CN108622856A - Hydrogen making by natural gas reformation periodic off-gases retracting device and recovery method - Google Patents
Hydrogen making by natural gas reformation periodic off-gases retracting device and recovery method Download PDFInfo
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- CN108622856A CN108622856A CN201810565502.7A CN201810565502A CN108622856A CN 108622856 A CN108622856 A CN 108622856A CN 201810565502 A CN201810565502 A CN 201810565502A CN 108622856 A CN108622856 A CN 108622856A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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Abstract
The invention discloses a kind of hydrogen making by natural gas reformation periodic off-gases retracting device and recovery methods, belong to chemical emission recycling field.Described device includes：Absorption tower, the unstripped gas entrance on absorption tower are connected with the first periodic off-gases output channel；First end entrance of First Heat Exchanger, First Heat Exchanger is connected with absorb the bottom of the tower outlet；The first end of desorber unit, desorber unit is connected with the outlet of the first end of First Heat Exchanger, and the second end of desorber unit is connected with the second end entrance of First Heat Exchanger, and the second end outlet of First Heat Exchanger is connected with the top entry on absorption tower；Hydrogen recovery unit, hydrogen recovery unit one end is connected with the top exit on absorption tower, the other end is connected with PSA unit.First PSA periodic off-gases generate rich amine solution and periodic off-gases purified gas after the decarburization of absorption tower, and rich amine solution is desorbed after First Heat Exchanger exchanges heat into desorber unit, obtain carbon dioxide；Periodic off-gases purified gas enters after hydrogen recovery unit reaction exports hydrogen product through PSA unit.
Description
Technical field
The present invention relates to chemical emission recovery technology field, more particularly to a kind of hydrogen making by natural gas reformation periodic off-gases recycling dress
It sets and recovery method.
Background technology
Hydrogen is the main raw material of industry and most important industrial gasses and special gas, in petrochemical industry, electronics work
Industry, metallurgical industry, food processing, float glass, Minute Organic Synthesis, aerospace etc. have a wide range of applications.Meanwhile
Hydrogen is also a kind of ideal secondary energy sources.Since the height of hydrogen is fuel, aerospace industry uses liquid hydrogen as fuel.Hydrogen Energy simultaneously
It is generally acknowledged clean energy resource, is showing one's talent as low-carbon and the zero carbon energy.
Gas water steam reformation (Steam Methane Reforming, SMR) is that cost is most in current process for making hydrogen
Low, the maximum method of hydrogen manufacturing amount.The industrial hydrogen of high-purity can be obtained subsequently through pressure-variable adsorption (PSA), but can arrange simultaneously
Amplification quantity PSA periodic off-gases, containing components such as carbon dioxide, hydrogen, carbon monoxide and methane in periodic off-gases, if be directly discharged into big
Gas not only causes energy waste, can also cause atmosphere pollution.Processing method traditional at present is defeated using periodic off-gases as fuel gas
Hydrogen and carbon dioxide content to reburner as fuel, but in PSA periodic off-gases is higher, therefore using PSA periodic off-gases as combustion
Material, the recovery rate for not only reducing hydrogen cause the waste of hydrogen resources, also, since carbon dioxide itself cannot burn also not
The combustion-supporting consumption that can also increase fuel.
Invention content
The object of the present invention is to provide a kind of hydrogen making by natural gas reformation periodic off-gases retracting device and recovery methods, to natural gas
Hydrogen and carbon dioxide in reformation hydrogen production PSA periodic off-gases are separated and recovered, and have both improved hydrogen recovery rate, while making dioxy
Change carbon to be recycled.
On the one hand, to achieve the above object, the present invention provides a kind of hydrogen making by natural gas reformation periodic off-gases retracting device, packets
It includes：
Absorption tower, the unstripped gas entrance on the absorption tower are connected with the first periodic off-gases output channel, for the first PSA to speed
Carbon dioxide in deflation, which with the poor amine liquid in the absorption tower react, generates rich amine solution and periodic off-gases purified gas；
First Heat Exchanger, the first end entrance of the First Heat Exchanger are connected with absorb the bottom of the tower outlet, and described the
One heat exchanger using the poor amine liquid in desorber unit with the rich amine solution for being exchanged heat；
The first end of desorber unit, the desorber unit is connected with the outlet of the first end of the First Heat Exchanger, institute
The second end for stating desorber unit is connected with the second end entrance of the First Heat Exchanger, and the second of the First Heat Exchanger brings out
Mouth is connected with the top entry on the absorption tower, and the desorber unit obtains poor amine for being desorbed to the rich amine solution
Liquid and carbon dioxide；
Hydrogen recovery unit, described hydrogen recovery unit one end is connected with the top exit on the absorption tower, the other end with
PSA unit is connected, and the hydrogen recovery unit is used to the carbon monoxide in the periodic off-gases purified gas being changed into carbon dioxide,
Become gas in generation, hydrogen product and the 2nd PSA periodic off-gases are exported after the PSA unit pressure-variable adsorption.
Further, the desorber unit includes：
Desorber, the inlet of the desorber are connected with the outlet of the first end of the First Heat Exchanger, the desorber
Outlet at bottom be connected with the second end entrance of the First Heat Exchanger, for the rich amine solution carry out air lift remove titanium dioxide
Carbon；
Reboiler, the reboiler are connected with the bottom of the desorber, for further to the rich amine solution decarburization；
First gas-liquid separator, first gas-liquid separator are connected with the top exit of the desorber, are used for gas-liquid
The carbon dioxide is obtained after isolating free water.
Further, the desorber unit further includes：
The entrance of first cooler, first cooler is connected with the top exit of the desorber, and described first is cold
But the outlet of device is connected with the entrance of first gas-liquid separator；
Reflux pump, the entrance of the reflux pump are connected with the liquid-phase outlet of first gas-liquid separator, the reflux pump
Outlet be connected with the reflux water inlet of the desorber.
Further, the hydrogen recovery unit includes：
Compressor, the entrance of the compressor are connected with the top exit on the absorption tower, for compressing the periodic off-gases
Purified gas；
The entrance of second gas-liquid separator, second gas-liquid separator is connected with the outlet of the compressor, is used for gas
Liquid detaches the periodic off-gases purified gas；
Second heat exchanger, the gaseous phase outlet phase of the first end entrance of second heat exchanger and second gas-liquid separator
Even, the middle change gas that second heat exchanger is used to generate using shift-converter and the periodic off-gases purified gas after gas-liquid separation
It exchanges heat；
Shift-converter, the entrance of the shift-converter are connected with the outlet of the first end of second heat exchanger, are used for
Carbon monoxide in the periodic off-gases purified gas is changed into carbon dioxide, the outlet of the shift-converter is changed with described second
Second end entrance of hot device is connected, and the second end outlet of the shift-converter is connected with PSA unit.
Further, the hydrogen recovery unit further includes third cooler, the entrance of the third cooler with it is described
The outlet of compressor is connected, and the outlet of the third cooler is connected with the entrance of second gas-liquid separator.
Further, the hydrogen recovery unit further includes：
Heater, the entrance of the heater are connected with the outlet of the first end of second heat exchanger, the heater
Outlet is connected with the entrance of the shift-converter；
The entrance of 4th cooler, the 4th cooler is connected with the outlet of the second end of second heat exchanger, described
The outlet of 4th cooler is connected with the entrance of the PSA unit.
Further, described device further includes：
First circulation pumps, and the entrance of the first circulation pump is connected with absorb the bottom of the tower outlet, the first circulation
The outlet of pump is connected with the first end of the First Heat Exchanger；
The entrance of second cooler, second cooler is connected with the outlet of the second end of the First Heat Exchanger, described
The outlet of second cooler is connected with the top entry on the absorption tower.
Further, described device further includes return line, and one end of the return line is connected to the first circulation
On pipeline between the outlet of pump and the first end entrance of the First Heat Exchanger；The other end of the return line is connected to institute
It states on the pipeline between the second end outlet of First Heat Exchanger and the entrance of second cooler.
Further, described device further includes liquid knockout, the entrance of the liquid knockout and the absorption tower top exit phase
Even, the first outlet of the liquid knockout is connected with the liquid return hole on the absorption tower, the second outlet of the liquid knockout and the pressure
The entrance of contracting machine is connected.
On the other hand, the present invention also provides a kind of hydrogen making by natural gas reformation periodic off-gases to recycle recovery method, including：
First PSA periodic off-gases enter through the first periodic off-gases output channel in absorption tower, and the poor amine liquid in absorption tower is inhaled
The carbon dioxide in the first PSA periodic off-gases is received, rich amine solution and periodic off-gases purified gas are generated；
The rich amine solution flows out and is divided into two-way by the absorbing tower bottom, wherein enter First Heat Exchanger all the way, with
Enter desorber unit from after the poor amine liquid heat exchange heating of desorber unit, another way flows into return line；
Into the rich amine solution of desorber unit, in desorber unit after air lift carbon dioxide, the poor amine after desorption
Liquid reenters institute after the First Heat Exchanger and rich amine solution heat exchange cooling after being mixed with the rich amine solution in the return line
It states in absorption tower for absorbing carbon dioxide in first periodic off-gases；The carbon dioxide that desorber unit desorbs, by
One gas-liquid separator separates obtain carbon dioxide product gas after going out free water；
The periodic off-gases purified gas is through entering hydrogen recovery unit at the top of the absorption tower, by the hydrogen recovery unit
Carbon monoxide in the periodic off-gases purified gas is changed into carbon dioxide, becomes gas in generation, the middle change gas passes through PSA unit
Hydrogen product and the 2nd PSA periodic off-gases are discharged after processing.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages：
The hydrogen making by natural gas reformation periodic off-gases retracting device provided in the embodiment of the present application, including：Absorption tower, the absorption
The unstripped gas entrance of tower is connected with the first periodic off-gases output channel, for by the first PSA periodic off-gases carbon dioxide with it is described
Poor amine liquid in absorption tower carries out reaction and generates rich amine solution and periodic off-gases purified gas；First Heat Exchanger, the First Heat Exchanger
First end entrance is connected with absorb the bottom of the tower outlet, and the First Heat Exchanger is used to utilize the poor amine liquid in desorber unit
It exchanges heat with the rich amine solution；Desorber unit, the first end of the desorber unit and the first of the First Heat Exchanger
It brings out mouth to be connected, the second end of the desorber unit is connected with the second end entrance of the First Heat Exchanger, and described first changes
The second end outlet of hot device is connected with the top entry on the absorption tower, and the desorber unit is used to carry out the rich amine solution
Desorption, obtains poor amine liquid and carbon dioxide；Hydrogen recovery unit, the top of described hydrogen recovery unit one end and the absorption tower
Outlet is connected, the other end is connected with PSA unit, and the hydrogen recovery unit is used for the oxidation in the periodic off-gases purified gas
Carbon is changed into carbon dioxide, becomes gas in generation, exports hydrogen product after the PSA unit pressure-variable adsorption and the 2nd PSA speeds to put
Gas.In this way, in hydrogen making by natural gas reformation PSA periodic off-gases hydrogen and carbon dioxide separate and recover, high-purity can be obtained
Carbon dioxide and hydrogen, both improved hydrogen recovery rate, while carbon dioxide being made to be recycled.
Description of the drawings
Fig. 1 is the structural schematic diagram of hydrogen making by natural gas reformation periodic off-gases retracting device provided by the embodiments of the present application；
Fig. 2 is hydrogen making by natural gas reformation periodic off-gases recovery method flow chart provided by the embodiments of the present application.
In figure, 1- the first periodic off-gases output channels, the absorption towers 2-, 3- first circulations pump, 4- First Heat Exchangers, 5- return ducts
Road, 6- desorbers, 7- reboilers, the first coolers of 8-, the first gas-liquid separators of 9-, 10-CO2Output channel, 11- condensed waters return
Flow tube road, 12- reflux pumps, 13- second circulations pump, the second coolers of 14-, 15- liquid knockouts, 16- compressors, the cooling of 17- thirds
Device, the second gas-liquid separators of 18-, 19- drainpipes, the second heat exchangers of 20-, 21- heaters, 22- shift-converters, 23- the 4th
Cooler, 24-PSA units, 25- hydrogen output channels, 26- the second periodic off-gases output channels.
Specific implementation mode
In order to in hydrogen making by natural gas reformation PSA periodic off-gases hydrogen and carbon dioxide separate and recover, obtain high-purity
The carbon dioxide and hydrogen of degree improve hydrogen recovery rate, and this application provides a kind of recycling of hydrogen making by natural gas reformation periodic off-gases to fill
It sets, described device includes：Absorption tower, the unstripped gas entrance on the absorption tower are connected with the first periodic off-gases output channel, and being used for will
Carbon dioxide in first PSA periodic off-gases, which with the poor amine liquid in the absorption tower react, generates rich amine solution and periodic off-gases purification
Gas；First end entrance of First Heat Exchanger, the First Heat Exchanger is connected with absorb the bottom of the tower outlet, first heat exchange
Device using the poor amine liquid in desorber unit with the rich amine solution for being exchanged heat；Desorber unit, the desorber unit
The first end outlet of first end and the First Heat Exchanger be connected, the second end of the desorber unit and first heat exchange
Second end entrance of device is connected, and the second end outlet of the First Heat Exchanger is connected with the top entry on the absorption tower, described
Desorber unit obtains poor amine liquid and carbon dioxide for being desorbed to the rich amine solution；Hydrogen recovery unit, the hydrogen
Recovery unit one end is connected with the top exit on the absorption tower, the other end is connected with PSA unit, and the hydrogen recovery unit is used
In the carbon monoxide in the periodic off-gases purified gas is changed into carbon dioxide, become gas in generation, is inhaled through the PSA unit transformation
Attached output hydrogen product and the 2nd PSA periodic off-gases.
Technical scheme is described in detail below by attached drawing and specific embodiment, it should be understood that the application
Specific features in embodiment and embodiment are the detailed description to technical scheme, rather than to present techniques
The restriction of scheme, in the absence of conflict, the technical characteristic in the embodiment of the present application and embodiment can be combined with each other.
Although it should be understood that may have been used term " first ", " second " etc. herein to describe each unit,
But these units should not be limited by these terms.The use of these items is only for by a unit and another unit
It distinguishes.For example, without departing substantially from the range of exemplary embodiment, it is single that first unit can be referred to as second
Member, and similarly second unit can be referred to as first unit.Term "and/or" used herein above include one of them or
The arbitrary and all combination of more listed associated items.
Embodiment one
The present embodiment provides a kind of hydrogen making by natural gas reformation periodic off-gases retracting devices, as shown in Figure 1, described device includes：
Absorption tower 2, First Heat Exchanger 4, desorber unit and hydrogen recovery unit；Wherein,
The unstripped gas entrance on the absorption tower 2 is connected with the first periodic off-gases output channel 1, is used for the first PSA periodic off-gases
In carbon dioxide and the poor amine liquid in the absorption tower 2 react and generate rich amine solution and periodic off-gases purified gas.Wherein, pass through
The first periodic off-gases output channel 1 being connected with the first PSA unit transports to the first PSA periodic off-gases in absorption tower 2, and the first PSA speeds
Carbon dioxide in deflation generates rich amine solution and periodic off-gases purified gas after being reacted with the poor amine liquid that 2 top of absorption tower enters.
Here, described " the first PSA off-gas " is that the PSA discharged by the first PSA unit in hydrogen making by natural gas reformation technique is discharged
Gas, the main component in periodic off-gases are hydrogen, nitrogen, carbon monoxide, carbon dioxide, methane, argon gas etc..Here, described "
One PSA unit " is the PSA unit in hydrogen making by natural gas reformation technique, not the application hydrogen making by natural gas reformation release gas recovery
In device described " PSA unit 24 ".Amine liquid is used for absorbing carbon dioxide, and the rich amine solution refers to the amine after absorbing carbon dioxide
Liquid；The poor amine liquid refers to the amine liquid after desorbing carbon dioxide；The periodic off-gases purified gas refers to that carbon dioxide is inhaled by amine liquid
Periodic off-gases after receipts.
The first end entrance (rich amine solution entrance) of the First Heat Exchanger 4 passes through pipeline and 2 outlet at bottom of the absorption tower
It is connected, the First Heat Exchanger 4 using the poor amine liquid of high temperature in desorber unit with the rich amine solution for being exchanged heat, with right
The rich amine solution heats up；Wherein, the First Heat Exchanger 4 is specially poor rich amine solution heat exchanger, realizes poor rich amine solution heat exchange,
To realize the optimization of energy consumption, the energy needed for rich amine solution desorption is reduced, while reducing the energy consumption of poor amine liquid cooling but.
The first end of the desorber unit is connected with the outlet of the first end of the First Heat Exchanger 4, the desorber list
The second end of member is connected with the second end entrance of the First Heat Exchanger 4, the second end of the First Heat Exchanger 4 export with it is described
The top entry on absorption tower 2 is connected, and the desorber unit obtains poor amine liquid and dioxy for being desorbed to the rich amine solution
Change carbon.
Here, referring to Fig. 1, the desorber unit includes：
Desorber 6, (rich amine solution goes out the inlet on 6 top of the desorber with the first end outlet of the First Heat Exchanger 4
Mouthful) be connected, the outlet at bottom of the desorber 6 is connected with the second end entrance (poor amine liquid entrance) of the First Heat Exchanger 4, uses
In to rich amine solution progress air lift carbon dioxide removal；Wherein, rich amine solution from absorption tower 2 with from the poor of desorber 6
After amine liquid exchanges heat in First Heat Exchanger 4, the rich amine solution after heat exchange enters in desorber 6, is desorbed in desorber 6, raw
At poor amine liquid and carbon dioxide.
Reboiler 7, the reboiler 7 are connected with the bottom of the desorber 6, for further de- to the rich amine solution
Carbon；Wherein, by reboiler 7 to the further heat penetration decarburization of rich amine solution, the poor amine liquid of high temperature is flowed by 6 bottom of desorber after decarburization
The poor amine liquid entrance for entering First Heat Exchanger 4, exchanges heat with rich amine solution, heats up to rich amine solution.
First gas-liquid separator 9, first gas-liquid separator 9 are connected with the top exit of the desorber 6, are used for gas
Liquid obtains the carbon dioxide after isolating free water；Wherein, first gas-liquid separator 9 is specially carbon dioxide product gas
Gas-liquid separator carries out gas-liquid separation to the carbon dioxide desorbed in desorber 6, isolates the production of the carbon dioxide after free water
Product pass through CO by gaseous phase outlet2Output channel 10 exports.
Here, in order to be cooled down to the carbon dioxide desorbed in desorber 6, referring to Fig. 1, the desorber unit is also
Including the first cooler 8, the entrance of first cooler 8 is connected with the top exit of the desorber 6, first cooling
The outlet of device 8 is connected with the entrance of first gas-liquid separator 9；Wherein, first cooler 8 is specially carbon dioxide production
Product Gas Cooler.
In order to which in the liquid reflux to desorber 6 of isolating the first gas-liquid separator 9, the desorber unit further includes
The entrance of reflux pump 12, the reflux pump 12 is gone out by condensate return pipeline 11 and the liquid phase of first gas-liquid separator 9
Mouth is connected, and the outlet of the reflux pump 12 is connected with the reflux water inlet of the desorber 6；Wherein, the reflux pump 12 is specific
It is pumped for condensate return.
In order to which the poor amine liquid for desorbing tower bottom to be delivered in First Heat Exchanger 4, the desorber unit further includes：Second
The entrance of circulating pump 13, second circulation pump 13 is connected with 6 bottom of the desorber, the second circulation pump 13 outlet and
The second end entrance (poor amine liquid entrance) of the First Heat Exchanger 4 is connected；Wherein, the second circulation pump 13 is specially poor amine liquid
Circulating pump.
Described hydrogen recovery unit one end is connected with the top exit on the absorption tower 2,24 phase of the other end and PSA unit
Even, the hydrogen recovery unit is used to the carbon monoxide in the periodic off-gases purified gas being changed into carbon dioxide, becomes in generation
Gas exports hydrogen product and the 2nd PSA periodic off-gases after 24 pressure-variable adsorption of the PSA unit.
Here, referring to Fig. 1, the hydrogen recovery unit includes：
Compressor 16, the entrance of the compressor 16 are connected with the top exit on the absorption tower 2, for compressing described speed
Deflation purified gas, to meet the requirement of shift-converter 22 and PSA unit 24 to pressure；
The entrance of second gas-liquid separator 18, second gas-liquid separator 18 is connected with the outlet of the compressor 16,
For the compressed periodic off-gases purified gas of gas-liquid separation；
Second heat exchanger 20, first end (the compression purification gas side) entrance of second heat exchanger 20 and second gas-liquid
The gaseous phase outlet of separator 18 is connected, the middle change gas and gas-liquid that second heat exchanger 20 is used to generate using shift-converter 22
The periodic off-gases purified gas after separation exchanges heat, to heat up to periodic off-gases purified gas；Wherein, second heat exchanger
20 be specially the compression middle change gas heat exchanger of purified gas-, has the advantageous effect for the energy consumption that recovers energy, reduces.
Shift-converter 22, the entrance of the shift-converter 22 and the first end of second heat exchanger 20 (are compressed net
Change gas side) outlet is connected, and for making the reaction of carbon monoxide in the periodic off-gases purified gas become carbon dioxide, the transformation is anti-
The outlet of device 22 is answered to be connected with second end (middle change gas side) entrance of second heat exchanger 20, the of the shift-converter 22
Two ends (middle change gas side) outlet is connected with PSA unit 24, and after the processing of PSA unit 24, hydrogen is exported by hydrogen output channel 25
Product exports the second periodic off-gases by the second periodic off-gases output channel 26.Wherein, the middle change gas refers to anti-in shift-converter 22
The gas that should be generated.
Here, in order to be cooled down to compressed periodic off-gases purified gas, the hydrogen recovery unit further includes that third is cold
But the entrance of device 17, the third cooler 17 is connected with the outlet of the compressor 16, the outlet of the third cooler 17
It is connected with the entrance of second gas-liquid separator 18.Wherein, the third cooler 17 is specially to compress purification Gas Cooler.
In order to which the periodic off-gases purified gas after heat exchanging further heats, to reach reaction temperature, the hydrogen recovery unit
Further include heater 21, the entrance of the heater 21 is connected with the outlet of the first end of second heat exchanger 20, the heating
The outlet of device 21 is connected with the entrance of the shift-converter 22；
In order to which the middle change gas generated to reaction further cools down, the hydrogen recovery unit further includes the 4th cooler 23,
The entrance of 4th cooler 23 is connected with the outlet of the second end of second heat exchanger 20 (middle change gas exports), and the described 4th
The outlet of cooler 23 is connected with the entrance of the PSA unit 24；Wherein, become air cooling during the 4th cooler 23 is specially
Device.
Further, described device further includes liquid knockout 15, and the entrance of the liquid knockout 15 goes out with 2 top of the absorption tower
Mouth is connected, and the first outlet (bottom) of the liquid knockout 15 is connected with the liquid return hole (top) on the absorption tower 2, the liquid knockout
15 second outlet (top) is connected with the entrance of the compressor 16, and the liquid knockout 15 is for removing in periodic off-gases purified gas
Free water.Wherein, periodic off-gases purified gas is entered by 2 tower top of absorption tower in liquid knockout 15, enters compressor after removing free water
It is compressed in 16；Free water is returned to by 15 bottom of liquid knockout in absorption tower 2.The purpose that liquid knockout 15 is arranged is to remove periodic off-gases
The free water and unhindered amina liquid carried in purified gas has and reduces the loss of amine liquid while reducing having for rear end hydrogen recycling energy consumption
Beneficial effect.
Further, in order to which the rich amine solution of absorb the bottom of the tower to be delivered in First Heat Exchanger, described device further includes：The
The entrance of one circulating pump 3, the first circulation pump 3 is connected with 2 outlet at bottom of the absorption tower, and the first circulation pump 3 goes out
Mouth is connected with the first end (rich amine solution entrance) of the First Heat Exchanger 4；Wherein, the first circulation pump 3 is specially rich amine solution
Circulating pump.
In order to make the poor amine liquid of desorber bottom of tower be down to predetermined temperature before flowing back to absorption tower, described device further includes：
Second cooler 14, the entrance of second cooler 14 and the second end outlet of the First Heat Exchanger 4 (poor amine liquid exports)
It is connected, the outlet of second cooler 14 is connected with the top entry on the absorption tower 2；Wherein, second cooler 14
Specially poor amine liquid cooler, for further cooling down to the poor amine liquid after First Heat Exchanger heat exchange cooling.
Further, enter suitable flow in desorber to adjust rich amine solution, improve the desorption efficiency of carbon dioxide, join
See that Fig. 1, described device further include return line 5, one end of the return line 5 is connected to the outlet of the first circulation pump 3
On pipeline between the first end entrance (rich amine solution entrance) of the First Heat Exchanger 4, the other end of the return line 5 connects
It is connected on pipeline of the second end outlet (poor amine liquid outlet) of the First Heat Exchanger 4 between the entrance of second cooler 14
On.Wherein, the return line 5 is specially rich amine solution return line, and excessive rich amine solution is by return line 5 and from desorption
The poor amine liquid mixing of tower 6 is transported to after cooling down in absorption tower 2 again, continues heat and mass with the first PSA periodic off-gases, to ensure
The carbon dioxide saturation degree of 2 bottom of tower rich amine solution of absorption tower.
Further, in order to which the condensed water that the second gas-liquid separator separates go out is discharged, described device further includes drainpipe 19,
The drainpipe 19 is connected with the gaseous phase outlet of second gas-liquid separator 18, and the drainpipe 19 is for discharging the second gas-liquid
Separator 18 isolates the condensed water in compression purified gas.
Through the above as can be seen that the embodiment of the present application is given birth to by the first PSA periodic off-gases decarburizations of absorption tower unit pair
At rich amine solution and periodic off-gases purified gas, rich amine solution is desorbed after First Heat Exchanger exchanges heat into desorber unit, is isolated
Carbon dioxide；In addition, periodic off-gases purified gas further extracts hydrogen therein through PSA unit after entering hydrogen recovery unit reaction
Gas, to improve hydrogen recovery rate.
Embodiment two
The present embodiment provides a kind of hydrogen making by natural gas reformation periodic off-gases recovery methods, as shown in Fig. 2, including the following steps：
Step S110：First PSA periodic off-gases enter through the first periodic off-gases output channel 1 in absorption tower 2, absorption tower 2
Carbon dioxide in first PSA periodic off-gases described in interior poor amine absorption generates rich amine solution and periodic off-gases purified gas；
Step S120：The rich amine solution flows out and is divided into two-way by 2 bottom of tower of the absorption tower, wherein being changed all the way into first
Enter desorber unit after hot device 4, with the poor amine liquid heat exchange heating from desorber unit, another way flows into return line 5；
Specifically, the rich amine solution is flowed out by 2 bottom of tower of the absorption tower is divided into two-way after 3 supercharging of first circulation pump,
A part enters desorber 6 after transporting to First Heat Exchanger 4 and the heat exchange heating of poor amine liquid；A part is back to by return line 5
Absorption tower 2, to ensure the carbon dioxide saturation degree of bottom of tower rich amine solution.
Step S130：Into the rich amine solution of desorber unit, in desorber unit after air lift carbon dioxide, desorption
Poor amine liquid afterwards is after the First Heat Exchanger 4 and rich amine solution heat exchange cooling, after being mixed with the rich amine solution in the return line 5
It reenters in the absorption tower 2 for absorbing carbon dioxide in first periodic off-gases；The dioxy that desorber unit desorbs
Change carbon, carbon dioxide product gas is obtained after the first gas-liquid separator 9 isolates free water；
Specifically, rich amine solution enters desorber 6, in desorber 6 after air lift carbon dioxide, in tower bottom reboiler
In 7 after heat penetration decarburization, the poor amine liquid of generation pumps 13 through second circulation, transports to First Heat Exchanger 4 and cools down with rich amine solution heat exchange
Afterwards, mixed with the rich amine solution in the return line 5, and after the second cooler 14 is cooled to predetermined temperature, again into
Enter in the absorption tower 2 for absorbing carbon dioxide in first periodic off-gases；The carbon dioxide desorbed in desorber 6, warp
It crosses after the first cooler 8 cools down after isolating free water into the first gas-liquid separator 9 and obtains carbon dioxide product gas；Wherein,
First gas-liquid separator 9 carries out gas-liquid separation to the carbon dioxide desorbed, and the condensed water isolated is back to through reflux pump 12
In desorber 6, the carbon dioxide product gas after separation passes through CO2Output channel 10 exports.
Step S140：The periodic off-gases purified gas enters hydrogen recovery unit through 2 top of the absorption tower, by the hydrogen
Carbon monoxide in the periodic off-gases purified gas is changed into carbon dioxide by gas recovery unit, becomes gas, the middle change gas in generation
Discharge hydrogen product and the 2nd PSA periodic off-gases after the processing of PSA unit 24.
Specifically, the periodic off-gases purified gas enters liquid knockout 15 through 2 top of the absorption tower removes free water, then
It is compressed through compressor 16, gas-water separation, the condensed water elimination isolated to drainpipe is carried out using the second gas-liquid separator 18
19, the compression purified gas isolated heats up by the second heat exchanger 20 and the heat exchange of middle change gas, is further heated into heater 21
To transformationreation temperature, into being reacted in shift-converter 22, the carbon monoxide compressed in purified gas is changed into titanium dioxide
Carbon, the middle change gas of generation is after second heat exchanger 20 cools down with compression purified gas heat exchange, into the 4th cooler 23
Further cooling, the middle change gas after cooling enters PSA unit 24, the hydrogen product generated after the processing of the PSA unit 24 by
Hydrogen output channel 25 is discharged, and the second periodic off-gases (as fuel) of generation are discharged by the second periodic off-gases output channel 26.Second
For off-gas compared with the first off-gas, hydrogen therein has obtained abundant recycling with carbon dioxide.
It should be noted that step S120, step S130, step S140 can be carried out at the same time.
The hydrogen making by natural gas reformation periodic off-gases recovery method of the present embodiment not only increases existing hydrogen making by natural gas reformation dress
The hydrogen product rate set, moreover it is possible to trapping and subsequent recycling be carried out to the carbon dioxide in PSA periodic off-gases, to reduce
Carbon emission amount, while reducing the consumption of fuel.
The hydrogen making by natural gas reformation periodic off-gases retracting device and method of the application, can effectively recycle hydrogen making by natural gas reformation
Carbon dioxide in PSA periodic off-gases and hydrogen, for the purity of carbon dioxide up to 99% or more, the rate of recovery is higher than 80%；Hydrogen it is pure
Degree is up to 99% or more, 80% or more hydrogen entirety extraction rate reached.
It should be noted last that the above specific implementation mode is merely illustrative of the technical solution of the present invention and unrestricted,
Although being described the invention in detail with reference to example, it will be understood by those of ordinary skill in the art that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit of the technical scheme of the invention and range, should all cover
In the scope of the claims of the present invention.
Claims (10)
1. a kind of hydrogen making by natural gas reformation periodic off-gases retracting device, which is characterized in that including：
Absorption tower, the unstripped gas entrance on the absorption tower are connected with the first periodic off-gases output channel, are used for the first PSA periodic off-gases
In carbon dioxide and the poor amine liquid in the absorption tower react and generate rich amine solution and periodic off-gases purified gas；
First end entrance of First Heat Exchanger, the First Heat Exchanger is connected with absorb the bottom of the tower outlet, and described first changes
Hot device using the poor amine liquid in desorber unit with the rich amine solution for being exchanged heat；
The first end of desorber unit, the desorber unit is connected with the outlet of the first end of the First Heat Exchanger, the solution
The second end for inhaling tower unit is connected with the second end entrance of the First Heat Exchanger, the second end of the First Heat Exchanger export and
The top entry on the absorption tower is connected, the desorber unit for being desorbed to the rich amine solution, obtain poor amine liquid and
Carbon dioxide；
Hydrogen recovery unit, described hydrogen recovery unit one end is connected with the top exit on the absorption tower, the other end and PSA are mono-
Member is connected；The hydrogen recovery unit is used to the carbon monoxide in the periodic off-gases purified gas being changed into carbon dioxide, generates
Middle change gas exports hydrogen product and the 2nd PSA periodic off-gases after the PSA unit pressure-variable adsorption.
2. hydrogen making by natural gas reformation periodic off-gases retracting device as described in claim 1, which is characterized in that the desorber unit
Including：
Desorber, the inlet of the desorber are connected with the outlet of the first end of the First Heat Exchanger, the bottom of the desorber
Portion outlet is connected with the second end entrance of the First Heat Exchanger, for carrying out air lift carbon dioxide removal to the rich amine solution；
Reboiler, the reboiler are connected with the bottom of the desorber, for further to the rich amine solution decarburization；
First gas-liquid separator, first gas-liquid separator are connected with the top exit of the desorber, are used for gas-liquid separation
The carbon dioxide is obtained after going out free water.
3. hydrogen making by natural gas reformation periodic off-gases retracting device as claimed in claim 2, which is characterized in that the desorber unit
Further include：
The entrance of first cooler, first cooler is connected with the top exit of the desorber, first cooler
Outlet be connected with the entrance of first gas-liquid separator；
Reflux pump, the entrance of the reflux pump are connected with the liquid-phase outlet of first gas-liquid separator, and the reflux pump goes out
Mouth is connected with the reflux water inlet of the desorber.
4. hydrogen making by natural gas reformation periodic off-gases retracting device as described in claim 1, which is characterized in that the hydrogen recycling is single
Member includes：
Compressor, the entrance of the compressor are connected with the top exit on the absorption tower, for compressing the periodic off-gases purification
Gas；
The entrance of second gas-liquid separator, second gas-liquid separator is connected with the outlet of the compressor, for gas-liquid point
From the periodic off-gases purified gas；
Second heat exchanger, the first end entrance of second heat exchanger are connected with the gaseous phase outlet of second gas-liquid separator,
The periodic off-gases purified gas after middle change gas and gas-liquid separation that second heat exchanger is used to generate using shift-converter into
Row heat exchange；
Shift-converter, the entrance of the shift-converter are connected with the outlet of the first end of second heat exchanger, are used for institute
It states the carbon monoxide in periodic off-gases purified gas and is changed into carbon dioxide, the outlet of the shift-converter and second heat exchanger
The second end entrance be connected, the outlet of the second end of the shift-converter is connected with PSA unit.
5. hydrogen making by natural gas reformation periodic off-gases retracting device as claimed in claim 4, which is characterized in that the hydrogen recycling is single
Member further includes third cooler, and the entrance of the third cooler is connected with the outlet of the compressor, the third cooler
Outlet be connected with the entrance of second gas-liquid separator.
6. hydrogen making by natural gas reformation periodic off-gases retracting device as claimed in claim 4, which is characterized in that the hydrogen recycling is single
Member further includes：
Heater, the entrance of the heater are connected with the outlet of the first end of second heat exchanger, the outlet of the heater
It is connected with the entrance of the shift-converter；
The entrance of 4th cooler, the 4th cooler is connected with the outlet of the second end of second heat exchanger, and the described 4th
The outlet of cooler is connected with the entrance of the PSA unit.
7. the hydrogen making by natural gas reformation periodic off-gases retracting device as described in one of claim 4-6, described device further includes removing liquid
Device,
The entrance of the liquid knockout is connected with the absorption tower top exit, the first outlet of the liquid knockout and the absorption tower
Liquid return hole be connected, the second outlet of the liquid knockout is connected with the entrance of the compressor.
8. the hydrogen making by natural gas reformation periodic off-gases retracting device as described in one of claim 1-6, which is characterized in that described device
Further include：
First circulation pumps, and the entrance of the first circulation pump is connected with absorb the bottom of the tower outlet, the first circulation pump
Outlet is connected with the first end of the First Heat Exchanger；
The entrance of second cooler, second cooler is connected with the outlet of the second end of the First Heat Exchanger, and described second
The outlet of cooler is connected with the top entry on the absorption tower.
9. hydrogen making by natural gas reformation periodic off-gases retracting device as claimed in claim 8, which is characterized in that described device further includes
Return line,
One end of the return line is connected to the first end entrance of the outlet and the First Heat Exchanger of the first circulation pump
Between pipeline on；The other end of the return line is connected to the second end outlet of the First Heat Exchanger and described second cold
But on the pipeline between the entrance of device.
10. a kind of hydrogen making by natural gas reformation periodic off-gases recovery method, which is characterized in that including：
First PSA periodic off-gases enter through the first periodic off-gases output channel in absorption tower, the poor amine absorption institute in absorption tower
The carbon dioxide in the first PSA periodic off-gases is stated, rich amine solution and periodic off-gases purified gas are generated；
The rich amine solution flows out and is divided into two-way by the absorbing tower bottom, wherein enter First Heat Exchanger all the way, and self solves
Enter desorber unit, another way inflow return line after inhaling the poor amine liquid heat exchange heating of tower unit；
Into the rich amine solution of desorber unit, in desorber unit after air lift carbon dioxide, the poor amine liquid warp after desorption
The First Heat Exchanger reenters the suction with after rich amine solution heat exchange cooling after being mixed with the rich amine solution in the return line
It receives in tower for absorbing carbon dioxide in first periodic off-gases；The carbon dioxide that desorber unit desorbs, by the first gas
Liquid/gas separator obtains carbon dioxide product gas after isolating free water；
The periodic off-gases purified gas is through entering hydrogen recovery unit at the top of the absorption tower, by the hydrogen recovery unit by institute
It states the carbon monoxide in periodic off-gases purified gas and is changed into carbon dioxide, become gas in generation, the middle change gas is handled by PSA unit
Hydrogen product and the 2nd PSA periodic off-gases are discharged afterwards.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111690449A (en) * | 2020-06-18 | 2020-09-22 | 北京颖泓科技发展有限公司 | Energy-saving natural gas MDEA decarburization system and decarburization process thereof |
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