CN106378063B - A kind of methanator and methanation process - Google Patents
A kind of methanator and methanation process Download PDFInfo
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- CN106378063B CN106378063B CN201510472723.6A CN201510472723A CN106378063B CN 106378063 B CN106378063 B CN 106378063B CN 201510472723 A CN201510472723 A CN 201510472723A CN 106378063 B CN106378063 B CN 106378063B
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Abstract
The invention discloses a kind of methanator and methanation process, the methanator includes shell, air inlet pipe, laterally catalysis reaction member, longitudinal direction are catalyzed reaction member, escape pipe, axial micro- reaction channel and radial micro- reaction channel, can be with supporting catalytic active component in axial micro- reaction channel and the micro- reaction channel of radial direction.Compared with prior art, not only catalyst usage amount is few for methanator of the invention, but also when carrying out methanation reaction using 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 when use methanator progress methanation reaction, 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：There is provided a kind of methanator, 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
Longitudinal catalysis reaction member and lateral catalysis reaction member；Longitudinal catalysis reaction member and lateral catalysis reaction member are
Setting up and down or lower upper setting, between be formed with unitary space；Longitudinal catalysis reaction member includes central tube and is set in center
At least one sleeve outside cylinder；Central tube have central tube, central tube with below unitary space or outlet fluid communication；
Pass through baffle fluid isolation between central tube and the barrel of sleeve and between the barrel of two neighboring sleeve and isolates afflux
Road and runner；Annular space is formed between the outer wall of outermost sleeve and the inner wall of shell；Central tube and sleeve all have more
A micro- reaction channel of radial direction being arranged radially, and only pass through the radial direction inside and outside the cylinder of central tube and inside and outside the cylinder of sleeve
Micro- reaction channel is in fluid communication；Air inlet pipe or unitary space pass through runner or annular space and radial micro- reaction channel below
Radial microchannel reaction gas inlet is in fluid communication, and the radial microchannel reacting product outlet of radial micro- reaction channel passes through afflux
Road or central tube with below unitary space or outlet fluid communication；Laterally catalysis reaction member includes at least one column
Body, cylinder is coaxial with shell, and the lateral surface of cylinder and the portion of medial side of shell are inconsistent or coincide；Two neighboring cylinder
Between be formed with gap；Cylinder is provided under the micro- reaction channel of axial direction axially across cylinder, air inlet pipe or unitary space and its
Between the unitary space or gap of side, between gap and gap and gap and between unitary space below or escape pipe only
It is in fluid communication by setting in the micro- reaction channel of the intracorporal axial direction of column, the axial direction that axial micro- reaction channel has diameter different is micro- logical
Road reaction gas inlet and axial microchannel reacting product outlet.
Preferably, the quantity of the sleeve is 2-500, and the quantity of the cylinder is 2-500.
Preferably, the side of the shell is provided at least a pair of of cooling medium entrance and cooling medium outlet, described cold
But medium inlet passes through the cooling across the cylinder and/or unitary space and/or gap and/or central tube and/or mass flow pathway
Medium pipeline and the cooling medium communication.
Preferably, the side of the shell is provided at least a pair of of cooling medium entrance and cooling medium outlet, described cold
But medium inlet is formed by chamber and the cooling by the inner wall of the cylinder and the outer wall of the micro- reaction channel of the axial direction
Media outlet is in fluid communication.
Preferably, the inner surface load of the micro- reaction channel of the radial direction has catalytic active component, and the micro- reaction of axial direction is logical
The inner surface load in road has catalytic active component.
Preferably, the diameter of the micro- reaction channel of the radial direction is micro- logical from the radial microchannel reaction gas inlet to radial direction
The direction of road reacting product outlet is gradually reduced, and the diameter of the micro- reaction channel of axial direction is from the axial microchannel reaction gas
The direction of entrance microchannel reacting product outlet in the axial direction is gradually reduced.
Preferably, the diameter of the micro- reaction channel of the radial direction is between 2-50 millimeters, the micro- reaction channel of axial direction it is straight
Diameter is between 2-50 millimeters.
Preferably, the diameter of the radial microchannel reaction gas inlet and the radial microchannel reacting product outlet
The ratio of diameter is (1.1-25)：1, the diameter of axial direction microchannel reaction gas inlet should be produced with the axial microchannel plate
The ratio of the diameter of object outlet is (1.1-25)：1.
Preferably, the total volume of the inner space of the micro- reaction channel of the radial direction is the total volume of longitudinal catalysis reaction member
30%-90%, the total volume of the inner space of the micro- reaction channel of axial direction is the total volume of laterally catalysis reaction member
30%-90%.
Preferably, the micro- reaction channel of the radial direction is the one of which in conical pipe, flaring pipe and Y tube, institute
Stating axial 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；Be provided in the unitary space at least one for be distributed from longitudinal catalysis reaction member to laterally catalysis instead
Answer unit or laterally gas distributor of the catalysis reaction member to longitudinal gas for being catalyzed reaction member flowing.
Preferably, it is provided between longitudinal catalysis reaction member or lateral catalysis reaction member and the inner bottom surface of the shell
Heat-barrier material area.
Second aspect of the present invention：A kind of methanation process is provided, which includes：It a, will be containing 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 into supplement after cooling down
Methanator carries out supplement methanation reaction, obtains the second product；C, by the second product obtained in step b after cooling down
Separating treatment is carried out, methanation product is obtained；Wherein, the main methanator of the 1#, the main methanator of 2# and supplement
At least one in methanator is selected from methanator described in any one of claim 1-12.
Preferably, which further includes：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 condition of the main methanation reaction is：Reaction temperature is 300-700 DEG C, reaction pressure 1.0-8.5
Megapascal；It is described supplement methanation reaction condition be：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 following advantages that：
1, methanation reaction is the quick strong exothermal reaction of volume-diminished, contains methanation reaction catalytic activity using coating
Conical pipe, Y tube or the micro- reaction channel of oviduct of component, as reactant is from conical pipe, Y tube or oviduct larger diameter
It holds to smaller diameter end and flows, reaction channel is smaller and smaller, the motive force that methanation reaction is converted to product direction is increased, by
It is increasing in product flow velocity, so that residence time of the product 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, Y tube or tubaeform micro- reaction channel,
The temperature of the Biased flow phenomenon in reactionless dead zone and gas, bed is more uniform, is not in hot spot, has fully ensured that whole service
Even running in period；
5, the feed stock conversion of the reactor is high, the conversion ratio of CO nearly 100%, target product CH4Selectivity be more than
95%, the more conventional fixed bed of unit reactor production intensity, fluidized bed are all high, can satisfy the life of existing coal system substitution natural gas
Production 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 a kind of structural schematic diagram (the laterally catalysis of specific embodiment of methanator provided by the invention
Reaction member is located above longitudinal catalysis reaction member)；
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 cross-sectional view (the i.e. face B-B in Fig. 1 of specific embodiment of methanator provided by the invention
Cross-sectional view)；
Fig. 4 is a kind of flow diagram of specific embodiment of methanation process provided by the invention (using shown in Fig. 1
Methanator)；
Fig. 5 is that the structural schematic diagram of another specific embodiment of methanator provided by the invention (is longitudinally urged
Change and be located at laterally catalysis reaction member above reaction member)；
Fig. 6 is cross-sectional view (the i.e. A-A in Fig. 5 of another specific embodiment of methanator provided by the invention
The cross-sectional view in face)；
Fig. 7 is cross-sectional view (the i.e. B-B in Fig. 5 of another specific embodiment of methanator provided by the invention
The cross-sectional view in face)；
Fig. 8 is the flow diagram of another specific embodiment of methanation process provided by the invention (using Fig. 5 institute
The methanator shown, not set cooling medium pipeline)；
Fig. 9 is a kind of specific embodiment (cone of micro- reaction channel used by methanator provided by the invention
Shape pipe) schematic diagram；
Figure 10 is a kind of specific embodiment (loudspeaker of micro- reaction channel used by methanator provided by the invention
Shape pipe) schematic diagram；
Figure 11 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
The longitudinal catalysis reaction member 5 of 1 shell, 2 air inlet pipe, 3 escape pipe 4 is laterally catalyzed reaction member
6 central tube, 7 sleeve, 8 central tube, 9 baffle, 10 mass flow pathway, 11 runner, 12 annular space
13 radial micro- 14 radial microchannel reaction gas inlets of reaction channel
The axial micro- reaction channel of 15 radial microchannel 16 cylinder of reacting product outlet 17
The axial 20 axial microchannel reacting product outlet of microchannel reaction gas inlet in 18 gap 19
21 first gas distributor, 22 second gas distributor, 23 third gas distributor
24 the 4th gas distributor, 25 heat-barrier material area, 26 unitary space
The main methanator 29 of main 28 2# of methanator of 27 1# supplements methanator
30 steam superheater, 31 boiler water-suppling heater, 32 2# cooler
33 1# cooler, 34 product separator, 35 drum
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：There is provided a kind of methanator, 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 longitudinal catalysis that 3 top of escape pipe below the air inlet pipe 2 is set in the shell 1
Reaction member 4 and laterally catalysis reaction member 5；Longitudinal catalysis reaction member 4 and lateral catalysis reaction member 5 are above to divide into
Set or lower upper setting, between be formed with unitary space 26；Longitudinal catalysis reaction member 4 includes central tube 6 and is set in central tube 6
At least one outer sleeve 7；Central tube 6 has central tube 8, central tube 8 and 3 fluid of unitary space 26 or escape pipe below
Connection；Between central tube 6 and the barrel of sleeve 7 and between the barrel of two neighboring sleeve 7 by 9 fluid isolation of baffle and every
Separate out mass flow pathway 10 and runner 11；Annular space 12 is formed between the outer wall of outermost sleeve 7 and the inner wall of shell 1；Center
Cylinder 6 and sleeve 7 all have the micro- reaction channel 13 of multiple radial directions being arranged radially, and central tube 6 cylinder is inside and outside and sleeve 7
Cylinder inside and outside only pass through radial micro- reaction channel 13 and be in fluid communication；Air inlet pipe 2 or unitary space 26 pass through point below
The radial microchannel reaction gas inlet 14 of runner 11 or annular space 12 and radial micro- reaction channel 13 is in fluid communication, radial micro- reaction
The radial microchannel reacting product outlet 15 in channel 13 is by mass flow pathway 10 or central tube 8 with unitary space 26 below or out
Tracheae 3 is in fluid communication；Laterally catalysis reaction member 5 includes at least one cylinder 16, and cylinder 16 and shell 1 are coaxial, and cylinder 16
Lateral surface and shell 1 portion of medial side it is inconsistent or coincide；Gap 18 is formed between two neighboring cylinder 16；Cylinder
16 are provided with the micro- reaction channel 17 of axial direction axially across cylinder, air inlet pipe 2 or unitary space 26 and unitary space below
Between 26 or gap 18, between gap 18 and gap 18 and gap and between unitary space 26 below or escape pipe 3 only
It is in fluid communication by the micro- reaction channel 17 of the axial direction being arranged in cylinder 16, the axis that axial micro- reaction channel 17 has diameter different
To microchannel reaction gas inlet 19 and axial microchannel reacting product outlet 20.
According to the first aspect of the invention, it should be noted that if longitudinal catalysis reaction member 4 is located at laterally catalysis reaction
The top (as shown in Figure 5) of unit 5, then air inlet 2 passes sequentially through annular space or runner, radial micro- reaction channel 13, central tube
Or mass flow pathway and unitary space 26 are in fluid communication, unitary space 26 passes sequentially through axial micro- reaction channel 17 and gap 18 and goes out
Tracheae 3 is in fluid communication；If longitudinal catalysis reaction member 4 is located at the lower section (as shown in Figure 1) of laterally catalysis reaction member 5, into
Port 2 passes sequentially through axial micro- reaction channel 17 and gap 18 and unitary space 26 is in fluid communication, and unitary space 26 successively leads to
It crosses annular space or runner, radial micro- reaction channel 13, central tube or mass flow pathway and escape pipe 3 is in fluid communication.
A kind of specific embodiment according to a first aspect of the present invention, the cylinder 16 can be by upper sealing panels and lower sealing plate
It constitutes, side wall can be overlapped with the partial sidewall of shell 1, can also be tightly connected with the side wall of shell 1.It can be in cylinder 16
It is hollow, can be solid, as long as axial micro- reaction channel 17 can be accommodated；The central tube and sleeve can also be close by top
Sealing plate, sealed bottom plate and side wall are constituted, in can be hollow, can also be solid, as long as radial micro- reaction channel can be accommodated
13, the diameter of the central tube, sleeve and central tube can be suitable arbitrary value.
According to the first aspect of the invention, under identical reaction condition and reactor diameter, increase cylinder 16 and sleeve 7
Quantity can increase time of contact of reaction gas and catalyst, reduce the effect that reaction gas flow velocity improves conversion ratio, because
This can adjust the quantity of cylinder 16 and sleeve 7 according to real reaction situation, and the quantity of the sleeve 7 can be 2-500,
Preferably 2-15, the quantity of the cylinder 16 can be 2-500, preferably 2-50.
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 are provided at least a pair of of cooling medium entrance and cooling medium outlet, the cooling medium
Entrance can be situated between by passing through the cylinder and/or unitary space and/or gap and/or central tube and/or the cooling of mass flow pathway
Matter pipeline and the cooling medium communication.Another specific embodiment according to a first aspect of the present invention, it is described
At least a pair of of cooling medium entrance and cooling medium outlet, the cooling medium entrance, which has can be set, in the side of shell to lead to
The outer wall of the inner wall and the micro- reaction channel of the axial direction of crossing the cylinder is formed by chamber and the cooling medium exports fluid
Connection.
According to the first aspect of the invention, in order to make the methanator can be used in producing methane, the radial direction
The inner surface of micro- reaction channel 13 can load catalytic active component, and the inner surface of the micro- reaction channel 17 of axial direction can also be with
Load has catalytic active component.The catalytic active component can use catalytic activity group well-known to those skilled in the art
Point, such as can be with metals such as the active nickel of methanation reaction, ruthenium and rhodiums；The load refer to can by dipping,
It is logical that active component by the catalyst containing active component or is directly loaded to micro- reaction by the methods of ion sputtering, coating or filling
In road.Wherein, active metal component coating loading process can be using well-known to those skilled in the art including metallic matrix
Two stages of pretreatment and catalyst deposit coating method.
According to the first aspect of the invention, in order to guarantee the efficiency of methanation reaction, the micro- reaction channel 13 of radial direction
Diameter can be between 2-50 millimeters, and the diameter of the micro- reaction channel 17 of axial direction can be between 2-50 millimeters.Due to methane
Changing reaction is the reaction that total volume reduces, therefore the diameter of the micro- reaction channel 13 of the radial direction can be from the radial microchannel plate
Answer gas access 14 to be gradually reduced to the direction of radial microchannel reacting product outlet 15, the micro- reaction channel 17 of axial direction it is straight
Diameter can be gradually reduced from the direction of the axial microchannel reaction gas inlet 19 microchannel reacting product outlet 20 in the axial direction
(guarantees that the diameter of microchannel reaction gas inlet is greater than the diameter of microchannel reacting product outlet, also include channel diameter
Constant situation after first reducing).The diameter of radial direction microchannel reaction gas inlet 14 should be produced with the radial microchannel plate
The ratio of the diameter of object outlet 15 can be (1.1-25)：1, preferably (2-10)：1, axial direction microchannel reaction gas enters
The ratio of the diameter of the diameter of mouth 19 and the axial microchannel reacting product outlet 20 can be (1.1-25)：1, preferably
(2-10)：1.It should be noted that if the reactor of invention is used for other reactions, it can be according to the concrete condition of the reaction
The diameter of axial micro- reaction channel and radial micro- reaction channel is set.
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 the micro- reaction channel 13 of radial direction can be single for longitudinal catalysis reaction
The total volume of the 30%-90% of the total volume of member 4, the inner space of the micro- reaction channel 17 of axial direction can be anti-for laterally catalysis
Answer the 30%-90% of the total volume of unit 5.
A kind of specific embodiment according to a first aspect of the present invention, the micro- reaction channel 13 of radial direction can be for selected from cones
One of which (respectively as shown in Fig. 9, Figure 10 and Figure 11) in shape pipe, flaring pipe and Y tube, the micro- reaction channel of axial direction
17 may be the one of which in conical pipe, flaring pipe and Y tube (respectively as shown in Fig. 9, Figure 10 and Figure 11)；It answers
It should be appreciated that the diameter of microchannel reaction gas inlet should be greater than the diameter of microchannel reacting product outlet.The taper
Pipe, flaring pipe and Y tube can use metal material pipe, ceramic material pipe, it is preferred to use not and in methanation reaction system
The metal tube that reacts of gas.It should be noted that the conventional use of conical pipe of those skilled in the art refers to that both ends are opened
The truncated cone-shaped hollow material of mouth, 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；Can be set in the unitary space 26 at least one for be distributed from indulge
Reaction member 5 is catalyzed to catalysis reaction member 4 to laterally catalysis reaction member 5 or laterally to flow to longitudinal catalysis reaction member 4
Gas gas distributor.The gas distributor can be using used in those skilled in the art's routine, and the present invention is no longer
It repeats, the preferred same position of gas distributor is simultaneously there are two settings.
According to the first aspect of the invention, the bottom of shell 1 is excessively heated in order to prevent, it is longitudinal be catalyzed reaction member 4 or
Heat-barrier material area 25 laterally can be set between catalysis reaction member 5 and the inner bottom surface of the shell 1.The heat-barrier material area
Can be placed in 25 the heat insulating ball of single material well-known to those skilled in the art or a variety of composites, heat-insulated felt rug or
The heat-barrier materials such as heat insulating belt.
Second aspect of the present invention：A kind of methanation process is provided, which includes：It a, will be containing 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 into supplement after cooling down
Methanator carries out supplement methanation reaction, obtains the second product；C, by the second product obtained in step b after cooling down
Separating treatment is carried out, methanation product is obtained；Wherein, the main methanator of the 1#, the main methanator of 2# and supplement
At least one in methanator is methanator provided by first aspect present invention.
According to the second aspect of the invention, in order to control the reaction temperature of methanator, boiler feedwater can be sent
Enter and carries out taking heat, generated steam in the main methanator of 1#, the main methanator of 2# and supplement methanator
It is sent into 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：Reaction temperature is 300-700
DEG C, reaction pressure is 1.0-8.5 megapascal；It is described supplement methanation reaction condition can be：Reaction temperature is 300-700 DEG C,
Reaction pressure is 1.0-8.5 megapascal.
The embodiment of the present invention is provided below in conjunction with attached drawing, but the present invention is not therefore subject to any restriction.
Embodiment 1
As shown in figure 4, the reaction unit of the present embodiment by the main methanator 27 of 1#, the main methanator 28 of 2#,
Supplement methanator 29, steam superheater 30, boiler water-suppling heater 31,2# cooler 32,1# cooler 33, product point
It is connected from device 34 with drum 35.Two main methanators are connected by the way of in parallel, total with supplement methanator
With a drum 35.
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 27 of 1# and carries out main methane
Change reaction, another strand of synthesis gas enters the main methanator 28 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 27 of 1# and the main methanator 28 of 2# be respectively 650 DEG C,
3.45MPa；
C, the main methanator 27 of 1# and 2# resulting first product of main methanator 28 pass through steam superheater
After 30 heat exchange, temperature is reduced to 400 DEG C, by supplementing methanator 29, further converts unreacted conjunction in the first product
At gas；Supplement the reaction temperature of methanator 29, pressure is 435 DEG C, 3.38MPa；
D, after supplementing methanator, the second product is cold through boiler water-suppling heater 31,1# cooler 32 and 2#
But after device 33 cools down, the isolated methanation product after product separator 34；
E, boiler feedwater is divided six strands, is respectively enterd in the form of two strands from top after the preheating of boiler water-suppling heater 31
The main methanator 27 of 1#, the main methanator 28 of 2#, supplement methanator 29, generate middle pressure steam and fully enter
Drum 35, three methanators share a drum 35；Water in drum is sent out after steam superheater heats.
The conversion ratio of carbon monoxide is 99% in the present embodiment, and the selectivity of methane is 95.5%, while by-product
11.4MPa, 530 DEG C of high pressure superheated steam.
4 methanators used by the present embodiment are as shown in Figure 1-3, structure is as follows：
As shown in Figure 1 to Figure 3, methanator include in shell 1, air inlet pipe 2, escape pipe 3 and shell 1 from top to bottom
The lateral catalysis reaction member of setting and longitudinal catalysis reaction member, be laterally catalyzed reaction member and longitudinal catalysis reaction member it
Between be formed with unitary space 26, third gas distributor 23 and the 4th gas distributor 24 are provided in unitary space.Laterally urge
Change reaction member setting there are two cylinder 16, forms gap 18 between cylinder 16.Longitudinal catalysis reaction member is provided with central tube
With 1 sleeve, there is in central tube central tube, sleeve and central tube to completely cut off runner out and mass flow pathway by baffle, sleeve outside
The inner wall of wall and shell forms annular space.The lower end of air inlet pipe 2 is provided with first gas distributor 21 and second gas distributor 22,
The bottom surface of longitudinal catalysis reaction member and shell 1 is provided with the heat-barrier material area 25 being made of heat-insulated felt rug.The cylinder 16 by
Upper sealing panel and lower sealing plate are constituted, and side wall is the partial sidewall of shell 1.It is hollow in cylinder 16, in accommodate 3240 (for
Clearly show that, be not entirely shown) the micro- reaction channel 17 of axial direction；The central tube and sleeve are by top sealing plate, sealed bottom plate
It is constituted with side wall, it is interior hollow, the micro- reaction channel 13 of several radial directions can be accommodated, axial micro- reaction used by the present embodiment is logical
Road 17 and radial micro- reaction channel 13 are conical pipe as shown in Figure 9, and supported active metals NiO amount is 5.5g/m in conical pipe2。
Methanator diameter of the housing 600mm is highly 1300mm, longitudinal height 300mm for being catalyzed reaction member, cone
Shape caliber is to micro- reaction channel inlet diameter 8mm, exit diameter 2mm, length 95mm；Individually the height of cylinder is
100mm, conical pipe axially micro- reaction channel inlet diameter 10mm, exit diameter 3mm, length 100mm.Radial micro- reaction
The total volume of the inner space in channel is the 42.3% of the total volume of longitudinal catalysis reaction member, the micro- reaction channel of axial direction
The total volume of inner space is the 41.7% of the laterally total volume of catalysis reaction member.
The present embodiment is provided with 2 pairs of cooling mediums in the housing sidewall (namely side wall of cylinder) of 2 16 sides of cylinder
Entrance and cooling medium outlet, each pair of cooling medium entrance and cooling medium outlet pass through the inner wall and axial direction of a cylinder respectively
The outer wall of micro- reaction member is formed by chamber in fluid communication.
Embodiment 2
As illustrated in figs. 5-7, embodiment 2 the difference from embodiment 1 is that, longitudinal catalysis reaction member of methanator
Positioned at the top of laterally catalysis reaction member, and laterally, reaction member is not provided with cooling medium entrance, cooling medium goes out for catalysis
Mouth and cooling medium pipeline.
As shown in figure 8, embodiment 2 the difference from embodiment 1 is that, boiler feedwater by boiler water-suppling heater 31 preheat
It exchanges heat afterwards with steam superheater 30, without being sent into methanator for cooling down.
Claims (17)
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 longitudinal catalysis reaction managing (3) and being arranged in the shell (1) below the air inlet pipe (2) above the escape pipe (3)
Unit (4) and laterally catalysis reaction member (5)；Longitudinal catalysis reaction member (4) and laterally catalysis reaction member (5) are upper
It is lower setting or lower upper setting, between be formed with unitary space (26)；
Longitudinal catalysis reaction member (4) includes central tube (6) and is set at least one sleeve (7) of central tube (6) outside；Center
Cylinder (6) have central tube (8), central tube (8) with below unitary space (26) or escape pipe (3) be in fluid communication；Central tube
(6) pass through baffle (9) fluid isolation between the barrel of sleeve (7) and isolate mass flow pathway (10) and runner (11), work as set
Pass through baffle (9) fluid isolation when cylinder (7) is more than one, between the barrel of two neighboring sleeve (7) and isolates mass flow pathway
(10) and runner (11)；Annular space (12) are formed between the outer wall of outermost sleeve (7) and the inner wall of shell (1)；Center
Cylinder (6) and sleeve (7) all have multiple micro- reaction channels of the radial direction being arranged radially (13), and inside and outside the cylinder of central tube (6)
And only it is in fluid communication by radial micro- reaction channel (13) inside and outside the cylinder of sleeve (7)；Air inlet pipe (2) or unitary space
(26) pass through the radial microchannel reaction gas of runner (11) or annular space (12) and radial micro- reaction channel (13) below
Entrance (14) is in fluid communication, and the radial microchannel reacting product outlet (15) of radial micro- reaction channel (13) passes through mass flow pathway (10)
Central tube (8) with below unitary space (26) or escape pipe (3) be in fluid communication；
Laterally catalysis reaction member (5) includes at least one cylinder (16), cylinder (16) and shell (1) coaxially, and cylinder (16)
Lateral surface and shell (1) portion of medial side it is inconsistent or coincide；When cylinder (16) is more than one, two neighboring cylinder
(16) gap (18) are formed between；Cylinder (16) is provided with the micro- reaction channel of axial direction (17) axially across cylinder, air inlet pipe
(2) or between unitary space (26) and unitary space (26) or gap (18) below, between gap (18) and gap (18)
And it is only micro- anti-by the axial direction being arranged in cylinder (16) between gap and unitary space (26) below or escape pipe (3)
Channel (17) are answered to be in fluid communication, the axial microchannel reaction gas inlet (19) that axial micro- reaction channel (17) has diameter different
With axial microchannel reacting product outlet (20).
2. methanator according to claim 1, which is characterized in that the quantity of the sleeve (7) is 2-500, described
The quantity of cylinder (16) is 2-500.
3. methanator according to claim 1, which is characterized in that the side of the shell (1) is provided at least a pair of
Cooling medium entrance and cooling medium outlet, the cooling medium entrance is by passing through the cylinder (16) and/or unitary space
(26) and/or the cooling medium pipeline of gap (18) and/or central tube (8) and/or mass flow pathway (10) goes out with the cooling medium
Mouth is in fluid communication.
4. methanator according to claim 1, which is characterized in that the side of the shell (1) is provided at least a pair of
Cooling medium entrance and cooling medium outlet, the cooling medium entrance are micro- by the inner wall of the cylinder (16) and the axial direction
The outer wall of reaction channel (17) is formed by chamber and the cooling medium communication.
5. methanator according to claim 1, which is characterized in that the inner surface of the micro- reaction channel of radial direction (13) is negative
It is loaded with catalytic active component, the inner surface load of the micro- reaction channel of axial direction (17) has catalytic active component.
6. methanator according to claim 1, which is characterized in that the diameter of the micro- reaction channel of radial direction (13) is from institute
It states radial microchannel reaction gas inlet (14) to be gradually reduced to the direction of radial microchannel reacting product outlet (15), the axis
To the diameter of micro- reaction channel (17) from the axial microchannel reaction gas inlet (19), microchannel reaction product goes out in the axial direction
The direction of mouth (20) is gradually reduced.
7. methanator according to claim 1, which is characterized in that the diameter of the micro- reaction channel of radial direction (13) is in 2-
Between 50 millimeters, the diameter of the micro- reaction channel of axial direction (17) is between 2-50 millimeters.
8. methanator according to claim 1, which is characterized in that the radial direction microchannel reaction gas inlet (14)
The ratio of diameter and the diameter of the radial microchannel reacting product outlet (15) is (1.1-25)：1, the axial direction microchannel plate
Answering the ratio of the diameter of gas access (19) and the diameter of the axial microchannel reacting product outlet (20) is (1.1-25)：1.
9. methanator according to claim 1, which is characterized in that the inner space of the micro- reaction channel of radial direction (13)
Total volume be longitudinal catalysis reaction member (4) total volume 30%-90%, the inside of the micro- reaction channel of axial direction (17)
The total volume in space is the 30%-90% of the laterally total volume of catalysis reaction member (5).
10. methanator according to claim 1, which is characterized in that the micro- reaction channel of radial direction (13) is selected from cone
One of which in shape pipe, flaring pipe and Y tube, the micro- reaction channel of axial direction (17) are selected from conical pipe, flaring pipe
With the one of which in Y tube.
11. 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；At least one is provided in the unitary space (26)
Reaction member (5) are catalyzed to longitudinal direction from longitudinal direction catalysis reaction member (4) to laterally catalysis reaction member (5) or laterally for being distributed
It is catalyzed the gas distributor of the gas of reaction member (4) flowing.
12. methanator according to claim 1, which is characterized in that longitudinal catalysis reaction member (4) or laterally catalysis are anti-
It answers and is provided with heat-barrier material area (25) between unit (5) and the inner bottom surface of the shell (1).
13. 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 supplement methanator and carries out supplement alkylation reaction, obtained
To 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 1-12.
14. methanation process according to claim 13, 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.
15. methanation process according to claim 13, wherein described be M value containing hydrocarbon is 2.85-3.5's
Carbon monoxide and/or carbon dioxide；The M value is for the volume of methanation synthesis gas institute hydrogen and containing in hydrocarbon
Ratio of the difference of the volume of carbon dioxide with the volume containing hydrocarbon.
16. methanation process according to claim 13, wherein the purified treatment successively includes hydrolysis, desulfurization, deoxidation
And denitration process.
17. methanation process according to claim 13, wherein the condition of the main methanation reaction is：Reaction temperature
It is 300-700 DEG C, reaction pressure is 1.0-8.5 megapascal；It is described supplement methanation reaction condition be：Reaction temperature is 300-
700 DEG C, reaction pressure is 1.0-8.5 megapascal.
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| CN109502546A (en) * | 2018-10-29 | 2019-03-22 | 山西潞安煤基合成油有限公司 | Methane and carbon dioxide dry reforming reactor |
| CN114762811A (en) * | 2021-01-13 | 2022-07-19 | 南京公汇科技有限公司 | Efficient impinging stream mixing device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3714031A (en) * | 1969-11-18 | 1973-01-30 | Shell Oil Co | Residual oil |
| CN2499385Y (en) * | 2001-08-24 | 2002-07-10 | 中国石油天然气股份有限公司 | Radial reactor for preparing synthesis gas by partial oxidation |
| 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 |
| CN202238008U (en) * | 2011-09-09 | 2012-05-30 | 华东理工大学 | Two-stage catalytic reaction system device with fixed-bed reactors |
| CN103657536A (en) * | 2013-12-10 | 2014-03-26 | 惠生工程（中国）有限公司 | Axial and radial combined type fixed bed catalytic reactor for olefince oxidative dehydrogenation |
| CN203540513U (en) * | 2013-09-23 | 2014-04-16 | 中国五环工程有限公司 | Micro-channel reactor for methanation process |
| CN204412216U (en) * | 2014-12-26 | 2015-06-24 | 中国天辰工程有限公司 | A kind of Axial and radial gas solid reactor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2311622A1 (en) * | 2000-06-15 | 2001-12-15 | Moussa Hoummady | Sub-nanoliter liquid drop dispensing system and method therefor |
-
2015
- 2015-08-04 CN CN201510472723.6A patent/CN106378063B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3714031A (en) * | 1969-11-18 | 1973-01-30 | Shell Oil Co | Residual oil |
| CN2499385Y (en) * | 2001-08-24 | 2002-07-10 | 中国石油天然气股份有限公司 | Radial reactor for preparing synthesis gas by partial oxidation |
| 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 |
| CN202238008U (en) * | 2011-09-09 | 2012-05-30 | 华东理工大学 | Two-stage catalytic reaction system device with fixed-bed reactors |
| CN203540513U (en) * | 2013-09-23 | 2014-04-16 | 中国五环工程有限公司 | Micro-channel reactor for methanation process |
| CN103657536A (en) * | 2013-12-10 | 2014-03-26 | 惠生工程（中国）有限公司 | Axial and radial combined type fixed bed catalytic reactor for olefince oxidative dehydrogenation |
| CN204412216U (en) * | 2014-12-26 | 2015-06-24 | 中国天辰工程有限公司 | A kind of Axial and radial gas solid reactor |
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