with several reaction tubes in methanol reactor A1, A2, copper-based catalysts are configured in reaction tube, pass through water cooling outside reaction tube But.
The methanol reactor C of another structure type is CN203227477U description catalyst is loaded between heat exchanger tube Isothermal fixed bed reactors or by catalyst loaded on the board-like synthetic tower of IMC isothermal on the outside of plank.Lead in heat exchanger tube or plank It is cooling to cross water.In the top of the methanol reactor C of another structure type synthesis gas entrance C1 ' complete configured with a unreacted Export C2, C3 with two liquid-vapor mixtures, bottom configured with an end product export C6 and two separation water refluxing opening C4, C5。
On vapour liquid separator B at least configured with two liquid-vapor mixture entrance B1, B2, two separation water out B3, B4 and One middle pressure steam exports B5.
Vapour liquid separator D is at least configured there are two liquid-vapor mixture entrance D1, D2, two separation water out D3, D4 and one A low-pressure steam outlet D5.
Gas-liquid separator H has end product entrance H1, circulating air outlet H2 and separation liquid outlet H3.
The complete conjunction of the synthesis gas and methanol steam mixture inlet L1 ', unreacted that gas-gas heat exchanger L ' has unreacted complete At gas and methanol steam mixture outlet L2 ', gaseous mixture entrance L3 ', mixed gas outlet L4 '.
Gas-gas heat exchanger E ' has the complete synthesis gas entrance E1 ' of unreacted, the complete syngas outlet E2 ' of unreacted, end product Entrance E3 ', end product export E4 '.
There is reduced-pressure flash tank I a separation liquid inlet I1, crude carbinol outlet I2 and flashed vapour to export I3.
The complete synthesis gas of synthesis gas and methanol steam mixture inlet M1, unreacted that air cooler M has unreacted complete and Methanol steam mixture outlet M2.
Gas-liquid separator N is with unreacted complete synthesis gas and methanol steam mixture inlet N1, the complete synthesis gas of unreacted Export N2 and separation liquid outlet N3.
Water cooling heat exchanger P has separation liquid inlet P1 and separation liquid outlet P2.
Fresh letter shoot 1 after compressors in series K with circulation letter shoot 2 and the mixing after connecing with gas-gas heat exchanger L ' L3 ' the connection of gas entrance, the mixed gas outlet L4 ' of gas-gas heat exchanger L by mixed gas pipeline 3b and water cooling methanol reactor A1, Gaseous mixture entrance A11, A21 connection at the top of A2, water cooling methanol reactor A1, A2 parallel running.
Liquid-vapor mixture outlet A12, the A22 on the top water cooling methanol reactor A1, A2 are conveyed by liquid-vapor mixture respectively Two liquid-vapor mixture entrances B1, B2 on pipe 13,13a and vapour liquid separator B are connected, two separation on vapour liquid separator B Water out B3, B4 by separation water delivery pipe 14,14a and the lower part water cooling methanol reactor A1, A2 separation water refluxing opening A13, A23 connection.
The unreacted of the bottom water cooling methanol reactor A1, A2 complete synthesis gas and methanol steam mixture outlet A14, A24 Pass through the conjunction complete with unreacted of the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4a and gas-gas heat exchanger L ' At gas and the L1 ' connection of methanol steam mixture inlet, the synthesis gas and methanol steam complete with unreacted of gas-gas heat exchanger L ' Mixture outlet L2 ' is complete by the unreacted of unreacted complete synthesis gas and methanol steam mixture delivery pipe 4b and air cooler M Synthesis gas connected with methanol steam mixture inlet M1, the complete synthesis gas of the unreacted of air cooler M and methanol steam mixture Export the M2 conjunction complete by the unreacted of unreacted complete synthesis gas and methanol steam mixture delivery pipe 4c and gas-liquid separator N It is connected at gas with methanol steam mixture inlet N1, the complete syngas outlet N2 of the unreacted of gas-liquid separator N is complete by unreacted Synthesis letter shoot 18a is connect with the complete synthesis gas entrance E1 ' of the unreacted of gas-gas heat exchanger E ', and gas-gas heat exchanger E ' has not anti- Syngas outlet E2 ' has been answered to pass through the top methanol reactor C of the complete synthesis letter shoot 18b of unreacted and another structure type The complete synthesis gas entrance C1 ' connection of unreacted.
The outlet of two liquid-vapor mixtures C2, C3 at the top of the methanol reactor C of another structure type pass through vapour-liquid respectively Two liquid-vapor mixture entrances D1, D2 of delivery pipe 15,15a and vapour liquid separator D are connected, two separation of vapour liquid separator D Water out D3, D4 pass through two of the bottom methanol reactor C of separation water delivery pipe 16,16a and another structure type respectively Separate water refluxing opening C4, C5 connection.
Another methanol reactor C bottom of structure type end product outlet C6 by end product delivery pipe 6a with The end product outlet E4 ' of the end product entrance E3 ' connection of gas-gas heat exchanger E ', gas-gas heat exchanger E ' is defeated by end product Pipe 6b and the entrance of air cooler F is sent to connect, the outlet of air cooler F passes through the entrance of end product delivery pipe 8 and water cooling heat exchanger G The outlet of connection, water cooling heat exchanger G is connect by end product delivery pipe 9 with the end product entrance H1 of gas-liquid separator H.
On the one hand the circulating air outlet H2 of gas-liquid separator H is connect with the one end for speeding to put pipe 10, on the other hand press with circulation The entrance of contracting machine J connects, and the outlet of recycle compressor J is connect with the other end of circulation letter shoot 2, point of gas-liquid separator H Liquid inlet I1, reduced-pressure flash tank I are separated with the connection of reduced-pressure flash tank I by separating liquid delivery tube 17 from liquid outlet H3 Crude carbinol outlet I2 and flashed vapour outlet I3 be separately connected crude carbinol delivery pipe 11 and flashed vapour outlet 12.
The separating liquid that the separation liquid outlet N3 of gas-liquid separator N passes through separation liquid delivery tube 19a and water cooling heat exchanger P The P1 connection of body entrance, the separation liquid outlet P2 of water cooling heat exchanger P by separation liquid delivery tube 19b with separate liquid delivery tube 17 connections.
Virgin gas by fresh letter shoot 1 enter compressor K, pressure rise to 7.9MPag, then with it is defeated from circulating air The circulating air of pipe 2 is sent to mix, mixed gas passes through gas-gas heat exchanger L ', preheats mixture temperature to 210 DEG C.After heating Inlet tower gas, that is, gaseous mixture in parallel two water cooling methanol reactors A1, A2 are entered with evenly distributing by mixed gas pipeline 3b In.H2 is 40~70mol% in inlet tower gas；CO is 5~25mol%；CO2 is 1~10mol%.
Inlet tower gas enters in the reaction tube of two water cooling methanol reactors A1, A2, and copper-based catalysts urges in reaction tube Change effect is lower to occur methanol synthesis reaction, and specific reaction equation is as follows:
Outside the pipe of the reaction tube of two water cooling methanol reactors A1, A2, methanol synthesis reaction is removed using boiled water and is put Heat out, while steam water interface enters vapour liquid separator B by liquid-vapor mixture delivery pipe 13,13a.In vapour liquid separator The separation of liquid-vapor mixture is carried out in B and the middle pressure steam for generating 2.6MPag passes through the middle pressure steam outlet on vapour liquid separator B B5 is sent to full factory's steam pipe network.
By separating, water delivery pipe 14, that 14a has respectively entered two water cooling methanol to the separation water of vapour liquid separator B separation is anti- It answers and is recycled in device A1, A2.
By two water cooling methanol reactor A1, A2 unreacteds in parallel complete synthesis gas and methanol steam mixture, temperature Degree is at 250 DEG C.Enter gas-gas heat exchanger L ' by the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4a, in gas gas It exchanges heat in heat exchanger L ' with the gaseous mixture of circulating air and unstripped gas, temperature is down to 140~130 DEG C, and unreacted after cooling is complete Synthesis gas and methanol steam mixture pass through unreacted complete synthesis gas and methanol steam mixture delivery pipe 4b and enter air cooler M, temperature is down to 70 DEG C, then enters gas-liquid separator N by the complete synthesis gas of unreacted and methanol steam mixture delivery pipe 4c It is interior, carry out the separation of gas-liquid mixture.Liquid after separation enters water cooling heat exchanger P by separating liquid delivery tube 19a, in water It is cooled to 40 DEG C in cold heat exchanger P, vacuum flashing is then entered by separation liquid delivery tube 19b, separation liquid delivery tube 17 The crude carbinol that tank I generate after vacuum flashing enters methanol tank or is sent into downstream methanol rectifier unit.
The complete synthesis gas of unreacted after separation enters gas-gas heat exchanger by the complete synthesis letter shoot 18a of unreacted E ' preheats mixture temperature to 210 DEG C, then enters another structure type by the complete synthesis letter shoot 18b of unreacted Methanol reactor C, Shanghai International Construction Engineering Consultation Corp.'s patent can be used in the methanol reactor C of the another kind structure type The isothermal fixed bed reactors or the technology catalyst being loaded between heat exchanger tube of (grant number CN203227477U) description The board-like synthetic tower structure of IMC isothermal of known Casale design in field.The complete synthesis gas of unreacted and methanol steam are mixed On the outside of the pipe or plank for closing the methanol reactor C that object enters another structure type, and copper-based on the outside of pipe or plank urge Under the action of agent, continue that methanol synthesis reaction occurs.Due to the generation drum in the methanol reactor C of another structure type Pressure is lower, so that reaction temperature is lower than water cooling methanol reactor A1, A2 temperature in parallel, thus in the thermodynamics of synthetic reaction Angle analysis so that available gas reaction in the complete synthesis gas and methanol steam mixture of unreacted more completely, outlet Methanol concentration be 12.3mol%.It is moved on the inside of the pipe or plank of the methanol reactor C of another structure type using boiled water Reaction heat is walked, liquid-vapor mixture is entered in vapour liquid separator D by vapour-liquid delivery pipe 15,15a, is carried out in vapour liquid separator D Vapor-liquid separation, and the low-pressure steam for generating 1.29MPag is sent out by the low-pressure steam outlet D5 of vapour liquid separator D.After reaction most The temperature of product is that 225 DEG C of methanol reactor C for leaving another structure type enter gas by end product delivery pipe 6a afterwards Gas heat exchanger E ' is cooled down, and preheats the gaseous mixture in gas-gas heat exchanger E '.The flow direction of reaction gas in methanol reactor C For axially or radially.And in the copper-based catalysts in two water cooling methanol reactor A1, A2 in parallel and methanol reactor C Copper-based catalysts are all the same, are high/low temperature activity copper-based catalysts.Or in two water cooling methanol reactor A1, A2 in parallel Copper-based catalysts be high temperature active copper-based catalysts, the copper-based catalysts in methanol reactor C are low temperature active cupper-based catalyst Agent.
End product after cooling enters air cooler F by end product delivery pipe 6b, then passes through end product delivery pipe 8 Into water cooling heat exchanger G, 40 DEG C are cooled in water cooling heat exchanger G.End product after cooling passes through end product delivery pipe 9 Into in gas-liquid separator H, the separation of gas-liquid mixture is carried out.Gas after separation one carry out speeding to put by speeding to put pipe 10； It is compressed in another gang of entrance recycle compressor J, it is anti-again that progress is then mixed with virgin gas by circulation letter shoot 2 It answers.Isolated liquid enters the crude carbinol that reduced-pressure flash tank I generate after vacuum flashing and enters methanol tank or be sent into downstream Methanol rectifying system.

Claims (31)

1. produce different brackets steam energy-saving ultra-large methane synthesizing method, it is characterized in that virgin gas after overcompression with Circulating air is mixed to form the first gaseous mixture, and the first gaseous mixture is synchronous after heating to enter two water cooling methanol reactors in parallel The middle methanol synthesis reaction that carries out generates the complete synthesis gas and methanol steam mixture of unreacted, the complete synthesis gas of the unreacted and Methanol steam mixture enters isothermal fixed bed reactors after cooling or after condensing and separating portion of product between section On the outside of heat exchanger tube or on the outside of the plank of the board-like synthetic tower of IMC isothermal, the copper-based catalysts on the outside of heat exchanger tube or on the outside of plank are urged The lower generation methanol synthesis reaction of change effect obtains end product, removes methanol on the inside of heat exchanger tube or on the inside of plank by boiled water Heat caused by reacting；The end product passes through refrigerated separation, and the portion gas isolated is as the circulating air, liquid Crude carbinol enters downstream rectification cell；
It is 240 DEG C~260 DEG C that the reaction, which forms the complete synthesis gas of unreacted and the temperature of methanol steam mixture,；It is described not anti- Temperature of the synthesis gas and methanol steam mixture answered after cooling is 210 DEG C~220 DEG C；
The virgin gas is 7.4~8.1MPag by compressed pressure；
Two water cooling methanol reactors send out the first liquid-vapor mixture, after first liquid-vapor mixture carries out vapor-liquid separation Generate the middle pressure steam that a pressure is 2.2MPag~2.7MPag；
The isothermal fixed bed reactors or the board-like synthetic tower of IMC isothermal send out the second liquid-vapor mixture, and second vapour-liquid is mixed It closes after object carries out steam-water separation and generates the low-pressure steam that a pressure is 1.1MPag~1.7MPag.
2. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that In the isothermal fixed bed reactors or the board-like synthetic tower of IMC isothermal, the flow direction of reaction gas is axially or radially.
3. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that It is configured with several reaction tubes in the water cooling methanol reactor, is configured with copper-based catalysts in the reaction tube, described the One gaseous mixture enters in the reaction tube, and it is anti-that methanol-fueled CLC occurs under the copper-based catalysts catalytic action in the reaction tube It answers, methanol is removed by boiled water outside the reaction tube and reacts generated heat.
4. the energy-saving ultra-large methane synthesizing method of production different brackets steam as claimed in claim 3, it is characterized in that Copper-based catalysts in two water cooling methanol reactors are all the same, are high/low temperature activity copper-based catalysts.
5. the energy-saving ultra-large methane synthesizing method of production different brackets steam as claimed in claim 3, it is characterized in that Copper-based catalysts in two water cooling methanol reactors are high temperature active copper-based catalysts, isothermal fixed bed reactors The copper-based catalysts on the outside of plank on the outside of heat exchanger tube or in the board-like synthetic tower of IMC isothermal are low temperature active copper-based catalysts.
6. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that The temperature that first gaseous mixture enters water cooling methanol reactor in parallel after heating is 210 DEG C~230 DEG C.
7. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that Each component content of first gaseous mixture after heating is H2For 40~70mol%；CO is 5~25mol%；CO2For 1~ 10mol%.
8. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that The water cooling methanol reactor removes the heat that methanol synthesis reaction is released using boiled water.
9. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that The complete synthesis gas of the unreacted and methanol steam mixture exchange heat with first gaseous mixture.
10. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that After the complete synthesis gas of the unreacted and methanol steam mixture and first gaseous mixture are exchanged heat, condensed using between section Enter heat exchanger tube outside or the IMC etc. of isothermal fixed bed reactors after separate section product, then after being exchanged heat with end product The board-like synthetic tower of temperature continues methanol synthesis reaction and obtains end product.
11. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that The complete synthesis gas of the unreacted and methanol steam mixture exchange heat with the circulating air.
12. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that The complete synthesis gas of the unreacted and methanol steam mixture exchange heat with the circulating air.
13. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that The end product is 30 DEG C~45 DEG C by temperature after cooling.
14. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that Heat exchange is carried out with first gaseous mixture in the end product cooling procedure.
15. the energy-saving ultra-large methane synthesizing method of production different brackets steam as described in claim 1, it is characterized in that Alcohol net value in the end product is 18~21mol%.
16. a kind of realize the energy-saving super large for producing different brackets steam described in any one of claim 1 to 15 claim The device of scale methane synthesizing method characterized by comprising
First cooling device, first cooling device have the first gaseous mixture entrance, the first mixed gas outlet, the first last production Object entrance, the outlet of the first end product, wherein the first gaseous mixture entrance connects one end and first of a fresh letter shoot One end of letter shoot is recycled, the fresh letter shoot sends virgin gas, and the first circulation letter shoot sends circulating air；
Two the first methanol reactors, the top of every one first methanol reactor are configured with the second gaseous mixture entrance, top configuration There is the outlet of the first liquid-vapor mixture, lower part is configured with the first separation water refluxing opening, the bottom synthesis complete configured with the first unreacted Gas and methanol steam mixture outlet, wherein every one second gaseous mixture entrance passes through one first mixed gas pipeline and described first The first mixed gas outlet connection in cooling device；
One first vapour liquid separator, first vapour liquid separator are at least configured there are two the first liquid-vapor mixture entrance, two First separation water out and a middle pressure steam outlet, two of them the first liquid-vapor mixture entrance pass through two first vapour respectively Liquid mixture delivery pipe is exported with first liquid-vapor mixture on a corresponding methanol reactor top and is connected, two first separation Water out passes through two first separation water delivery pipes respectively and separates water refluxing opening company with the first of corresponding methanol reactor lower part It connects；Medium pressure steam (vapor) outlet sends out middle pressure steam；
One second methanol reactor, the top of second methanol reactor configured with the complete synthesis gas of first unreacted and Methanol steam mixture inlet and two the second liquid-vapor mixture outlets, bottom is configured with the first end product outlet and two A second separation water refluxing opening, the complete synthesis gas of first unreacted and methanol steam mixture inlet pass through the first unreacted The complete synthesis of first unreacted of complete synthesis gas and methanol steam mixture delivery pipe and two the first methanol reactor bottoms Gas is connected with methanol steam mixture outlet；First end product outlet passes through the first end product delivery pipe and described the The first end product entrance connection in one cooling device；
One second vapour liquid separator, second vapour liquid separator are at least configured there are two the second liquid-vapor mixture entrance, two Second separation water out and a low-pressure steam outlet, two of them the second liquid-vapor mixture entrance pass through two second vapour respectively Liquid mixture delivery pipe is exported with the second liquid-vapor mixture corresponding in second methanol reactor and is connected, two second separation Water out passes through two second separation water delivery pipes respectively and separates water reflux in second methanol reactor corresponding second Mouth connection, the low-pressure steam outlet send out low-pressure steam；
There is the second end product entrance and the second end product to export for second cooling device, second cooling device, and second End product entrance is exported by the first end product in the second end product delivery pipe and first cooling device and is connected；
There is third end product entrance and third end product to export for third cooling device, the third cooling device, third End product entrance is exported by the second end product in third end product delivery pipe and second cooling device and is connected；
One third gas-liquid separator, the third gas-liquid separator have the 4th end product entrance, first circulation gas outlet and Liquid outlet is separated, wherein the 4th end product entrance passes through the 4th end product delivery pipe and the third cooling device In third end product export connection；On the one hand connection one speeds to put pipe for the first circulation gas outlet, on the other hand passes through one Recycle compressor is connect with the other end of the first circulation letter shoot；
One reduced-pressure flash tank, the reduced-pressure flash tank have a separation liquid inlet, crude carbinol outlet and flashed vapour outlet, institute It states separation liquid inlet and is connect by separating liquid delivery tube with the separation liquid outlet on the third gas-liquid separator, it is described Flashed vapour is sent out in crude carbinol outlet output crude carbinol, the flashed vapour outlet；
First methanol reactor is water cooling methanol reactor；
Second methanol reactor is the isothermal fixed bed of CN203227477U description being loaded on catalyst between heat exchanger tube Catalyst is loaded on the board-like synthetic tower of IMC isothermal on the outside of plank by reactor.
17. device as claimed in claim 16, which is characterized in that first cooling device is gas-gas heat exchanger, and second is cold But device is air cooler, and third cooling device is water cooling heat exchanger.
18. device as claimed in claim 16, which is characterized in that it further include the 4th cooling device, the 4th cooling device It is mixed with the complete synthesis gas of the second unreacted and methanol steam mixture inlet, the second unreacted complete synthesis gas and methanol steam Close object outlet, third gaseous mixture entrance or second circulation gas entrance, third mixed gas outlet or the outlet of second circulation gas, described the The complete synthesis gas of two unreacteds and methanol steam mixture inlet pass through the complete synthesis gas and methanol steam of second unreacted The mixture delivery pipe synthesis gas complete with the first unreacted of two the first methanol reactor bottoms and methanol steam mixture go out Mouthful connection, the complete synthesis gas of second unreacted and methanol steam mixture outlet by the complete synthesis gas of third unreacted and Methanol steam mixture the delivery pipe synthesis gas and methanol steam complete with the first unreacted of second methanol reactor mix The connection of object entrance, the third gaseous mixture entrance are mixed by first in the second mixed gas pipeline and first cooling device It closes gas outlet connection or second circulation gas entrance is connect by second circulation letter shoot with the first circulation letter shoot； The third mixed gas outlet passes through the second gaseous mixture entrance in third mixed gas pipeline and two the first methanol reactors Connection or second circulation gas outlet recycle second in letter shoot and two the first methanol reactors by third and mix Conjunction gas entrance connects and passes through third mixed gas pipeline to be connect with the second gaseous mixture entrance in two the first methanol reactors.
19. the device as described in claim 16 or 18, which is characterized in that a compression of connecting in the fresh letter shoot Machine.
20. device as claimed in claim 16, which is characterized in that be configured with several first in the water cooling methanol reactor Reaction tube, is configured with copper-based catalysts in first reaction tube, and first gaseous mixture enters first reaction tube It is interior, occur methanol synthesis reaction under the copper-based catalysts catalytic action in first reaction tube, outside first reaction tube It is cooling by boiled water.
21. device as claimed in claim 16, which is characterized in that the reaction gas in second methanol reactor, which flows to, is Axially or radially form.
22. device as claimed in claim 20, which is characterized in that the copper-based catalysts in first methanol reactor and Copper-based catalysts in dimethanol reactor are identical, are high/low temperature activity copper-based catalysts.
23. device as claimed in claim 20, which is characterized in that the copper-based catalysts in first methanol reactor are height Warm activity copper-based catalysts, the copper-based catalysts in second methanol reactor are low temperature active copper-based catalysts.
24. the device as described in claim 16 or 18, which is characterized in that in a preferred embodiment of the invention, described First cooling device, the 4th cooling device are gas-gas heat exchanger, and the second cooling device is air cooler, and third cooling device is water cooling Heat exchanger.
25. a kind of realize the energy-saving super large for producing different brackets steam described in any one of claim 1 to 15 claim The device of scale methane synthesizing method characterized by comprising
5th cooling device, the 5th cooling device have the 4th gaseous mixture entrance, the 4th mixed gas outlet, third unreacted Complete synthesis gas and methanol steam mixture inlet, third unreacted complete synthesis gas and methanol steam mixture outlet, wherein The 4th gaseous mixture entrance connects one end of a fresh letter shoot and one end of first circulation letter shoot, the virgin gas Delivery pipe sends virgin gas, and the first circulation letter shoot sends circulating air；
Two the first methanol reactors, the top of every one first methanol reactor are configured with the second gaseous mixture entrance, top configuration There is the outlet of the first liquid-vapor mixture, lower part is configured with the first separation water refluxing opening, the bottom synthesis complete configured with the first unreacted Gas and methanol steam mixture outlet, wherein every one second gaseous mixture entrance passes through one first mixed gas pipeline and the described 5th Third mixed gas outlet connection in cooling device；The complete synthesis gas of first unreacted of two the first methanol reactor bottoms and Methanol steam mixture outlet and after connecing by the 4th unreacted complete synthesis gas and methanol steam mixture delivery pipe with it is described The synthesis gas that the third unreacted of 5th cooling device is complete is connected with methanol steam mixture inlet；
One first vapour liquid separator, first vapour liquid separator are at least configured there are two the first liquid-vapor mixture entrance, two First separation water out and a middle pressure steam outlet, two of them the first liquid-vapor mixture entrance pass through two first vapour respectively Liquid mixture delivery pipe is exported with first liquid-vapor mixture on a corresponding methanol reactor top and is connected, two first separation Water out passes through two first separation water delivery pipes respectively and separates water refluxing opening company with the first of corresponding methanol reactor lower part It connects；Medium pressure steam (vapor) outlet sends out middle pressure steam；
6th cooling device, the synthesis gas and methanol steam mixture that the 6th cooling device has the 4th unreacted complete enter Mouth, the 4th unreacted complete synthesis gas and methanol steam mixture outlet, the 4th unreacted of the 6th cooling device are complete Synthesis gas and methanol steam mixture inlet pass through the complete synthesis gas and methanol steam mixture delivery pipe and institute of the 5th unreacted The complete synthesis gas of third unreacted for stating the 5th cooling device is connected with methanol steam mixture outlet；
4th gas-liquid separation device, the synthesis gas and methanol steam that the 4th gas-liquid separation device has the 5th unreacted complete are mixed Conjunction object entrance, the complete syngas outlet of the first unreacted and the first separation liquid outlet, the 5th of the 4th gas-liquid separation device the The complete synthesis gas of unreacted and methanol steam mixture inlet pass through the complete synthesis gas and methanol steam mixture of the 6th unreacted The delivery pipe synthesis gas and methanol steam mixture outlet complete with the 4th unreacted of the 6th cooling device are connect；
The top of one second methanol reactor, second methanol reactor enters configured with a complete synthesis gas of the first unreacted Mouth and two the second liquid-vapor mixtures outlets, bottom is configured with the first end product outlet and two second separation water reflux Mouthful；
One second vapour liquid separator, second vapour liquid separator are at least configured there are two the second liquid-vapor mixture entrance, two Second separation water out and a low-pressure steam outlet, two of them the second liquid-vapor mixture entrance pass through two second vapour respectively Liquid mixture delivery pipe is exported with the second liquid-vapor mixture corresponding in second methanol reactor and is connected, two second separation Water out passes through two second separation water delivery pipes respectively and separates water reflux in second methanol reactor corresponding second Mouth connection, the low-pressure steam outlet send out low-pressure steam；
7th cooling device, the 7th cooling device have the 5th end product entrance, the outlet of the 5th end product, second not Synthesis gas entrance, the complete syngas outlet of the second unreacted are reacted, the 5th end product entrance of the 7th cooling device is logical The the first end product outlet for crossing the 5th end product delivery pipe and second methanol reactor bottom connects, and the described 7th is cold But the complete synthesis gas entrance of the second unreacted of device passes through the complete synthesis letter shoot of the first unreacted and the 4th gas-liquid separation The complete syngas outlet connection of first unreacted of device；The complete syngas outlet of the second unreacted of 7th cooling device passes through The complete synthesis letter shoot of second unreacted connects with the complete synthesis gas entrance of the first unreacted at the top of second methanol reactor It connects；
There is the second end product entrance and the second end product to export for second cooling device, second cooling device, and second End product entrance is exported by the 5th end product in the 6th end product delivery pipe and the 7th cooling device and is connected；
There is third end product entrance and third end product to export for third cooling device, the third cooling device, third End product entrance is exported by the second end product in the 7th end product delivery pipe and second cooling device and is connected；
One third gas-liquid separator, the third gas-liquid separator have the 4th end product entrance, first circulation gas outlet and Second separation liquid outlet, wherein the 4th end product entrance is cooling by the 8th end product delivery pipe and the third Third end product in device exports connection；On the one hand connection one speeds to put pipe for the first circulation gas outlet, on the other hand logical A recycle compressor is crossed to connect with the other end of the first circulation letter shoot；
There is third separation liquid inlet, crude carbinol outlet and flashed vapour to go out for one reduced-pressure flash tank, the reduced-pressure flash tank Mouthful, the third separation liquid inlet is separated by the first separation liquid delivery tube with second on the third gas-liquid separator Liquid outlet connection, the crude carbinol outlet output crude carbinol, flashed vapour is sent out in the flashed vapour outlet；
8th cooling device, the 8th cooling device have a 4th separation liquid inlet, the 4th separation liquid outlet, and described the Four separation liquid inlets separate liquid outlet with the first of the 4th gas-liquid separation device by the second separation liquid delivery tube 4th separation liquid outlet of connection, the 8th cooling device separates liquid delivery tube and first separating liquid by third The connection of body delivery pipe；
First methanol reactor is water cooling methanol reactor；
Second methanol reactor is the isothermal fixed bed of CN203227477U description being loaded on catalyst between heat exchanger tube Catalyst is loaded on the board-like synthetic tower of IMC isothermal on the outside of plank by reactor.
26. device as claimed in claim 25, which is characterized in that a compressor of connecting in the fresh letter shoot.
27. device as claimed in claim 25, which is characterized in that be configured with several first in the water cooling methanol reactor Reaction tube, is configured with copper-based catalysts in first reaction tube, and first gaseous mixture enters first reaction tube It is interior, occur methanol synthesis reaction under the copper-based catalysts catalytic action in first reaction tube, outside first reaction tube It is cooling by boiled water.
28. device as claimed in claim 25, which is characterized in that the reaction gas in second methanol reactor, which flows to, is Axially or radially form.
29. device as claimed in claim 25, which is characterized in that the copper-based catalysts in first methanol reactor and Copper-based catalysts in dimethanol reactor are identical, are high/low temperature activity copper-based catalysts.
30. device as claimed in claim 25, which is characterized in that the copper-based catalysts in first methanol reactor are height Warm activity copper-based catalysts, the copper-based catalysts in second methanol reactor are low temperature active copper-based catalysts.
31. device as claimed in claim 25, which is characterized in that second cooling device is air cooler, the cooling dress of third It is set to water cooling heat exchanger, the 5th cooling device is gas-gas heat exchanger, the 6th cooling device is air cooler, and the 7th cooling device is gas Gas heat exchanger, the 8th cooling device are water cooling heat exchanger.
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