CN109721029A - A kind of fluidized system and method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic - Google Patents
A kind of fluidized system and method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- 210000001367 artery Anatomy 0.000 title claims abstract description 19
- 210000003462 vein Anatomy 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000008187 granular material Substances 0.000 claims abstract description 29
- 230000009467 reduction Effects 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000002407 reforming Methods 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 230000005426 magnetic field effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000010349 pulsation Effects 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- 238000001833 catalytic reforming Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011943 nanocatalyst Substances 0.000 claims description 3
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- 238000011946 reduction process Methods 0.000 claims description 3
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- 238000011069 regeneration method Methods 0.000 description 12
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Abstract
A kind of fluidized system and method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic are related to a kind of methyl hydride catalyzed hydrogen production system employing reforming technology of fluidized bed and method.The present invention solves existing technology there are catalyst use efficiencies the problems such as low, fluidization quality is low in fluidized bed, reaction rate is low, and catalytically reforming hydrogen producing reaction-regenerative device is complicated.The lower part of fluidized-bed reactor of the invention is equipped with cone shaped distributor, interior bellows are connect with cone shaped distributor horizontal segment, outer bellows are connect with cone shaped distributor tilting section, and heater is mounted on the outside of fluidized-bed reactor, and stabilizing magnetic field generator is mounted on the outside of heater；The outlet of two mutually independent air-stream generating devices is connect with inside and outside bellows respectively.The present invention first carries out the reduction of catalyst granules；Catalytically reforming hydrogen producing reaction is carried out again；Finally carrying out catalyst goes carbon distribution to react.The present invention is used for methyl hydride catalyzed reformation hydrogen production.
Description
Technical field
The present invention relates to the fluidized-bed reactors and method of a kind of methyl hydride catalyzed reformation hydrogen production, and in particular to a kind of pulsation gas
The methyl hydride catalyzed reforming reaction of stream coupled magnetic field reacts integrated device and method with catalyst regeneration.
Background technique
Hydrogen gradually plays important role as a kind of clean energy resource on world energy sources stage, has burning
Calorific value is high, the advantages that having good burning performance, is more, storing mode is more using form, is widely used in petroleum, chemical industry, space flight, doctor
The every field such as medicine, metallurgy.With the intensification to environmental problem attention degree, non-renewable energy burning is gradually increased in China in recent years
The discharge standard of the pollutants such as nitrogen oxides, the oxysulfide of release, demand of the hydrogen in China also gradually rise.Methane water
Vapor catalyzed reforming hydrogen producing technology is one of current most widely used hydrogen manufacturing mode, and China's natural gas rich reserves are main
Ingredient is methane, and impurity content is few, can produce synthesis gas by catalytic reforming reaction, and then produce hydrogen, and utilize it
Optimization hydrogen manufacturing can reduce methane and CO2Deng discharge, for economizing on resources and protecting environment that there is double meaning.
Industrial methyl hydride catalyzed reforming hydrogen producing technology problem encountered is mainly that reaction rate is low, catalyst carbon deposition is lost
It is living, and device complexity etc..Compared with fixed bed, the good heat and mass ability of fluidized-bed reactor and internal isothermal environment have
Conducive to the area carbon for overcoming catalyst, the regeneration difficulty of catalyst is reduced, improves reaction rate.But the fluidised form in fluidized bed
Change effect is influenced by factors such as fluidized particles characteristic, structure of reactor and inlet gas conditions, and catalyst granules is anti-
Should with often will appear the de-fluidized phenomenons such as slugging, channel, local dead zone in regenerative process, seriously affected the gas in reactor
Gu contacting efficiency.Some researches show that introduce magnetic field energy and reduce fluidized bed endoparticle minimum fluidization velocity, inhibit material well
The formation of back-mixing and bubble, and then gas-solid contact efficiency is improved, reduce the formation of catalyst surface carbon distribution.
But there is also some problems for the methyl hydride catalyzed reforming hydrogen production device of magnetically fluidized bed, when as thinner such as catalyst granules, instead
It answers device bottom particles to be not easy to fluidize, will form local dead zone, so that fluidization quality reduces；Under magnetic fields, inter-particle collision subtracts
Weak, agglomerate effect and sintering phenomenon can occur for the catalyst granules that carbon distribution is formed under high temperature, so that the utilization rate of catalyst reduces,
And then lead to the reduction of reaction rate；Under strong magnetic induction intensity effect, the long magnetic linkage structure of formation will cause gas short circuit, so that
Gas residence time shortens, and reaction rate is caused to reduce；Catalyst regeneration process is complicated, and the catalyst of inactivation needs to be sent into specific
Regenerating unit regenerated, increase industrial work amount；Catalyst regeneration low efficiency, hardly possible fluidisation, easy-sintering etc. when regeneration.
Gather in conclusion the existing methyl hydride catalyzed reforming hydrogen production device of magnetically fluidized bed easily forms particle there are catalyst granules
Group, long magnetic linkage structure, catalyst granules collision weaken, and utilization efficiency is low, high temperature easy-sintering, and fluidization quality is low, anti-in fluidized bed
Answer rate low, the problems such as catalytically reforming hydrogen producing reaction-regenerative device is complicated.
Summary of the invention
There are catalyst granules easily to be formed in order to solve the methyl hydride catalyzed reforming hydrogen production device of existing magnetically fluidized bed by the present invention
Particle agglomeration, long magnetic linkage structure, catalyst granules collision weaken, and utilization efficiency is low, high temperature easy-sintering, fluidization quality in fluidized bed
It is low, reaction rate is low, the problem of catalytically reforming hydrogen producing reaction-regenerative device complexity.Provide a kind of combined reinforced methane of arteries and veins magnetic
The fluidized system and method for catalytically reforming hydrogen producing.
The technical scheme is that a kind of fluidized system of the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic, it includes
Magnetically fluidized bed reactor and two air-stream generating devices, magnetically fluidized bed reactor include fluidized-bed reactor, stabilizing magnetic field generation
The lower inside of device, heater, cone shaped distributor, interior bellows, outer bellows and bed material layer, fluidized-bed reactor is equipped with taper cloth wind
The horizontal segment of plate, interior bellows and cone shaped distributor connects, and the lower end of fluidized-bed reactor is equipped with outer bellows, outer bellows and taper cloth
The tilting section of aerofoil connects, and bed material layer is equipped in fluidized-bed reactor, and heater is mounted on the outside of fluidized-bed reactor, stablizes
Magnetic field generator is mounted on the outside of heater；Two air-stream generating device structures are identical, the gas in each air-stream generating device
Stream is the mixing of continuous flow and square waveform pulse pneumatic, and two air-stream generating devices are in parallel and respectively with interior bellows and outside
Bellows connection.
Further, the period of the square waveform pulse pneumatic of pulse airflow generating device is by solenoid valve and controller control
System.
Further, two air-stream generating devices are connected by the 4th globe valve with inlet gas, air-stream generating device packet
Continuous flow generator and square waveform pulsating airflow generator are included, square waveform pulsating airflow generator includes controller, electricity
Magnet valve, gas buffer tank, the first globe valve and the first rotor flowmeter；Continuous flow generator includes the second globe valve, second
Spinner flowmeter and third globe valve；Third globe valve is installed on the first entrance gas piping on air-stream generating device, the
One inlet gas pipeline is equipped with the first branch line and second branched pipe road, the first branch line and second branched pipe in parallel
Connect after road is in parallel with one end of output gas pipeline, the other end of output gas pipeline passes through outer bellows and cone shaped distributor
The other end of the connection of tilting section air inlet or output gas pipeline passes through the horizontal segment air inlet of interior bellows and cone shaped distributor
Connection, solenoid valve, gas buffer tank, the first globe valve and the first rotor flowmeter are sequentially mounted on the first branch line, are controlled
Device processed is mounted on solenoid valve, and the second globe valve and the second spinner flowmeter are mounted on second branched pipe road.
The present invention also provides a kind of method of the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic, it the following steps are included:
Step 1: the reduction of catalyst granules；
It is bed material by the magnetic Ni-based or cobalt-based nano-catalyst particles with catalysis, is sent into fluidized-bed reactor
Bottom, entrance is passed through gas, which is H2With CO mixed gas, and with square waveform pulsation synthesis gas stream fluidized bed
In reactor, the reduction of catalyst is carried out under the steady magnetic field effect that stabilizing magnetic field generator generates；
Step 2: catalytically reforming hydrogen producing reaction；
It first passes to vapor to drain the residual gas in reduction process fluidized-bed reactor and gas pipeline, then by methane
Be sent into magnetically fluidized bed reactor by a certain percentage with vapor, stabilizing magnetic field generator generate steady magnetic field effect under into
Row catalytically reforming hydrogen producing reaction, after reaction to synthesis gas recycling, purification and the purification of generation；
Step 3: catalyst goes carbon distribution to react；
It first passes to vapor to drain the residual gas in fluidized-bed reactor and gas pipeline, gas will be burnt with rectangle
Waveform is pulsed in synthesis gas streaming fluidized bed reactor, is carried out under the steady magnetic field effect that stabilizing magnetic field generator generates anti-
It answers, high temperature burns gas and reacts with catalyst surface carbon distribution, removes catalyst surface carbon distribution；Vapor is finally passed through to drain
Gas in reactor and pipeline, in case reduction.
Further, the particle size range of the catalyst granules in step 1 is 100-300 μm；Inlet gas is H2It is mixed with CO
Gas is closed, the molar ratio of inlet gas is 1-2:1.
Further, for step 1 in reduction, reduction temperature is 200-500 DEG C, and reduction pressure is 0.1-2.0MPa, steady
Magnetic field strength is in 0.2-2.0T.
Further, the ratio that methane and vapor are 0.1-0.5:1 in molar ratio is mixed in step 2, with rectangular wave
The form of shape pulsation synthesis air-flow is sent into fluidized-bed reactor 1.
Further, the magnetic field strength that catalytically reforming hydrogen producing reacts in step 2 is 0.2-2.0T, temperature 500-800
DEG C, pressure 0.1-2.0MPa.
Further, the magnetic field strength in step 3 is 0.2-2.0T.
Further, it is 500-1000 DEG C that the high temperature in step 3, which burns the temperature range of gas, reaction pressure 0.1-
2.0MPa。
The present invention has following improvement effect compared with prior art:
1) in magnetically fluidized bed reactor, long magnetic linkage structure and particle agglomeration effect be will form when magnetic field strength is excessive, in bed
It answers, inlet gas of the invention is the mixing of pulse pneumatic and continuous flow, and intermittent pulse pneumatic can destroy longer magnetic
Chain structure and big particle agglomeration, the shorter magnetic linkage structure of formation are able to suppress the bubble in reactor, improve air flow shortcircuit
The phenomenon that, improve the opereating specification of magnetic field strength；
2) under magnetic fields, intermittent pulse pneumatic strengthens the destruction and recombination of magnetic linkage, improves the collision of particle
Frequency improves the sintering phenomenon of catalyst under high temperature, improves the utilization efficiency of catalyst granules, it is anti-to improve catalytic reforming
The reaction rate that should be reacted with catalyst regeneration.
3) inlet gas is additionally arranged tilting section air-flow, the pulse pneumatic of tilting section by cone shaped distributor structure by the present invention
The transverse movement of catalyst in reactor particle is enhanced, the tangential force that air-flow generates makes long magnetic linkage structure and big particle poly-
The destruction of group is more easier；Crossflow can reduce catalyst granules in the adsorption effect of fluidized bed wall surface, enhancing simultaneously
The Radial Flow of grain, enhances the fluidization quality of bottom, eliminates the de-fluidized phenomenon such as local dead zone, channel, improve reaction
Heat and mass effect inside device.
4) two air-stream generating devices are mutually indepedent in the present invention, to be sent into cone shaped distributor horizontal segment and tilting section gas
Stream is mutually indepedent, and continuous and pulse pneumatic adjusting is mutually indepedent in each flow generator, so that can when actual motion
With according to response situation adjust different location, different characteristics air-flow parameter, enhance the controllability and air-flow of device
Opereating specification and adaptability to magnetic field strength.
5) oscillation of bed of the invention is realized by pulse pneumatic, with traditional mechanical oscillating phase ratio, is increased
The transverse movement of bed material, reduces noise, is conducive to improve reactor service life.
6) the device of the invention realizes the reaction of methyl hydride catalyzed reformation hydrogen production and catalyst regeneration device integration, without into
The transfer of row catalyst granules regenerates, and simplifies methyl hydride catalyzed process for making hydrogen.
In conclusion the method for the present invention be able to suppress because magnetic field strength it is excessive caused by catalyst granules agglomerate, long magnetic
Chain structure increases the collision of catalyst granules, improves the utilization efficiency of catalyst granules, sintering of catalyst shows under improvement high temperature
As improving the fluidization quality and reaction rate in reactor, while simplify catalyst regeneration.
Detailed description of the invention
Fig. 1 is schematic structural view of the invention；
Fig. 2 air-stream generating device airflow waveform schematic diagram, wherein Fig. 2 (a) is continuous flow waveform diagram；Fig. 2 (b) is pulsation
Airflow waveform figure.
Specific embodiment
Specific embodiment 1: illustrating that present embodiment, a kind of arteries and veins magnetic joint of present embodiment are strong in conjunction with Fig. 1 to Fig. 2
Change the fluidized system of methyl hydride catalyzed reformation hydrogen production, it includes magnetically fluidized bed reactor and two air-stream generating devices, magnetic current
Bed reactor includes fluidized-bed reactor 1, stabilizing magnetic field generator 2, heater 3, cone shaped distributor 4, interior bellows 5, outer bellows 6
Cone shaped distributor 4, interior bellows 5 are equipped with the lower inside of bed material layer 7 (referring to the bed of catalyst particles bed of material), fluidized-bed reactor 1
It is connect with the horizontal segment of cone shaped distributor 4, the lower end of fluidized-bed reactor 1 is equipped with outer bellows 6, outer bellows 6 and cone shaped distributor 4
Tilting section connection, bed material layer 7 is equipped in fluidized-bed reactor 1, heater 3 is mounted on the outside of fluidized-bed reactor 1, stablizes
Magnetic field generator 2 is mounted on the outside of heater 3；
Two air-stream generating device structures are identical, and the air-flow in each air-stream generating device is continuous flow and rectangular wave
The mixing of shape pulse pneumatic, two air-stream generating devices are in parallel and connect respectively with interior bellows 5 and outer bellows 6；
Two air-stream generating devices of present embodiment are mutually indepedent, first is that being sent by the horizontal segment of cone shaped distributor anti-
Device is answered, second is that the tilting section by cone shaped distributor is sent into reactor.Air-stream generating device can generate two strands of air-flows, be to connect respectively
Continuous air-flow and square waveform pulse pneumatic, the period of square waveform pulse pneumatic are controlled by solenoid valve and controller.Pass through taper
Inlet gas is additionally arranged tilting section air-flow by air distributor structure, and the pulse pneumatic of tilting section enhances the lateral fortune in reactor
It is dynamic, the tangential force that tilting section pulse pneumatic generates make because magnetic field strength it is excessive caused by long magnetic linkage structure and big particle agglomeration
Destruction be more easier.The present invention can be improved methyl hydride catalyzed reformation hydrogen production efficiency and catalyst regeneration efficiency, inhibit particle poly-
Group and catalyst granules sintering, while simplifying reaction-regenerative device.
Specific embodiment 2: embodiment is described with reference to Fig. 1, the square of the pulse airflow generating device of present embodiment
The period of shape waveform pulse pneumatic is controlled by solenoid valve 9 and controller 8, and controller controls the time of solenoid valve valve opening and closing.Such as
This setting, so that pulse pneumatic frequency is more accurate controllable.Other compositions and connection relationship are same as the specific embodiment one.
Specific embodiment 3: embodiment is described with reference to Fig. 1, two air-stream generating devices of present embodiment pass through
4th globe valve 16 is connected with inlet gas, and each air-stream generating device includes continuous flow generator and square waveform pulsation
Flow generator, square waveform pulsating airflow generator include controller 8, solenoid valve 9, gas buffer tank 10, the first globe valve
11 and the first rotor flowmeter 12；Continuous flow generator includes the second globe valve 13, the second spinner flowmeter 14 and third ball
Shape valve 15 is equipped with third globe valve 15, first entrance flue on the first entrance gas piping 17 on air-stream generating device
Road 17 is equipped with the first branch line 18 and second branched pipe road 19, the first branch line 18 and second branched pipe road 19 in parallel
It is connect after parallel connection with one end of output gas pipeline 20, the other end of output gas pipeline 20 passes through outer bellows 6 and taper cloth wind
The water that the tilting section air inlet of plate 4 connects or the other end of output gas pipeline 20 passes through interior bellows 5 and cone shaped distributor 4
Flat section air inlet connection, solenoid valve 9, gas buffer tank 10, the first globe valve 11 and the first rotor flowmeter 12 are sequentially mounted on
On first branch line 18, controller 8 is mounted on solenoid valve 9, and the second globe valve 13 and the second spinner flowmeter 14 are mounted on
So set, the air-stream generating device for being sent into cone shaped distributor horizontal segment and tilting section is mutually indepedent on second branched pipe road 19,
And its continuous and pulse pneumatic adjusting is mutually indepedent, enhances the controllability of device and the opereating specification of air-flow and to magnetic
The adaptability of field intensity.Other compositions and connection relationship are the same as one or two specific embodiments.
Specific embodiment 4: embodiment is described with reference to Fig. 1, a kind of combined reinforced methane of arteries and veins magnetic of present embodiment
The method of catalytically reforming hydrogen producing, it the following steps are included:
Step 1: the reduction of catalyst granules；
It is bed material by the magnetic Ni-based or cobalt-based nano-catalyst particles with catalysis, is sent into fluidized-bed reactor
1 bottom, entrance are passed through gas, which is H2With CO mixed gas, and with square waveform pulse synthesis air-flow (synthesis gas
Stream) it is sent into fluidized-bed reactor 1, the reduction of catalyst is carried out under the steady magnetic field effect that stabilizing magnetic field generator 2 generates；
Step 2: catalytically reforming hydrogen producing reaction；
It first passes to vapor to drain the residual gas in reduction process fluidized-bed reactor 1 and gas pipeline, then by first
Alkane and vapor are sent by a certain percentage in magnetically fluidized bed reactor 1, in the steady magnetic field effect that stabilizing magnetic field generator 2 generates
Lower progress catalytically reforming hydrogen producing reaction, after reaction to synthesis gas recycling, purification and the purification of generation；
Step 3: catalyst goes carbon distribution to react；
It first passes to vapor to drain the residual gas in fluidized-bed reactor 1 and gas pipeline, gas will be burnt with square
Shape waveform pulse synthesis gas streaming fluidized bed reactor 1 in, stabilizing magnetic field generator 2 generate steady magnetic field effect under into
Row reaction, high temperature burn gas and react with catalyst surface carbon distribution, remove catalyst surface carbon distribution；Finally it is passed through vapor
The gas in reactor and pipeline is drained, in case reduction.
Specific embodiment 5: embodiment is described with reference to Fig. 1, one the step of present embodiment in catalyst granules
Particle size range be 100-300 μm；Inlet gas is H2With CO mixed gas, the molar ratio of inlet gas is 1-2:1.So set
It sets, improves the total surface area of catalyst granules, improve the rate of reduction of catalyst granules.Other compositions and connection relationship and tool
Any one of body embodiment one to four is identical.
Specific embodiment 6: embodiment is described with reference to Fig. 1, one in reduction the step of present embodiment, reduction
Temperature is 200-500 DEG C, and reduction pressure is 0.1-2.0MPa, and Static magnetic field is in 0.2-2.0T.So set, effectively inhibiting
The generation of bubble formation and channeling controls back-mixing, increases the residence time of particle, improve gas-solid contact efficiency, improves
Reduction efficiency.Other compositions and connection relationship are identical as any one of specific embodiment one to five.
Specific embodiment 7: embodiment is described with reference to Fig. 1, two the step of present embodiment in methane and water are steamed
Gas is the ratio mixing of 0.1-0.5:1 in molar ratio, is sent into fluidisation in the form of square waveform pulsation synthesis air-flow (synthesis air-flow)
In bed reactor 1.So set, intermittent pulse pneumatic can destroy because magnetic field strength it is excessive caused by long magnetic linkage structure and big
Particle agglomeration, improve the opereating specification of magnetic field strength, strengthen the destruction and recombination of magnetic linkage, improve particle collision frequency
Rate improves the sintering phenomenon of catalyst under high temperature, improves the utilization efficiency of catalyst granules.Other compositions and connection relationship
It is identical as any one of specific embodiment one to six.
Specific embodiment 8: embodiment is described with reference to Fig. 1, two the step of present embodiment in magnetic field strength be
0.2-2.0T, temperature are 500-800 DEG C, and pressure is that 0.1-2.0MPa carries out catalytically reforming hydrogen producing reaction.So set, effectively dropping
Low bubble size and quantity improve the fluidization quality in reactor, effectively control back-mixing, improve reaction gas and catalyst particles
The contacting efficiency of grain, improves methyl hydride catalyzed reformation hydrogen production efficiency.Other compositions and connection relationship and specific embodiment one to seven
Any one of it is identical.
Specific embodiment 9: embodiment is described with reference to Fig. 1, three the step of present embodiment in magnetic field strength be
0.2-2.0T.So set, increasing gas-solid contact efficiency, increases and burn gas and the catalyst granules with area carbon
Reaction time improves catalyst surface carbon distribution reaction rate.In other compositions and connection relationship and specific embodiment one to eight
Any one is identical.
Specific embodiment 10: embodiment is described with reference to Fig. 1, three the step of present embodiment in high temperature burn gas
The temperature range of body is 500-1000 DEG C, reaction pressure 0.1-2.0MPa.So set, improving going for catalyst surface carbon distribution
Except efficiency, the oxidizing reaction rate of carbon distribution is improved.It is other composition and connection relationship with it is any one in specific embodiment one to nine
Item is identical.
In the present invention, stream condition is as follows:
| Cycle T (s) | In a cycle, valve switch time ratio | |
| Horizontal segment pulse pneumatic | 5-30 | 1:3-6 |
| Tilting section pulse pneumatic | 5-30 | 1:3-10 |
In order to guarantee the stable operation of magnetically fluidized bed, the amplitude of pulse pneumatic be should not be too large, and the pulsation period should not be too short, and one
The time that a period inner valve is opened also unsuitable too long (especially tilting section pulse pneumatic), otherwise can destroy magnetic stablizing bed knot
Structure, so that fluidization quality deteriorates in bed.In order to guarantee catalytic reforming reaction and catalyst regeneration reaction go on smoothly, must protect
Certain reaction gas flow is demonstrate,proved, therefore cone shaped distributor horizontal segment air-flow should account for 80% or more of overall reaction gas flow, and even
The flow velocity of continuous property air-flow should be higher than that pulse pneumatic flow velocity three times or more, remaining parameter see the above table shown in principle.
Matching between reasonable pulse pneumatic and continuous flow, both can guarantee that the stable operation of magnetically fluidized bed and methane were urged
Change reforming reaction and catalyst regeneration reaction go on smoothly, and can destroy because magnetic field strength it is excessive caused by long magnetic linkage structure
With big particle agglomeration, the opereating specification of magnetic field strength is improved, the destruction and recombination of magnetic linkage is strengthened, improves the collision of particle
Frequency, the sintering phenomenon for improving catalyst under high temperature improve methyl hydride catalyzed reformation to improve the utilization efficiency of catalyst granules
The reaction rate of reaction and catalyst regeneration reaction.
Using the specific embodiment of above-mentioned parameter:
1, the reduction of catalyst granules: using the magnetic Ni-based or cobalt-base catalyst particle with catalysis as bed material,
It is characterized in that partial size is 200 μm；It is sent to fluidized-bed reactor bottom, inlet gas H2With CO mixed gas, molar ratio
The reduction that carries out catalyst is sent into fluidized-bed reactor for 1.5:1 (flow parameter see on), and temperature is 350 DEG C, and pressure is
0.1MPa, Static magnetic field 1T.
2, catalytically reforming hydrogen producing reacts: after reduction, first passing to vapor and restores the remnants in reactor and pipeline
Gas drains, and it is anti-that the ratio (flow parameter see on) that methane and vapor are 0.2:1 in molar ratio is then sent into magnetically fluidized bed
It answers in device, is 1T in magnetic field strength, temperature is 700 DEG C, and pressure carries out catalytically reforming hydrogen producing reaction, reaction under the conditions of being 0.1MPa
After reaction product is recycled, purified and is purified.
3, catalyst goes carbon distribution to react, and after catalytic reforming reaction, first passing to vapor will be in reactor and pipeline
Residual gas drains, and then Air for burning coke (flow parameter see on) is sent into fluidized-bed reactor, in magnetic field strength 1T, temperature
800 DEG C, under reaction pressure 0.1MPa, high temperature burns gas and reacts with catalyst surface carbon distribution, removes catalyst surface area
Carbon.It is finally passed through vapor and drains gas in reactor and pipeline, in case reduction.
So implement, catalyst granules agglomerate big under magnetic fields, the formation of long magnetic linkage structure can be inhibited, increase is urged
The collision of catalyst particles, the phenomenon that improving sintering of catalyst under high temperature, and then improve the utilization efficiency of catalyst granules and anti-
The fluidization quality and reaction rate in device are answered, and methanation catalyst regenerating unit and process can be made to simplify.
Claims (10)
1. a kind of fluidized system of the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic, it is characterised in that: it includes magnetically fluidized bed
Reactor and two air-stream generating devices,
Magnetically fluidized bed reactor includes fluidized-bed reactor (1), stabilizing magnetic field generator (2), heater (3), cone shaped distributor
(4), the lower inside of interior bellows (5), outer bellows (6) and bed material layer (7), fluidized-bed reactor (1) is equipped with cone shaped distributor
(4), interior bellows (5) connect with the horizontal segment of cone shaped distributor (4), and the lower end of fluidized-bed reactor (1) is equipped with outer bellows (6),
Outer bellows (6) connect with the tilting section of cone shaped distributor (4), are equipped with bed material layer (7) in fluidized-bed reactor (1), heater (3)
It is mounted on the outside of fluidized-bed reactor (1), stabilizing magnetic field generator (2) is mounted on the outside of heater (3)；
Two air-stream generating device structures are identical, and the air-flow in each air-stream generating device is continuous flow and square waveform arteries and veins
It takes offence the mixing of stream, two air-stream generating devices are in parallel simultaneously to be connect with interior bellows (5) and outer bellows (6) respectively.
2. a kind of fluidized system of the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 1, feature
Be: the period of the square waveform pulse pneumatic of pulse airflow generating device is controlled by solenoid valve (9) and controller (8).
3. a kind of fluidized system of the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 2, feature
Be: two air-stream generating devices are connected by the 4th globe valve (16) with inlet gas, and each air-stream generating device includes
Continuous flow generator and square waveform pulsating airflow generator, square waveform pulsating airflow generator include controller (8), electricity
Magnet valve (9), gas buffer tank (10), the first globe valve (11) and the first rotor flowmeter (12)；
Continuous flow generator includes the second globe valve (13), the second spinner flowmeter (14) and third globe valve (15),
Third globe valve (15), first entrance flue are installed on first entrance gas piping (17) on air-stream generating device
Road (17) is equipped in parallel the first branch line (18) and second branched pipe road (19), the first branch line (18) and second point
It is connect after bye-pass (19) is in parallel with one end of output gas pipeline (20), the other end of output gas pipeline (20) passes through exogenous wind
Case (6) is connect with the tilting section air inlet of cone shaped distributor (4) or the other end of output gas pipeline (20) passes through interior bellows
(5) it is connect with the horizontal segment air inlet of cone shaped distributor (4), solenoid valve (9), gas buffer tank (10), the first globe valve (11)
It being sequentially mounted on the first branch line (18) with the first rotor flowmeter (12), controller (8) is mounted on solenoid valve (9),
Second globe valve (13) and the second spinner flowmeter (14) are mounted on second branched pipe road (19).
4. a kind of method of the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic, it is characterised in that: it the following steps are included:
Step 1: the reduction of catalyst granules；
It is bed material by the magnetic Ni-based or cobalt-based nano-catalyst particles with catalysis, is sent into fluidized-bed reactor (1)
Bottom, entrance is passed through H2With CO mixed gas, and with square waveform pulsation synthesis gas streaming fluidized bed reactor (1) in,
The reduction of catalyst is carried out under the steady magnetic field effect that stabilizing magnetic field generator (2) generate；
Step 2: catalytically reforming hydrogen producing reaction；
It first passes to vapor to drain the residual gas in reduction process fluidized-bed reactor (1) and gas pipeline, then by methane
It is sent into vapor in magnetically fluidized bed reactor (1), makees in the steady magnetic field that stabilizing magnetic field generator (2) generate by a certain percentage
Methyl hydride catalyzed reformation hydrogen production reaction is carried out under, after reaction to synthesis gas recycling, purification and the purification of generation；
Step 3: catalyst goes carbon distribution to react；
It first passes to vapor to drain the residual gas in fluidized-bed reactor (1) and gas pipeline, gas will be burnt with rectangle
Waveform is pulsed in synthesis gas streaming fluidized bed reactor (1), under the steady magnetic field effect that stabilizing magnetic field generator (2) generate
It is reacted, high temperature burns gas and reacts with catalyst surface carbon distribution, removes catalyst surface carbon distribution；Finally it is passed through water steaming
Gas drains the gas in reactor and pipeline, in case reduction.
5. the method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 4, it is characterised in that: step 1
In catalyst granules particle size range be 100-300 μm；Inlet gas is H2With CO mixed gas, the molar ratio of inlet gas
For 1-2:1.
6. the method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 5, it is characterised in that: step 1
In reduction, reduction temperature is 200-500 DEG C, and reduction pressure is 0.1-2.0MPa, and Static magnetic field is in 0.2-2.0T.
7. the method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 6, it is characterised in that: step 2
It is middle to mix the ratio that methane and vapor are 0.1-0.5:1 in molar ratio, it is sent in the form of square waveform pulses synthesis air-flow
In fluidized bed reactor 1.
8. the method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of the arteries and veins magnetic according to claim 4 or 7, it is characterised in that: step
The magnetic field strength of catalytic reforming reaction is 0.2-2.0T in rapid two, and temperature is 500-800 DEG C, pressure 0.1-2.0MPa.
9. the method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 8, it is characterised in that: step 3
In magnetic field strength be 0.2-2.0T.
10. the method for the combined reinforced methyl hydride catalyzed reformation hydrogen production of arteries and veins magnetic according to claim 9, it is characterised in that: step
The temperature range that high temperature in three burns gas is 500-1000 DEG C, reaction pressure 0.1-2.0MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694840A (en) * | 2020-05-21 | 2021-11-26 | 国家能源投资集团有限责任公司 | Fluidizing device for solid particles and method for fluidizing solid particles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059753A (en) * | 1990-09-11 | 1992-03-25 | 科蒂克股份公司 | Gasification substance gasification and/or gas conversion process and device and the high-temperature heat-exchanging of implementing this method |
| CN2934206Y (en) * | 2006-04-21 | 2007-08-15 | 中国石油天然气股份有限公司 | Methane catalyzed partial oxidation produced synthetic gas circulating fluidized bed device |
| CN101468329A (en) * | 2007-12-29 | 2009-07-01 | 唐山易通科技开发有限公司 | Air impulsive motion dense medium fluidized bed and sorting method thereof |
| CN101837955A (en) * | 2010-03-19 | 2010-09-22 | 青岛科技大学 | Method for producing hydrogen through coupled catalytic reforming and membrane separation reaction, and device thereof |
| CN105664957A (en) * | 2016-01-09 | 2016-06-15 | 中南大学 | Preparation method of methane autothermal reforming mixed catalyst for magnetically fluidized bed reactor |
-
2019
- 2019-03-21 CN CN201910218448.3A patent/CN109721029B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059753A (en) * | 1990-09-11 | 1992-03-25 | 科蒂克股份公司 | Gasification substance gasification and/or gas conversion process and device and the high-temperature heat-exchanging of implementing this method |
| CN2934206Y (en) * | 2006-04-21 | 2007-08-15 | 中国石油天然气股份有限公司 | Methane catalyzed partial oxidation produced synthetic gas circulating fluidized bed device |
| CN101468329A (en) * | 2007-12-29 | 2009-07-01 | 唐山易通科技开发有限公司 | Air impulsive motion dense medium fluidized bed and sorting method thereof |
| CN101837955A (en) * | 2010-03-19 | 2010-09-22 | 青岛科技大学 | Method for producing hydrogen through coupled catalytic reforming and membrane separation reaction, and device thereof |
| CN105664957A (en) * | 2016-01-09 | 2016-06-15 | 中南大学 | Preparation method of methane autothermal reforming mixed catalyst for magnetically fluidized bed reactor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694840A (en) * | 2020-05-21 | 2021-11-26 | 国家能源投资集团有限责任公司 | Fluidizing device for solid particles and method for fluidizing solid particles |
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