CN106693839B - A kind of methanator and methanation process - Google Patents
A kind of methanator and methanation process Download PDFInfo
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- CN106693839B CN106693839B CN201510472721.7A CN201510472721A CN106693839B CN 106693839 B CN106693839 B CN 106693839B CN 201510472721 A CN201510472721 A CN 201510472721A CN 106693839 B CN106693839 B CN 106693839B
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Abstract
The invention discloses a kind of methanator and methanation process, the methanator include shell, air inlet pipe, central tube, central tube, escape pipe, cooling medium entrance, cooling medium outlet and micro- reaction channel and including or do not include sleeve, can be with supporting catalytic active component in micro- reaction channel.Compared with prior art, not only catalyst usage amount is few for methanator of the invention, but also using the methanation process of the methanator, bed pressure drop is low, and gas residence time is short, and reaction bed space utilization rate is high, without gas bias current and short circuit phenomenon.
Description
Technical field
The present invention relates to a kind of methanator and methanation process.
Background technique
Methanator is one of the core equipment of natural gas from coal project.Methanation reaction is that strong heat release is anti-
It answers, there is CO and CO during synthesis gas methanation reaction2Competition methanation reaction and high temperature under coal gas against the current become
Reaction is changed, efficient heat and mass transfer is control CO and CO2Compete the key of methanation and high temperature Reversed Water-gas Shift.Study table
It is bright, the CO or CO of every conversion 1%2Producible adiabatic temperature rise has respectively reached 70 DEG C or 60 DEG C.In order to control methanation reaction
Temperature recycles a large amount of thermal energy generated in reaction, and industrialization methanation process is contacted using multiple fixed bed methanators,
Methanation reaction is carried out step by step.Realize that there are Davy company of Britain, Denmark in the company of methanation patented technology business applicationThe Lugri company of company and Germany.
There are mainly of two types for methanator at present, and one is axially-located bed reactor, another kind is radial solid
Fixed bed reactor.Axial methanator design, process are relatively easy, easy to operate, but there are reactor apparatus rulers
Very little huge, bed pressure drop is big, be easy to appear local run aways, move heat slowly, conversion ratio is low, enlarge-effect is obvious and reactor need to
The problems such as wanting material grade high.Radial bed reactor ratio of height to diameter is larger, bed pressure drop is small, reactant is when catalyst bed stops
Between it is short, but reactant difficult to realize it is in the radial direction be uniformly distributed, the production intensity of unit catalyst bed it is lower.
Low in the presence of heat transfer, mass-transfer efficiency in traditional chemical industry in order to overcome the problems, such as, twentieth century the 80s and 90s rises
Micro- Chemical Engineering Technology.Core component of the microreactor as micro- Chemical Engineering Technology, it is anti-as the chemistry of magnitude using millimeter, micron
Answer system.One side microreactor has minute yardstick, biggish specific surface, diffusion length is short, the residence time is short, resistance is small etc.
Feature, mass transfer, heat transfer and reaction effect the 1-3 order of magnitude high compared with common response device；It on the other hand, can be according to actual industry
Production capacity requirement, is integrated by the microreactor module with functionalization and the increase and decrease of quantity reaches control and adjusts life
It produces, is advantageously implemented the maximum utilization efficiency of equipment, while shortening the process time of equipment.
Micro passage reaction is also rarely reported as one kind in microreactor, by it with methanation reaction.
CN201320593757.7 discloses a kind of micro passage reaction for methanation process, which is fixed on reaction
In support plate in the middle part of device, it is difficult to eliminate the stress for generation of expanding with heat and contract with cold；CN201110030881.8 discloses a kind of microchannel
The method of reactor and its synthesis gas full methanation, the microreactor is by several reaction channels and moves passage of heat alternating parallel row
The pressure drop of cloth, reactor is larger, while being difficult to bear high pressure.
Therefore, per volume of catalyst production intensity, the equipment size for reducing reactor, shortening gas are improved in catalyst
Superficial residence time reduces reactor pressure decrease loss, improves the transformation efficiency of reactant, and sufficiently extend catalyst uses the longevity
Life, meeting the needs of reactor is enlarged is a technical problem to be solved urgently.
Summary of the invention
The object of the present invention is to provide a kind of methanator and methanation process, which is not only catalyzed
Agent usage amount is few, and using the methanation process of the methanator, bed pressure drop is low, and gas residence time is short, reaction
Bed space utilization rate is high, without gas bias current and short circuit phenomenon.
To achieve the goals above, first aspect present invention: a kind of methanator is provided, which is characterized in that this is anti-
Answering device includes radial cylinder-shaped seal and pressure bearing shell, the air inlet pipe for extending into from the case top enclosure interior, from the shell
Body bottom extend into the escape pipe of enclosure interior and is arranged in the shell below the air inlet pipe above the escape pipe
Catalysis reaction member；The catalysis reaction member include central tube and including or do not include being set in outside central tube at least
One sleeve；Central tube has central tube, is in fluid communication between central tube and escape pipe；Between central tube and the barrel of sleeve with
And passes through baffle fluid isolation between the barrel of two neighboring sleeve and isolate mass flow pathway and runner；Outermost sleeve
Annular space is formed between the inner wall of the outer wall and shell of outer wall or central tube；Central tube and sleeve all have multiple be arranged radially
Micro- reaction channel, and be only in fluid communication by micro- reaction channel inside and outside the cylinder of central tube and inside and outside the cylinder of sleeve；
Air inlet pipe is in fluid communication by the microchannel reaction gas inlet of runner or annular space and micro- reaction channel, micro- reaction channel it is micro-
Pathway reaction product exit passes through mass flow pathway or central tube and outlet fluid communication；The side of the shell is provided at least one
A cooling medium entrance, the bottom surface of the shell be provided at least one cooling medium outlet, the cooling medium entrance with it is cold
But pass through the cooling medium pipeline across the central tube and/or sleeve and/or central tube and/or mass flow pathway between media outlet
It is in fluid communication.
Preferably, the quantity of the sleeve is 2-500.
Preferably, the side of the shell has been oppositely disposed 1# cooling medium entrance and 2# cooling medium entrance；It is described
The bottom surface of shell is symmetrically provided with the outlet of 1# cooling medium and the outlet of 2# cooling medium；The 1# cooling medium entrance with it is described
2# cooling medium entrance is formed by cooling medium pipeline with the outer wall of the inner wall and micro- reaction channel of the central tube
Chamber in fluid communication；The chamber is by cooling medium pipeline and the 1# cooling medium exports and 2# cooling medium outlet stream
Body connection.
Preferably, by being arranged in the central tube and by one between the cooling medium entrance and cooling medium outlet
Pipeline cylinder made of root cooling medium pipeline coiling is in fluid communication.
Preferably, by being arranged in the mass flow pathway and surrounding between the cooling medium entrance and cooling medium outlet
The cooling medium pipeline of the central tube and/or the sleeve is in fluid communication.
Preferably, the inner surface load of micro- reaction channel has catalytic active component.
Preferably, the diameter of micro- reaction channel goes out from the microchannel reaction gas inlet to microchannel reaction product
The direction of mouth is gradually reduced.
Preferably, the diameter of micro- reaction channel is between 2-50 millimeters.
Preferably, the ratio of the diameter of the diameter of the microchannel reaction gas inlet and the microchannel reacting product outlet
Value is (1.1-25): 1.
Preferably, the total volume of the inner space of micro- reaction channel is the volume of the catalysis reaction member
30%-90%.
Preferably, micro- reaction channel is the one of which in conical pipe, flaring pipe and Y tube.
Preferably, the lower part of the air inlet pipe is provided at least one for being distributed the reaction gas for being sent into the reactor
Gas distributor.
Preferably, the upper end of the annular space be opening and with air inlet fluid communication, the bottom end closure of annular space.
Preferably, heat-barrier material area is provided between the bottom of the catalysis reaction member and the bottom of the shell.
Second aspect of the present invention: providing a kind of methanation process, which includes: a, will contain containing hydrocarbon and hydrogen
The main methanator of 1# and the main methanation of 2# in parallel are respectively fed to after the purified processing of the methanation synthesis gas of gas and preheating
Reactor carries out main methanation reaction, obtains the first product；B, the first product obtained in step a is sent at least after cooling down
One supplement methanator carries out supplement methanation reaction, obtains the second product；C, by the second product obtained in step b
Separating treatment is carried out after cooling down, and obtains methanation product；Wherein, the main methanator of the 1#, the main methanation reaction of 2#
At least one in device and supplement methanator is methanator provided by first aspect present invention.
Preferably, the technique further include: by boiler feedwater be sent into the main methanator of 1#, the main methanator of 2# and
It carries out taking heat in supplement methanator, generated steam is sent into drum.
Preferably, described containing hydrocarbon is carbon monoxide and/or carbon dioxide that M value is 2.85-3.5；The M value
For the volume of methanation synthesis gas institute hydrogen and the difference containing the volume of carbon dioxide in hydrocarbon contains together oxidation of coal
Close the ratio of object product.
Preferably, the purified treatment successively includes hydrolysis, desulfurization, deoxidation and denitration process.
Preferably, the quantity of the supplement methanator is 1-2 platform.
Preferably, the condition of the main methanation reaction are as follows: reaction temperature is 300-700 DEG C, reaction pressure 1.0-8.5
Megapascal；The condition of the supplement methanation reaction are as follows: reaction temperature is 300-700 DEG C, and reaction pressure is 1.0-8.5 megapascal.
Compared with prior art, methanator and methanation process provided by the invention have the advantages that
1, methanation reaction is the quick strong exothermal reaction of volume-diminished, contains methanation reaction catalytic activity using coating
The micro- reaction channel of conical pipe or oviduct of component, as reactant is from conical pipe or oviduct larger diameter end to small diameter
End flowing, reaction channel is smaller and smaller, the motive force that methanation reaction is converted to product direction is increased, since gas flow rate is got over
Come it is bigger so that residence time of the product gas in micro- reaction channel is shorter；
2, using coating methanation reaction catalytic active component in micro- reaction channel inner surface, active metal usage amount is same
Etc. processing capacities routine fixed bed reactors amount used 5%-25%, significantly reduce catalyst production cost；
3, since the residence time is shorter in the reactor for reaction gas, extending the service life of catalyst, (service life can be with
Improve 15%-20%), bed pressure drop is low compared with the radial reactor of same treating capacity (50%-85%)；
4, the conversion zone that the reactor is made of the identical taper of several sizes or tubaeform micro- reaction channel, it is reactionless
The temperature of the Biased flow phenomenon in dead zone and gas, bed is more uniform, is not in hot spot, has fully ensured that the whole service period
Even running；
5, the feed stock conversion of the reactor is high, the conversion ratio of CO nearly 100%, target product CH4Selectivity be more than
95%, unit reactor produces the more conventional fixed bed of intensity, the fluidisation height of bed, can satisfy the production of existing coal system substitution natural gas
Process；
6, can be required according to actual industrial capacity, by micro- reaction channel module with functionalization it is integrated with
And the increase and decrease of quantity reaches control and adjusts production, is advantageously implemented the maximum utilization efficiency of equipment, without obvious enlarge-effect, together
When shorten equipment process time, further decrease reactor production cost；
7, coal system substitution natural gas and gas employing methanation of coke oven technique can not only be applied to, it may also be used for methanol-fueled CLC,
The fixed-bed catalytics exothermic reactions such as CO transformation, F- T synthesis.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is that a kind of structural schematic diagram of specific embodiment of methanator provided by the invention (has one
Sleeve and micro- reaction channel are conical pipe)；
Fig. 2 is a kind of cross-sectional view (the i.e. face A-A in Fig. 1 of specific embodiment of methanator provided by the invention
Cross-sectional view)；
Fig. 3 is a kind of flow diagram of specific embodiment of methanation process provided by the invention (using shown in Fig. 1
Methanator, have 1# supplement methanator and 2# supplement methanator)；
Fig. 4 is that a kind of structural schematic diagram of specific embodiment of methanator provided by the invention (does not have set
Cylinder, micro- reaction channel are conical pipe)；
Fig. 5 is a kind of cross-sectional view (the i.e. face A-A in Fig. 4 of specific embodiment of methanator provided by the invention
Cross-sectional view)；
Fig. 6 is a kind of flow diagram of specific embodiment of methanation process provided by the invention (using shown in Fig. 4
Methanator, have 1# supplement methanator)；
Fig. 7 is that a kind of structural schematic diagram of specific embodiment of methanator provided by the invention (does not have set
Cylinder, micro- reaction member are flaring pipe)；
Fig. 8 is a kind of cross-sectional view (the i.e. face A-A in Fig. 7 of specific embodiment of methanator provided by the invention
Cross-sectional view)；
Fig. 9 is a kind of flow diagram of specific embodiment of methanation process provided by the invention (using shown in Fig. 7
Methanator, have 1# supplement methanator)；
Figure 10 is a kind of specific embodiment (cone of micro- reaction channel used by methanator provided by the invention
Shape pipe) schematic diagram；
Figure 11 is a kind of specific embodiment (loudspeaker of micro- reaction channel used by methanator provided by the invention
Shape pipe) schematic diagram；
Figure 12 is a kind of specific embodiment (Y of micro- reaction channel used by methanator provided by the invention
Shape pipe) schematic diagram.
Description of symbols
1 shell, 2 air inlet pipe, 3 escape pipe, 4 central tube, 5 sleeve
The micro- reaction channel of 6 central tube, 7 mass flow pathway, 8 runner, 9 annular space 10
11 microchannel reaction gas inlet, 12 microchannel reacting product outlet
13 heat-barrier material area, 14 first gas distributor, 15 second gas distributor
The main methanator of main 17 2# of methanator of 16 1#
18 1# supplement 19 2# of methanator and supplement methanator
20 drum, 21 steam superheater, 22 boiler water-suppling heater
23 2# cooler, 24 1# cooler, 25 product separator
26 baffles
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
First aspect present invention: a kind of methanator is provided, which is characterized in that the reactor includes radial cylinder-shaped
Seal and pressure bearing shell 1, the air inlet pipe 2 that enclosure interior is extend at the top of the shell 1 extend into shell from 1 bottom of shell
The escape pipe 3 in internal portion and the catalysis reaction that 3 top of escape pipe below the air inlet pipe 2 is set in the shell 1
Unit；The catalysis reaction member include central tube 4 and including or do not include at least one sleeve being set in outside central tube 4
5；Central tube 4 has central tube 6, is in fluid communication between central tube 6 and escape pipe 3；Between central tube 4 and the barrel of sleeve 5 with
And passes through 26 fluid isolation of baffle between the barrel of two neighboring sleeve 5 and isolate mass flow pathway 7 and runner 8；It is outermost
Annular space 9 is formed between the outer wall of sleeve 5 or the outer wall of central tube 4 and the inner wall of shell 1；Central tube 4 and sleeve 5 all have more
A micro- reaction channel 10 being arranged radially, and it is micro- anti-only to pass through this inside and outside the cylinder of central tube 4 and inside and outside the cylinder of sleeve 5
Channel 10 is answered to be in fluid communication；Air inlet pipe 2 passes through runner 8 or the microchannel reaction gas inlet of annular space 9 and micro- reaction channel 10
11 are in fluid communication, and the microchannel reacting product outlet 12 of micro- reaction channel 10 is flowed by mass flow pathway 7 or central tube 6 and escape pipe 3
Body connection；The side of the shell 1 is provided at least one cooling medium entrance, and the bottom surface of the shell 1 is provided at least one
A cooling medium outlet, by passing through the central tube 4 and/or sleeve between the cooling medium entrance and cooling medium outlet
5 and/or the cooling medium pipeline of central tube 6 and/or mass flow pathway 7 be in fluid communication.
A kind of specific embodiment according to a first aspect of the present invention, the central tube 4 and the sleeve 5 can be by
The top sealing plate of sealed connection, sealed bottom plate and side wall are constituted, in can be hollow, can be solid, as long as can accommodate
Micro- reaction channel 10.The diameter of the diameter of the central tube 4 and the diameter ratio of central tube 6 and the central tube 4 with
Any ratio that the diameter ratio of the sleeve 5 all can be suitble to.
According to the first aspect of the invention, under identical reaction condition and reactor diameter, the quantity for increasing sleeve 5 can
To increase the time of contact of reaction gas and catalyst, reaction gas flow velocity is reduced, to reach reduction pressure drop, improves conversion ratio
Effect, therefore the quantity of sleeve 5 can be adjusted according to real reaction situation, the quantity of the sleeve 5 preferred 2-500,
Further preferably 2-15.
Since methanation reaction is exothermic reaction, it is therefore desirable to reduce the temperature of methanator, those skilled in the art
The conventional method of member is to be cooled down using cooling medium to methanator.One kind according to a first aspect of the present invention is specific
Embodiment, the side of the shell 1 can be oppositely disposed 1# cooling medium entrance and 2# cooling medium entrance；The shell
The bottom surface of body 1 can also be symmetrically provided with the outlet of 1# cooling medium and the outlet of 2# cooling medium；The 1# cooling medium entrance
With the 2# cooling medium entrance by cooling medium pipeline with the central tube 4 inner wall and micro- reaction channel 10 it is outer
Wall is formed by chamber in fluid communication；The chamber is exported by cooling medium pipeline and the 1# cooling medium and 2# is cooling is situated between
Matter communication.
A kind of specific embodiment according to a first aspect of the present invention, the cooling medium entrance and cooling medium export it
Between can by be arranged in the central tube 6 and the pipeline cylinder as made of a cooling medium pipeline coiling be in fluid communication.Institute
Stating can also be by being arranged in the mass flow pathway 7 and around the central tube between cooling medium entrance and cooling medium outlet
4 and/or the sleeve 5 cooling medium pipeline be in fluid communication.It should be noted that with a pair of cooling medium entrance and cooling Jie
It can be in fluid communication by more cooling medium pipelines between matter outlet.
According to the first aspect of the invention, described micro- anti-in order to make the methanator can be used in producing methane
Catalytic active component can have been loaded by answering the inner surface in channel 10.The catalytic active component can use those skilled in the art
Known catalytic active component, such as can be with metals such as the active nickel of methanation reaction, ruthenium and rhodiums；The load
Referring to can will be active by the catalyst containing active component or directly by the methods of dipping, ion sputtering, coating or filling
Component loads in micro- reaction channel.Wherein, active metal component coating loading process can use those skilled in the art institute
The coating method in well known two stages of pretreatment and catalyst deposit including metallic matrix.
According to the first aspect of the invention, in order to guarantee the efficiency of methanation reaction, the diameter of micro- reaction channel 10
It can be between 2-50 millimeters.Due to methanation reaction be total volume reduce reaction, micro- reaction channel 10 it is straight
Diameter can be gradually reduced from the microchannel reaction gas inlet 11 to the direction of microchannel reacting product outlet 12 (to be guaranteed micro- logical
The diameter of road reaction gas inlet 11 is greater than the diameter of microchannel reacting product outlet 12, also includes that channel diameter first reduces
Constant situation afterwards).The diameter of the diameter of the microchannel reaction gas inlet 11 and the microchannel reacting product outlet 12
Ratio can be (1.1-25): 1, preferably (2-10): 1.It should be noted that if the reactor of invention is used for other
Reaction, can be arranged the diameter of micro- reaction channel 10 according to the concrete condition of the reaction.
According to the first aspect of the invention, since methanation reaction is exothermic reaction, in order to balance reaction efficiency and methane
Change the temperature control of reactor, the total volume of the inner space of micro- reaction channel 10 can be the catalysis reaction member
The 30%-90% of volume, preferably 50%-85%.
A kind of specific embodiment according to a first aspect of the present invention, micro- reaction channel 10 can be for selected from tapers
One of which in pipe, flaring pipe and Y tube (respectively as shown in Figure 10, Figure 11 and Figure 12)；It should be understood that described micro-
The diameter of pathway reaction gas access 11 is greater than the diameter of the microchannel reacting product outlet 12.It is the conical pipe, tubaeform
Pipe and Y tube can use metal material pipe, ceramic material pipe, it is preferred to use not occur with the gas in methanation reaction system
The metal tube of reaction.It should be noted that the conventional use of conical pipe of those skilled in the art refers to the truncated cone-shaped of both ends open
Hollow material, rather than axial cross section is the profile of taper.
According to the first aspect of the invention, the lower part of the air inlet pipe 2 can be set at least one for be distributed feeding
The gas distributor of the reaction gas of the reactor.The gas distributor can be using used in those skilled in the art's routine
, the present invention repeats no more, there are two the gas distributor is preferably provided with.
According to the first aspect of the invention, the upper end of the annular space 9 can be in fluid communication for opening and with air inlet pipe 2, ring
The bottom end of gap 9 can be closed.
According to the first aspect of the invention, the bottom of shell 1 is excessively heated in order to prevent and prevents central tube 4 and sleeve
5 move down, and can set between the bottom of catalysis reaction member (i.e. central tube 4 and sleeve 5) and the bottom of the shell 1
It is equipped with heat-barrier material area 13.Can be placed in the heat-barrier material area 13 single material well-known to those skilled in the art or
The heat-barrier materials such as the heat insulating ball of a variety of composites, heat-insulated felt rug or heat insulating belt.
Second aspect of the present invention: providing a kind of methanation process, which includes: a, will contain containing hydrocarbon and hydrogen
The main methanator of 1# and the main methanation of 2# in parallel are respectively fed to after the purified processing of the methanation synthesis gas of gas and preheating
Reactor carries out main methanation reaction, obtains the first product；B, the first product obtained in step a is sent at least after cooling down
One supplement methanator carries out supplement methanation reaction, obtains the second product；C, by the second product obtained in step b
Separating treatment is carried out after cooling down, and obtains methanation product；Wherein, the main methanator of the 1#, the main methanation reaction of 2#
At least one in device and supplement methanator is methanator provided by first aspect present invention.Preferably,
The quantity of the supplement methanator is 1-2 platform.
It according to the second aspect of the invention, can be by boiler feedwater (i.e. in order to control the reaction temperature of methanator
Cooling medium) it is sent into the main methanator of 1#, the main methanator of 2# and supplement methanator and carries out taking heat, institute
The steam of generation is sent into drum, and the preferably multiple methanators of the present invention share a drum.
According to the second aspect of the invention, it is described containing hydrocarbon can be it is well-known to those skilled in the art containing
The gas of carbon monoxide and/or carbon dioxide, is generally from industrial tail gas, preferably M value be 2.85-3.5 carbon monoxide and/
Or carbon dioxide；The M value can be for the volume of methanation synthesis gas institute hydrogen and containing titanium dioxide in hydrocarbon
Ratio of the difference of the volume of carbon with the volume containing hydrocarbon, i.e. M=(V (H2)-V(CO2))/(V(CO+CO2)), because if
Methanation reaction carries out completely, V (H2): V (CO2)=4:1, V (H2): V (CO)=3:1, and M value is 3 or so, it is meant that it is carbon containing
Oxygen compound and hydrogen almost just fully reacting.
According to the second aspect of the invention, the purified treatment can successively include water well-known to those skilled in the art
Solution, desulfurization, deoxidation and denitration process.
According to the second aspect of the invention, the condition of the main methanation reaction can be with are as follows: reaction temperature 300-700
DEG C, reaction pressure is 1.0-8.5 megapascal；The condition of the supplement methanation reaction can be with are as follows: and reaction temperature is 300-700 DEG C,
Reaction pressure is 1.0-8.5 megapascal.
The present invention is further illustrated by embodiment below in conjunction with attached drawing, but therefore the present invention is not taken office
What is limited.
Embodiment 1
As shown in figure 3, the reaction unit of the present embodiment by the main methanator 16 of 1#, the main methanator 17 of 2#,
It is cold that 1# supplements methanator 18,2# supplement methanator 19, steam superheater 21, boiler water-suppling heater 22,2#
But device 23,1# cooler 24, product separator 25 are connected with drum 20.Two main methanators phase by the way of in parallel
Even, a drum 20 is shared with two supplement methanators.
Operating procedure is as follows:
A, by H2/ CO volume ratio is 3.0 (M=3.0), the synthesis gas that pressure 3.5MPa, temperature are 250 DEG C, total volume
Flow rate is 10m3/ h is divided into two strands and enters main methanator, one enters the main methanator 16 of 1# and carries out main methane
Change reaction, another strand of synthesis gas enters the main methanator 17 of 2# and carry out main methanation reaction, two main methanators
Micro- reaction channel size it is identical, operating condition is identical；
B, reaction temperature, the pressure of the main methanator 16 of 1# and the main methanator 17 of 2# be 650 DEG C,
3.45MPa；
C, the main methanator 16 of 1# and 2# resulting first product of main methanator 17 pass through steam superheater
After 21 heat exchange, temperature is reduced to 400 DEG C, sequentially passes through 1# supplement methanator 18,2# supplements methanator 19, into one
Unreacted synthesis gas in step the first product of conversion；1# supplements the reaction temperature of methanator 18, pressure is 435 DEG C,
3.38MPa, 2# supplement the reaction temperature of methanator 19, pressure is 350 DEG C, 3.36MPa；
D, after two-stage supplements methanator, the second product is through boiler water-suppling heater 22,23 and of 1# cooler
After 2# cooler 24 cools down, the isolated methanation product after product separator 25；
E, boiler feedwater is divided stereotyped writing, is respectively enterd in the form of two strands from top after the preheating of boiler water-suppling heater 22
The main methanator 16 of 1#, the main methanator 17 of 2#, 1# supplement methanator 18 and 2# supplement methanation reaction
Device 19 generates middle pressure steam and fully enters drum 20, and four methanators share a drum 20；Water in drum is through steaming
It is sent out after the heating of vapour superheater.
The conversion ratio of carbon monoxide is 99% in the present embodiment, and the selectivity of methane is 95%, while by-product 11.4MPa,
530 DEG C of high pressure superheated steam.
4 methanators used by the present embodiment are as depicted in figs. 1 and 2, and structure is as follows:
As depicted in figs. 1 and 2, methanator includes shell 1, air inlet pipe 2, escape pipe 3 and catalysis reaction member.Into
The lower end of tracheae 2 is provided with first gas distributor 14 and second gas distributor 15, is catalyzed the bottom surface of reaction member and shell 1
Between be provided with the heat-barrier material area 13 being made of heat-insulated felt rug.Being catalyzed reaction member includes coaxial central tube 4 and 1 sleeve
5,4 center of central tube has central tube 6, completely cuts off runner 8 out and mass flow pathway 7 by baffle 26 between central tube 4 and sleeve 5,
The side wall of sleeve 5 and shell 1 forms gap 9.Micro- reaction channel 10 used by the present embodiment is conical pipe as shown in Figure 10,
Supported active metals NiO amount is 5.5g/m in conical pipe2。
Methanator diameter of the housing is 910mm, and the height of central tube and sleeve is 1200mm, and center pipe diameter is
150mm, central tube diameter are 450mm, and sleeve diameter 855mm, the used micro- reaction channel length of conical pipe is 150mm,
Conical pipe inlet diameter 10mm, exit diameter 4mm, the total volume of all conical pipes account for the ratio of catalysis reaction member volume
It is 50.2%.
There are two heat exchange zones in the present embodiment, and one is central tube 6, the other is mass flow pathway 7.Cooling medium is from shell
The cooling medium entrance in 1 outside enters inside shell 1, is then divided into two strands, one is set in mass flow pathway 7 around central tube
4 cooling medium pipeline cools down to methanator, in another centrally disposed pipe 6 of stock-traders' know-how by a cooling medium
Pipeline cylinder made of pipeline coiling cools down to methanator.
Embodiment 2
As shown in fig. 6, the reaction unit of the present embodiment by the main methanator 16 of 1#, the main methanator 17 of 2#,
1# supplements methanator 18, steam superheater 21, boiler water-suppling heater 22,2# cooler 23,1# cooler 24, product
Separator 25 is connected with drum 20.Two main methanators are connected by the way of in parallel, with supplement methanator
Share a drum 20.
Operating procedure is as follows:
It a, is 3.0MPa by pressure, the conjunction that temperature is 250 DEG C, the carbon monoxide containing M=2.95, carbon dioxide and hydrogen
At gas, total volume flow rate 10m3/ h is divided into two strands and enters main methanator, one enters the main methanator 16 of 1#
Main methanation reaction is carried out, another strand of synthesis gas enters the main methanator 17 of 2# and carry out main methanation reaction, two main first
Micro- reaction channel size of alkylation reactors is identical, and operating condition is identical；
B, reaction temperature, the pressure of the main methanator 16 of 1# and the main methanator 17 of 2# be respectively 550 DEG C,
2.96MPa；
C, the main methanator 16 of 1# and 2# resulting first product of main methanator 17 pass through steam superheater
After 21 heat exchange, temperature is reduced to 400 DEG C, supplements methanator 18 by 1# and further converts unreacted conjunction in the first product
At gas, the reaction temperature that 1# supplements methanator 18 is 370 DEG C, reaction pressure 2.93MPa；
D, after level-one supplements methanator, the second product is through boiler water-suppling heater 22,23 and of 1# cooler
After 2# cooler 24 cools down, the isolated methanation product after product separator 25；
E, boiler feedwater divides 6 strands, respectively enters 1# from top in the form of two strands after the preheating of boiler water-suppling heater 22
The main methanator 17 of main methanator 16,2# and 1# supplement methanator 18, generate middle pressure steam all into
Enter drum 20.Three methanators share a drum 20.
The conversion ratio of carbon monoxide is 100% in the present embodiment, and titanium dioxide charcoal percent conversion is 97.5%, the selection of methane
Property is 97.5%, while by-product 5.8MPa, 470 DEG C of high pressure superheated steam.
3 methanators used by the present embodiment are as shown in Figure 4 and Figure 5, and structure is as follows:
Methanator includes shell 1, air inlet pipe 2, escape pipe 3 and catalysis reaction member.The lower end of air inlet pipe 2 is arranged
Have a first gas distributor 14 and second gas distributor 15, be catalyzed between reaction member and the bottom surface of shell 1 be provided with by every
The heat-barrier material area 13 that hot felt rug is constituted.Catalysis reaction member is provided with central tube 4, and 4 center of central tube has central tube 6, in
The side wall of heart cylinder 4 and shell 1 forms annular space 9.Micro- reaction channel 10 used by the present embodiment is conical pipe as shown in Figure 10,
Supported active metals NiO amount is 10g/m in conical pipe2。
The height of methanator central tube is 1000mm, and center pipe diameter is 400mm, and used conical pipe is micro- anti-
Answering passage length is 300mm, conical pipe inlet diameter 10mm, exit diameter 4mm, and the total volume of all conical pipes accounts for center
The ratio of 4 volumes of cylinder is 70.7%.
There is a heat exchange zone in the present embodiment, in centrally disposed cylinder 4.Two bursts of cooling mediums are respectively from 1 outside of shell
1# cooling medium entrance and 2# cooling medium entrance enter in shell 1, the 1# cooling medium entrance and the 2# are cooling to be situated between
Matter entrance is formed by by two cooling medium pipelines with the outer wall of the inner wall and micro- reaction channel 10 of the central tube 4
Chamber in fluid communication, the cooling medium pipeline and the 1# cooling medium which passes through heat-barrier material area 13 by two export
With 2# cooling medium communication, cooling medium is sent out into methanator.
Embodiment 3
As Figure 7-9, the present embodiment the difference from example 2 is that, micro- reaction channel be loudspeaker as shown in figure 11
Shape pipe, reaction condition and other parameters are all the same.
CO conversion ratio in raw material of synthetic gas is 100%, and titanium dioxide charcoal percent conversion is 98%, substitutes the selection of natural gas
Property reaches 97.5%, while by-product 5.8MPa, 470 DEG C or so of high-temperature steam.
Methanator provided by the invention is compact-sized, active metal dosage is few；The methanator is carried out
When methanation reaction, bed pressure drop is small, without obvious enlarge-effect, per volume of catalyst production intensity is big, feed stock conversion is high,
Product is short in the catalyst surface residence time, can remove reaction heat in time, catalyst is avoided superheat region occur, extends catalysis
The service life of agent can satisfy the production process of existing coal system substitution natural gas.
Claims (20)
1. a kind of methanator, which is characterized in that the reactor includes radial cylinder-shaped seal and pressure bearing shell (1), from institute
It states and extend into the air inlet pipe (2) of enclosure interior at the top of shell (1), extend into the outlet of enclosure interior from the shell (1) bottom
The catalysis managing (3) and being arranged in the shell (1) below the air inlet pipe (2) above the escape pipe (3) reacts single
Member；
The catalysis reaction member include central tube (4) and including or do not include being set at least one of central tube (4) outside
Sleeve (5)；Central tube (4) has central tube (6), is in fluid communication between central tube (6) and escape pipe (3)；Central tube (4) and set
Pass through baffle (26) fluid isolation between the barrel of cylinder (5) and between the barrel of two neighboring sleeve (5) and isolates afflux
Road (7) and runner (8)；Shape between the outer wall of outermost sleeve (5) or the outer wall of central tube (4) and the inner wall of shell (1)
At there is annular space (9)；Central tube (4) and sleeve (5) all have multiple micro- reaction channels (10) being arranged radially, and central tube
(4) only it is in fluid communication by micro- reaction channel (10) inside and outside cylinder and inside and outside the cylinder of sleeve (5)；Air inlet pipe (2) is logical
The microchannel reaction gas inlet (11) for crossing runner (8) or annular space (9) and micro- reaction channel (10) is in fluid communication, and micro- reaction is logical
The microchannel reacting product outlet (12) in road (10) is in fluid communication by mass flow pathway (7) or central tube (6) and escape pipe (3)；
The side of the shell (1) is provided at least one cooling medium entrance, and the bottom surface of the shell (1) is provided at least one
A cooling medium outlet, by passing through the central tube (4) and/or covering between the cooling medium entrance and cooling medium outlet
The cooling medium pipeline of cylinder (5) and/or central tube (6) and/or mass flow pathway (7) is in fluid communication.
2. methanator according to claim 1, which is characterized in that the quantity of the sleeve (5) is 2-500.
3. methanator according to claim 1, which is characterized in that the side of the shell (1) has been oppositely disposed 1#
Cooling medium entrance and 2# cooling medium entrance；The bottom surface of the shell (1) is symmetrically provided with the outlet of 1# cooling medium and 2#
Cooling medium outlet；The 1# cooling medium entrance and the 2# cooling medium entrance pass through cooling medium pipeline with the center
The inner wall of cylinder (4) and the outer wall of micro- reaction channel (10) are formed by chamber in fluid communication；The chamber is situated between by cooling
Matter pipeline and 1# cooling medium outlet and 2# cooling medium communication.
4. methanator according to claim 1, which is characterized in that the cooling medium entrance and cooling medium export it
Between by setting in the central tube (6) and the pipeline cylinder as made of a cooling medium pipeline coiling is in fluid communication.
5. methanator according to claim 1, which is characterized in that the cooling medium entrance and cooling medium export it
Between by setting in the mass flow pathway (7) and around the central tube (4) and/or the cooling medium pipeline of the sleeve (5)
It is in fluid communication.
6. methanator according to claim 1, which is characterized in that the inner surface load of micro- reaction channel (10) has
Catalytic active component.
7. methanator according to claim 1, which is characterized in that the diameter of micro- reaction channel (10) is from described micro-
Pathway reaction gas access (11) is gradually reduced to the direction of microchannel reacting product outlet (12).
8. methanator according to claim 1, which is characterized in that the diameter of micro- reaction channel (10) is in 2-50 milli
Between rice.
9. methanator according to claim 1, which is characterized in that the diameter of the microchannel reaction gas inlet (11)
Ratio with the diameter of the microchannel reacting product outlet (12) is (1.1-25): 1.
10. methanator according to claim 1, which is characterized in that the inner space of micro- reaction channel (10)
Total volume is the 30%-90% of the volume of the catalysis reaction member.
11. methanator according to claim 1, which is characterized in that micro- reaction channel (10) be selected from conical pipe,
One of which in flaring pipe and Y tube.
12. methanator according to claim 1, which is characterized in that the lower part of the air inlet pipe (2) is provided at least one
A gas distributor for being used to be distributed the reaction gas for being sent into the reactor.
13. methanator according to claim 1, which is characterized in that the upper end of the annular space (9) is opening and and air inlet
It manages (2) to be in fluid communication, the bottom end closure of annular space (9).
14. methanator according to claim 1, which is characterized in that the bottom of the catalysis reaction member and the shell
Heat-barrier material area (13) are provided between the bottom of body (1).
15. a kind of methanation process, the technique include:
A, parallel connection will be respectively fed to containing the purified processing of the methanation synthesis gas containing hydrocarbon and hydrogen and after preheating
The main methanator of 1# and the main methanator of 2# carry out main methanation reaction, obtain the first product；
B, the first product obtained in step a is sent into after cooling down at least one supplement methanator and carries out supplement methane
Change reaction, obtains the second product；
C, the second product obtained in step b is subjected to after cooling down separating treatment, obtains methanation product；
Wherein, at least one in the main methanator of the 1#, the main methanator of 2# and supplement methanator
For selected from methanator described in any one of claim 1-14.
16. methanation process according to claim 15, the technique further include: it is anti-that the main methanation of 1# is sent into boiler feedwater
It answers and carries out taking heat in the main methanator of device, 2# and supplement methanator, generated steam is sent into drum.
17. methanation process according to claim 15, wherein described be M value containing hydrocarbon is 2.85-3.5's
Carbon monoxide and carbon dioxide；
Or described containing hydrocarbon is carbon dioxide that M value is 2.85-3.5；The M value is the methanation synthesis gas institute
The ratio of the volume of hydrogen and difference containing the volume of carbon dioxide in hydrocarbon with the volume containing hydrocarbon.
18. methanation process according to claim 15, wherein the purified treatment successively includes hydrolysis, desulfurization, deoxidation
And denitration process.
19. methanation process according to claim 15, wherein the quantity of the supplement methanator is 1-2 platform.
20. methanation process according to claim 15, wherein the condition of the main methanation reaction are as follows: reaction temperature
It is 300-700 DEG C, reaction pressure is 1.0-8.5 megapascal；The condition of the supplement methanation reaction are as follows: reaction temperature 300-
700 DEG C, reaction pressure is 1.0-8.5 megapascal.
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| EP0711595B1 (en) * | 1994-11-08 | 1998-01-14 | Basf Aktiengesellschaft | Reactor for carrying out heterogenous catalytic reactions in gas phase |
| CN101880552A (en) * | 2010-06-29 | 2010-11-10 | 中国科学院广州能源研究所 | Gasification device and method for preparing hydrogen-rich synthetic gas from biomass |
| CN102133512A (en) * | 2010-01-21 | 2011-07-27 | 华东理工大学 | Reactor applied to gas-phase exothermic reaction |
| CN203540513U (en) * | 2013-09-23 | 2014-04-16 | 中国五环工程有限公司 | Micro-channel reactor for methanation process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0711595B1 (en) * | 1994-11-08 | 1998-01-14 | Basf Aktiengesellschaft | Reactor for carrying out heterogenous catalytic reactions in gas phase |
| CN102133512A (en) * | 2010-01-21 | 2011-07-27 | 华东理工大学 | Reactor applied to gas-phase exothermic reaction |
| CN101880552A (en) * | 2010-06-29 | 2010-11-10 | 中国科学院广州能源研究所 | Gasification device and method for preparing hydrogen-rich synthetic gas from biomass |
| CN203540513U (en) * | 2013-09-23 | 2014-04-16 | 中国五环工程有限公司 | Micro-channel reactor for methanation process |
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