CN104528647B - The method and apparatus that a kind of synthesis gas separates hydrogen making and high-purity CO - Google Patents
The method and apparatus that a kind of synthesis gas separates hydrogen making and high-purity CO Download PDFInfo
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- CN104528647B CN104528647B CN201510014562.6A CN201510014562A CN104528647B CN 104528647 B CN104528647 B CN 104528647B CN 201510014562 A CN201510014562 A CN 201510014562A CN 104528647 B CN104528647 B CN 104528647B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
- F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0257—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0261—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/72—Refluxing the column with at least a part of the totally condensed overhead gas
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/02—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams using a pump in general or hydrostatic pressure increase
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/12—External refrigeration with liquid vaporising loop
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/14—External refrigeration with work-producing gas expansion loop
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/42—Quasi-closed internal or closed external nitrogen refrigeration cycle
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- General Engineering & Computer Science (AREA)
- Separation By Low-Temperature Treatments (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a kind of method that synthesis gas separates hydrogen making and high-purity CO, wherein, the synthesis gas is the gaseous mixture by pre-processing；Method includes：H2And low boiling impurity is isolated from tower top by rectifying, CH4、O2And high-boiling-point impurity is isolated from tower reactor by secondary rectifying, N2And the high-boiling-point impurity not being removed is isolated from tower top by three rectifying, CO is isolated from tower reactor by three rectifying；Wherein, the adjoint energy transfer process of this process passes through the isolated N2The Process of absorption or liberation of heat of circulation loop realize.It is main to include dehydrogenation tower C1, the continuous rectification equipment of deoxidation methane tower C2 and denitrification column C3 and realize the relevant device of energy transmission present invention also offers a kind of device of the above method.Instant invention overcomes the defect of conventional method, equipment investment is saved, reduce energy consumption, improve added value of product, realize recycling economy effect.
Description
Technical field
Gas separation is carried out the present invention relates to a kind of method that gas is separate, more particularly to a kind of being acted on by cryogenic liquefying
Method, in particular it relates to the method and apparatus that a kind of synthesis gas separates hydrogen making and high-purity CO.
Background technology
With the development of Chinese large-sized chemical field, steamed as raw material enters water-filling with natural gas, coal and other hydrocarbons
Gas Reforming catalyst convert or partial oxidation produced by the total amount of synthesis gas also increasing severely, except containing not filling in these synthesis gas
Divide the carbon monoxide of conversion, also usually contain hydrogen, nitrogen, methane, oxygen and carbon dioxide etc..Due to various many in synthesis gas
The impurity composition of sample, often limits further using for it, in the case of big number, has substantial amounts of mixed gas white daily
Burn in vain emptying, cause the waste of resource and the aggravation of greenhouse effects.
In fact, the gas of high-purity has become important basic chemical feedstock, especially carbon monoxide and hydrogen,
The chemical processes such as carbonylation synthesis have been widely used in, it is important as a series of basic organic chemical industry products and intermediate
Raw material.Wherein, the source of carbon monoxide is substantially by the gas containing a certain amount of CO2, CO, H2, N2, CH4, O2, H2O etc.
Mixture, using deep cooling separating method, so as to obtain the CO of high-purity, this method is applied to large-scale industrial production, and
And can more efficiently obtain the CO of high-purity.
At present, deep cooling separating method is throttled generally by by the synthesis gas of certain pressure, expanded, to produce
Lower temperature is so that synthesis gas is completely or partially liquefied, and then H2, CH4, CO are separated.Wherein, the core of separation by deep refrigeration
It is the difference using boiling point between each component in synthesis gas, the separation of admixture of gas is realized by rectifying column.In order to prevent
Impurity contained in composite gas component solidify at low temperature so as to block heat exchanger and pipeline, it is necessary to unstripped gas enter ice chest before carry out it is pre-
Treatment, removing heavy hydrocarbon, CO2, H2O and H2S etc..
Chinese patent CN104011488 A disclose a kind of method by low temperature distillation supply gaseous carbon monoxide and set
It is standby, including, material synthesis gas are cooled down first, most of hydrogen is then removed in methane wash column, and enter
Enter the middle part of domethanizing column in stripper after further removing hydrogen, then obtain methane rich in tower reactor, methane rich is through liquid
Pump pressurization rear portion is allocated as being methane wash column phegma that part is continued re-heat and goes out device as fuel gas, in demethanizer overhead
Rich carbon monoxide is obtained, rich carbon monoxide goes out device into carbon monoxide cycle compressor boost, product carbon monoxide through re-heat
Extracted out from recycle compressor intergrade.The cold supplement of device is cooled down for the carbon monoxide of recycle compressor outlet in heat exchanger
Extracted out from middle part and enter expander to low pressure return heat exchanger re-heat.
In method described above, because of lower boiling nitrogen as carbon monoxide is enriched to demethanizer overhead together, because
Nitrogen in the carbon monoxide of this device production cannot solve further to be removed, it is necessary to increase device in the flow, and rich
Carbon monoxide go out device pressure it is relatively low need to be pressurized in recycle compressor after cooling box from intergrade extract out.The first of the invention
Alkane scrubbing tower is free of reboiler, thus cannot in a tower once removing, it is necessary to increase stripper, in stripper top discharge
Hydrogen-rich gas, the gas cannot use therefore device hydrogen recovery rate relatively low as product gas.
In addition, CN101568788B discloses a kind of separation by low temperature distillation comprises at least hydrogen, nitrogen and carbon monoxide
The method and apparatus of mixture, although achieve certain separating effect, but the equipment for using does not have further imperfection, especially
It is starting to be separated during hydrogen obtains C1 and C2 containing methane, carbon monoxide and nitrogen mixture, it is necessary to set for main
C2 towers remove remaining hydrogen, and a part of raw hydrogen enters hydrogen content ＞ 1.5% in C1 tower bottoms, thus C2 tower raw materials
In C2 removed overheads, the thick hydrogen in this part cannot function as hydrogen product and use, and reduce hydrogen recovery rate.
The content of the invention
In order to solve the method and apparatus that prior art is proposed in separating-purifying synthesis gas, in actual applications not
Foot, there is provided a kind of energy-efficient method and apparatus that hydrogen making and high-purity CO are separated from synthesis gas, the present invention
The method and apparatus that hydrogen making and high-purity CO are separated there is provided a kind of synthesis gas, be first with containing H2, CO, N2,
The synthesis gas of the admixture of gas of CH4, O2 etc. is raw material, it is possible to which, while producing hydrogen and carbon monoxide, auxiliary obtains nitrogen
It is exactly in short using dehydrogenation tower C1, deoxidation-methane tower C2 and denitrification column C3 continuous rectification preparing hydrogens with the method for fuel gas
Gas and high-purity CO, while nitrogen and fuel gas are also separated from synthesis gas, overcome the defect of conventional method,
Equipment investment is saved, energy consumption is reduced, added value of product is improve, it is achieved thereby that recycling economy effect.
It is an object of the present invention to provide a kind of method that synthesis gas high for impurity content is separate.
It is another object of the present invention to obtain a kind of to participate in the high-purity of synthesis or research as raw material or intermediate
Degree H2, on the other hand, methods described is for separating H2With high-recovery.
It is another object of the present invention to obtain a kind of CO of high-purity.
The purpose of the present invention also includes that auxiliary obtains the nitrogen and fuel gas that can be reused.
The present invention also aims on the basis of stating purpose in realization, there is provided one kind reduces energy ezpenditure and simultaneously reduces throwing
The method for providing cost.
Above-mentioned purpose has been realized the present invention also aims to provide a kind of device.
The theme of the first aspect of the present invention is a kind of method that synthesis gas separates hydrogen making and high-purity CO, its
It is characterised by, the synthesis gas is by mainly containing H after pretreatment2、CO、N2、CH4、O2And a small amount of other gaseous impurities is mixed
Close gas；
Methods described includes：H2And low boiling impurity is isolated from tower top by rectifying, CH4、O2And high-boiling-point impurity
, the N isolated from tower reactor by secondary rectifying2And the high-boiling-point impurity not being removed is separated by three rectifying from tower top
Obtain, CO is isolated from tower reactor by three rectifying；
Wherein, the adjoint energy transfer process of this process passes through the isolated N2Circulation loop suction, put
Heat is realized.
A preferred embodiment according to the first aspect of the invention, wherein, on the synthesis gas, the pretreatment bag
Purifying, other pretreatment operations dry and well known by persons skilled in the art are included, is mainly used in removing heavy hydrocarbon, CO2、H2O and H2S
Deng.
A preferred embodiment according to the first aspect of the invention, wherein, the CO is by isolated purity
More than 98%, can reach more than 99.999%.
The H2By isolated purity be more than 93%, and after after main heat exchanger EH1 re-heats cooling box enter
PSA hydrogen purification apparatus are purified.
The theme of the second aspect of the present invention is that a kind of synthesis gas as described in relation to the first aspect separates hydrogen making and height is single
The device of the method for carbonoxide, it is characterised in that described device includes being provided with overhead condensation evaporator K1, K2, K3 and tower reactor again
Dehydrogenation tower C1, the deoxidation-methane tower C2 and denitrification column C3 continuous rectification equipment of boiling device B1, B2, B3；
Also include to realize N2Circulation loop and energy transfer process and the recycle compressor CP1 that sets, main heat exchanger
EH1, turbo-expander TP1, choke valve V1, V2, V3, return tank SP1 and carbon monoxide screens pump BP1；
Wherein, specifically, after recycle compressor CP1 is pressurized and is cooled to normal temperature, nitrogen 201 enters low-pressure nitrogen 220
Enter in main heat exchanger EH1 and cool down, wherein, enter deoxidation-methane in the middle part extraction section medium pressure nitrogen gas 202 of main heat exchanger EH1
Cooled down in the tower reactor reboiler B2 of tower C2, so that the liquid portion evaporation rectifying in C2 in the tower reactor of deoxidation-methane tower C2, and
Lift the methane concentration in tower reactor liquid, carbon monoxide content is reduced；Medium pressure nitrogen gas 204 after cooling is again introduced into denitrification column
Cooled down in the tower reactor reboiler B3 of C3, so that the liquid portion evaporation rectifying in C3 in the tower reactor of denitrification column C3, and make tower reactor
Carbonomonoxide concentration lifting, nitrogen content reduce to obtain qualified carbon monoxide fluid product in liquid；Middle pressure after cooling
After the middle hydraulic fluid nitrogen 203 that liquid nitrogen 205 is out liquefied and is subcooled with the cold end in the main heat exchanger EH1 converges, pressure liquid nitrogen 207 enters
Enter the low-temperature receiver as overhead condensation evaporator K2 in the overhead condensation evaporator K2 of deoxidation-methane tower C2, rich pressure liquid nitrogen
211 are divided into two strands of pressure liquid nitrogen 212 and pressure liquid nitrogen 213 throttles to normal pressure through choke valve and respectively enters the tower top of dehydrogenation tower C1
In the overhead condensation evaporator K3 of condenser/evaporator K1 and denitrification column C3, as the low-temperature receiver of overhead condensation evaporator K1 and K3；C2
From the middle part of main heat exchanger EH1 after the re-heat of part in the entrance main heat exchanger of pressure nitrogen gas 208 EH1 evaporated in tower condenser/evaporator
Extract pressure nitrogen gas 209 out, the cold damage for producing cold supplementary device is expanded into nitrogen gas turbine expanding machine TP1, it is low after expansion
Pressure nitrogen 210 and the mixed low-pressure nitrogen 219 of low-pressure nitrogen 218 and 217 of evaporation in overhead condensation evaporator K1 and K3, enter
Enter main heat exchanger EH1 low-pressure nitrogen passage re-heat to normal temperature obtain low-pressure nitrogen 220 after, followed into recycle compressor CP1
Ring is used.
A preferred embodiment according to the second aspect of the invention, wherein, the carbon monoxide liquid is through carbon monoxide
Canned motor pump BP1 superchargings refer to be forced into higher than discharge pressure needed for product gas.
Medium pressure nitrogen gas in the tower reactor reboiler B2 of the entrance deoxidation-methane tower C2 is with the tower reactor for entering denitrification column C3 again
Medium pressure nitrogen gas in boiling device B3 is sequential series connection, is converged with liquid nitrogen 203 by expenditure and pressure after progressively cooling down.
Described device also includes dehydrogenation tower C1, deoxidation-methane tower C2, denitrification column C3, condenser/evaporator K1, K2, K3, tower reactor
Reboiler B1, B2, B3, the pipeline and valve being connected between main heat exchanger EH1, turbo-expander TP1 and carbon monoxide screens pump BP1
Door.
Pressure nitrogen gas 202 in the tower reactor reboiler of the entrance deoxidation-methane tower boil again in the tower reactor for entering denitrification column
Separate one nitrogen before device B3 to mix with the nitrogen after the tower reactor reboiler B3 coolings of denitrification column, change separates the stream of one nitrogen
Measure to change the load of the tower reactor reboiler B3 of denitrification column.
The one of the method and apparatus of hydrogen making and high-purity CO is separated according to a kind of synthesis gas of the present invention
Individual preferred embodiment, wherein, specifically, methods described includes：
Step 1：By the synthesis air cooling, after being then fed into the tower reactor reboiler B1 of dehydrogenation tower C1 cooling down again, warp
Choke valve V1 decompressions enter rectifying in dehydrogenation tower C1, wherein, the thick hydrogen obtained in tower top enters overhead condensation evaporator K1 and liquid
Nitrogen exchanges heat so that being mixed in most of carbon monoxide therein, nitrogen condensation turns into liquid and be back to lower top of tower, and uncooled
Hydrogen through main heat exchanger EH1 re-heats to normal temperature as output of products；
Step 2：It is back in dehydrogenation tower C1 tower reactor reboilers B1 and contains a small amount of hydrogen (hydrogeneous ＜ 5 × 10-6(V/V))
Imported in deoxidation-methane tower C2 after synthesis gas-liquid warp knuckle stream valve V2 decompression, wherein, tower top obtain containing micro amount of oxygen and basic
Carbon monoxide, nitrogen, the mixture of Microamounts of Hydrogen without methane, exchange heat into overhead condensation evaporator K2 with liquid nitrogen, part
Mixture is condensed into phegma of the liquid as C2, and portion gas mixture imports rectifying in denitrification column C3 through choke valve V3；Tower
In kettle extract part isolate rich in methane (CH4 ＞ 99.9 × 10-2(V/V) liquid) is made after main heat exchanger EH1 re-heats
For fuel gas is used；
Step 3：Gaseous mixture rectifying in denitrification column C3 after the throttling of V3 valves, wherein, containing in tower reactor reboiler B3
The carbon monoxide liquid for having micro amount of oxygen and nitrogen imports re-heat in main heat exchanger EH1 and makees after being pressurized through carbon monoxide screens pump BP1
It is output of products；Obtain being exchanged heat with liquid nitrogen during the nitrogen containing micro CO enters overhead condensation evaporator K3 in tower top, portion
Nitrogen mixture is divided to be condensed into phegma of the liquid as C3, denitrogenation tower top is obtained containing H2＜ 5 × 10-6(V/V), ＜ containing CO 5 ×
10-6(V/V) high pure nitrogen, into main heat exchanger EH1 re-heats after as nitrogen circulating system nitrogen supplement and system meter
Source of the gas is used.
Separated according to a kind of synthesis gas of the present invention hydrogen making and high-purity CO method and apparatus it is another
One preferred embodiment, wherein：
It is continuous using the dehydrogenation tower C1 of overhead condenser with pressure and tower bottom reboiler, deoxidation-methane tower C2 and denitrification column C3
Rectifying hydrogen making and high-purity CO；Medium pressure nitrogen gas is circulated to vaporize the synthesis in deoxidation-methane tower C2 and denitrification column C3
Gas, and enter condenser/evaporator after being throttled through choke valve after the nitrogen after cooling down is liquefied as dehydrogenation tower, methane tower and denitrogenation
The low-temperature receiver of tower；The aqueous carbon monoxide of high-purity is obtained from denitrogenation tower reactor reboiler B3, is added by carbon monoxide screens pump BP1
Main heat exchanger EH1 is vaporized with as output of products after being depressed into required pressure；From purity 93% obtained in the dehydrogenation top of tower with
On hydrogen after main heat exchanger EH1 re-heats cooling box into PSA hydrogen purification apparatus purify；Into deoxidation-methane tower C2's
Medium pressure nitrogen gas in tower reactor reboiler B2 and the medium pressure nitrogen gas in the tower reactor reboiler B3 for entering denitrification column C3 are sequential series company
Connect progressively cooling deutomerite stream and enter C1, the condenser/evaporator K1, K2, K2 of C2, C3 tower are used as rectifying column C1, the phegma of C2, C3
Low-temperature receiver, after the nitrogen under pressure re-heat that condenser/evaporator K2 is evaporated enter turbo-expander expand offer device cold.
The method and apparatus that a kind of synthesis gas of the present invention separates hydrogen making and high-purity CO, as a result of
Above-mentioned technical proposal, with advantages below and beneficial effect：
1st, the present invention is cooled down in reboiler before dehydrogenation tower is entered and is maintained superheat state laggard using the synthesis gas of overheat
Enter rectifying column middle part, make the most of hydrogen recovery rate higher by evaporation acquisition of low boiling hydrogen in tower reactor, using band overhead condensation
Three tower continuous produtions of device and tower reactor reboiler can simultaneously produce hydrogen and carbon monoxide, and obtain nitrogen and fuel gas,
Production capacity is greatly improved；
2nd, the present invention produces cold using the pressure nitrogen gas expansion of nitrogen supercharging, deoxidation-methane tower condenser/evaporator evaporation
The circulatory system；Liquid nitrogen can obtain heat transfer temperature difference higher as rectifying column condenser low-temperature receiver and carbon monoxide cycle ratio, can
To improve condenser evaporating pressure, the pressure nitrogen gas expansion evaporated using deoxidation-methane tower condenser/evaporator is produced cold and maintained
Device cold balancing, therefore using nitrogen circulation amount of the present invention 10-20% lower than other process units；
3rd, dehydrogenation tower C1 separates the low boiling impurities such as hydrogen from tower top in the present invention, and deoxidation-methane tower C2 divides from bottom of towe
From CH4、O2Deng high-boiling-point impurity, and the further separation for passing through denitrification column C3, can process containing the gaseous mixture more than impurity, it is right
The requirement of gaseous mixture to be dealt with is lower relative to existing technologies, has a wide range of application, and is suitable to large-scale promotion and application；
4th, C1 tower of the setting with tower reactor reboiler and overhead condenser disclosed by the invention, hydrogen takes off substantially in C1 towers
Only, hydrogeneous ＜ 5 × 10 in dehydrogenation tower bottom synthesis gas-6, thus hydrogen of the present invention recovery rate in C1 towers exceedes (V/V)
99.9%；
5th, product carbon monoxide of the invention is directly to evaporate multiple in main heat exchanger EH1 after pump pressurizes from C3 tower reactors
Band die pressing product carbon monoxide is obtained after heat, the wind of carbon monoxide compressor operation safety is avoided using nitrogen circulation compressor
Danger.
Brief description of the drawings
Fig. 1 is the corresponding method and device schematic diagram of the embodiment of the present invention 1.
Wherein：C1 dehydrogenation towers；C2 deoxidations-methane tower；C3 denitrification columns；K1, K2, K3 overhead condensation evaporator；B1、B2、B3
Tower reactor reboiler；EH1 main heat exchangers；TP1 turbo-expanders；BP1 carbon monoxide screens pumps；SP1 return tanks；CP1 circulation compressions
Machine；V1, V2, V3 choke valve；101st, 102,103,104 synthesis gas；105th, 106 hydrogen；107th, the synthesis gas after 108 dehydrogenations；
109th, 110 be N2/CO based on gaseous mixture；111st, 112 methane rich (fuel gas)；113rd, 114,115 carbon monoxide；201、202、
Hydraulic fluid nitrogen, 206,207,211,212,213 pressure liquid nitrogen in 204 medium pressure nitrogen gas, 203,205；208th, 209 pressure nitrogen gas；214、
215 low pressure liquid nitrogens；216th, 217,218,210,219,220 low-pressure nitrogen.
Wherein：Middle pressure finger pressure >=1.6MPa, low pressure finger pressure is less than 0.1MPa, and pressure nitrogen, nitrogen under pressure finger pressure are situated between
In between 0.1MPa-1.6MPa.
Specific embodiment
The invention provides a kind of method that synthesis gas separates hydrogen making and high-purity CO, it is characterised in that institute
It is by mainly containing H after pretreatment to state synthesis gas2、CO、N2、CH4、O2And the gaseous mixture of a small amount of other gaseous impurities；
Methods described includes：H2And low boiling impurity is isolated from tower top by rectifying, CH4、O2And high-boiling-point impurity
, the N isolated from tower reactor by secondary rectifying2And the high-boiling-point impurity not being removed is separated by three rectifying from tower top
Obtain, CO is isolated from tower reactor by three rectifying；
Wherein, the adjoint energy transfer process of this process passes through the isolated N2Circulation loop suction, put
Heat is realized.
According to a preferred embodiment of the present invention, wherein, on the synthesis gas, the pretreatment includes purifying, dry
Other pretreatment operations dry and well known by persons skilled in the art, are mainly used in removing heavy hydrocarbon, CO2, H2O and H2S etc..
Present invention also offers the side that a kind of synthesis gas as described in relation to the first aspect separates hydrogen making and high-purity CO
The device of method, it is characterised in that described device include being provided with overhead condensation evaporator K1, K2, K3 and tower reactor reboiler B1, B2,
Dehydrogenation tower C1, the deoxidation-methane tower C2 and denitrification column C3 continuous rectification equipment of B3；
Also include to realize N2Circulation loop and energy transfer process and the recycle compressor CP1 that sets, main heat exchanger
EH1, turbo-expander TP1, choke valve V1, V2, V3, return tank SP1 and carbon monoxide screens pump BP1；
Wherein, specifically, after recycle compressor CP1 is pressurized and is cooled to normal temperature, nitrogen 201 enters low-pressure nitrogen 220
Enter in main heat exchanger EH1 and cool down, wherein, enter deoxidation-methane tower C2 in the middle part extraction section nitrogen 202 of main heat exchanger EH1
Tower reactor reboiler B2 in cool down so that the liquid portion evaporation rectifying in C2 in the tower reactor of deoxidation-methane tower C2, and makes tower
Methane concentration lifting in kettle liquid body, carbon monoxide content are reduced；Medium pressure nitrogen gas 204 after cooling is again introduced into denitrification column C3's
Cooled down in tower reactor reboiler B3, so that the liquid portion evaporation rectifying in denitrification column C3 in the tower reactor of denitrification column C3, and make tower
Carbonomonoxide concentration lifting, nitrogen content reduce to obtain qualified carbon monoxide fluid product in kettle liquid body；In after cooling
After the middle hydraulic fluid nitrogen 203 that hydraulic fluid nitrogen 205 is out liquefied and is subcooled with the cold end in the main heat exchanger EH1 converges, pressure liquid nitrogen 207
Into in the overhead condensation evaporator K2 of deoxidation-methane tower C2 as the low-temperature receiver of overhead condensation evaporator K2, rich pressure fluid
Nitrogen 211 is divided into two strands of pressure liquid nitrogen 212 and pressure liquid nitrogen 213 throttles to normal pressure through choke valve and respectively enters the tower of dehydrogenation tower C1
In the overhead condensation evaporator K3 of top condenser/evaporator K1 and denitrification column C3, as the low-temperature receiver of overhead condensation evaporator K1 and K3；
The pressure nitrogen gas 208 evaporated in deoxidation-methane tower C2 tower condenser/evaporators are changed into after part re-heat in main heat exchanger EH1 from master
Pressure nitrogen gas 209 are extracted at the middle part of hot device EH1 out, are expanded into nitrogen gas turbine expanding machine TP1 and are produced the cold of cold supplementary device
Damage, the low-pressure nitrogen 210 after expansion is mixed with the low-pressure nitrogen 218 and 217 of evaporation in overhead condensation evaporator K1 and K3
Low-pressure nitrogen 219, into main heat exchanger EH1 low-pressure nitrogen passage re-heat to normal temperature obtain low-pressure nitrogen 220 after, into circulation
Recycled in compressor CP1.
According to the corresponding method and device schematic diagram of Fig. 1 embodiment of the present invention 1, synthesis gas of the present invention is separated
The method and apparatus of hydrogen making and high-purity CO are further explained and illustrate.
Embodiment 1
Middle pressure (general pressure is between 2.5-5MPa) contains H2、CO、N2、CH4、O2And the raw material of a small amount of other gaseous impurities is closed
- 100 to -140 DEG C are cooled in main heat exchanger EH1 into gas 101, are then fed into being cooled down in the tower reactor reboiler B1 of dehydrogenation tower C1
Synthesis gas 103 after to a little higher than reboiler kettle liquid saturation temperature enters rectifying in dehydrogenation tower C1 after being depressurized through choke valve V1,
Tower top obtains ((~92%H2)) thick hydrogen exchanged heat with low pressure liquid nitrogen 214 into overhead condensation evaporator K1, then by major part
Carbon monoxide, nitrogen turn into liquid through overhead condensation evaporator K1 condensations, be then refluxed for lower top of tower, overhead condensation evaporation
(~the 93%H of uncooled hydrogen 105 in device K12) exported as product hydrogen 106 through main heat exchanger EH1 re-heats to normal temperature；
It is back in dehydrogenation tower C1 bottoms tower reactor reboilers B1 and contains a small amount of hydrogen (hydrogeneous ＜ 5 × 10-6(V/V) conjunction)
Gas-liquid is obtained after being decompressed to 0.15-0.5MPa through choke valve V2 into gas-liquid 107 (main component is carbon monoxide, methane, nitrogen)
State flow 108 imports rectifying in deoxidation-methane tower C2；An oxidation of methane is obtained containing micro amount of oxygen and is substantially free of in tower top
Carbon, nitrogen, Microamounts of Hydrogen mixture enter overhead condensation evaporator K2 in liquid nitrogen heat exchange, part mixes be condensed into liquid work
It is the phegma of deoxidation-methane tower C2, portion gas gaseous mixture 109 imports rectifying in denitrification column C3 through choke valve V3；Deoxidation-first
In alkane tower C2 tower reactors extract part isolate rich in methane (CH4 ＞ 99.9 × 10-2(V/V) liquid 111) is through main heat exchanger
Used as fuel gas 112 after EH1 re-heats；
Gaseous mixture 110 rectifying, bottom column in denitrification column C3 (pressure is between 0.06-0.3MPa) after the throttling of V3 valves
In kettle reboiler B3 containing carbon monoxide liquid 113 (purity~98%CO, reach as high as more than 99.999%CO) through an oxygen
Change carbon canned motor pump BP1 and be pressurized to liquid 114 after 0.2-5MPa and import re-heat in main heat exchanger EH1 and exported as product 115；In tower
Top obtain the nitrogen containing micro CO enter in condenser/evaporator K3 with liquid nitrogen heat exchange, part nitrogen mixture is condensed into liquid
Body as denitrification column C3 phegma, denitrogenation tower top obtained containing H2＜ 5 × 10-6(V/V), ＜ containing CO 5 × 10-6(V/V) high-purity
Nitrogen, into main heat exchanger EH1 re-heats after as nitrogen circulating system nitrogen supplement and system meter source of the gas use；
Low-pressure nitrogen 220 (pressure~0.01MPa) is pressurized to 2.5-5MPa and is cooled to by circulating nitrogen gas compressor CP1
(201) are into being cooled in (temperature~-100 of main heat exchanger middle part extraction section medium pressure nitrogen gas 202 in main heat exchanger EH1 after normal temperature
DEG C to -130 DEG C) into after being cooled to the temperature of a little higher than deoxidation-methane tower C2 tower bottoms in deoxidation-methane tower reboiler B2,
The liquid portion in the tower reactor of deoxidation-methane tower C2 is evaporated the rectifying in C2, make methane concentration lifting, an oxygen in tower reactor liquid
Change carbon content to reduce；Medium pressure nitrogen gas (or liquid) 204 after cooling is again introduced into further being cooled down in denitrification column reboiler B3, makes
Liquid portion evaporation rectifying in denitrification column C3 in the tower reactor of denitrification column C3, make carbonomonoxide concentration lifting in tower reactor liquid,
Nitrogen content reduces to obtain qualified carbon monoxide fluid product 113；Middle hydraulic fluid nitrogen 205 after cooling with main heat exchanger
The middle hydraulic fluid nitrogen 203 that cold end is out liquefied and is subcooled in EH1 converges rear pressure liquid nitrogen 207 and enters deoxidation-methane tower condensation steaming
As the low-temperature receiver of deoxidation-methane tower C2 tower condenser/evaporators in hair device K2, rich pressure liquid nitrogen 211 is divided into two strands of pressure liquid nitrogen
212 and pressure liquid nitrogen 213 throttled to normal pressure through choke valve pour into respectively dehydrogenation tower C1 tower condenser/evaporator K1 and C3 tower condensation
Evaporator K3, as dehydrogenation tower C1 and the low-temperature receiver of denitrification column C3 tower condenser/evaporators；
The pressure nitrogen gas 208 (pressure 0.08MPa-0.5MPa) evaporated in deoxidation-methane tower C2 tower condenser/evaporators enter
Part re-heat extracts 209 out to -140 DEG C to -165 DEG C from heat exchanger middle part in main heat exchanger, into nitrogen gas turbine expanding machine TP1
Be expanded to the cold damage that 0.015MPa to 0.05MPa produces cold supplementary device, nitrogen 210 after expansion and condenser/evaporator K1 and
Low-pressure nitrogen 219 enters back into main heat exchanger low-pressure nitrogen passage re-heat to normal after the low-pressure nitrogen 218,217 evaporated in K3 mixes
Enter in circulating nitrogen gas compressor CP1 after warm low-pressure nitrogen 220 and recycle.
Following table is the specific data of embodiment 1：
The achievable low energy consumption ground hydrogen making of the present invention, carbon monoxide；98% and more than 99.999% can be produced
Carbon monoxide product；Carbon monoxide compressor can be set so as to reach when carbon monoxide pressure is produced higher than 0.2MPa
Energy-conservation and investment reduction, the purpose of enhancing safety in operation.
Specific embodiment of the invention has been described in detail above, but it is intended only as example, and the present invention is not limited
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications carried out to the present invention and
Replacement is also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (6)
1. a kind of synthesis gas separates the device of hydrogen making and high-purity CO, it is characterised in that the synthesis gas be by
H is mainly contained after pretreatment2、CO、N2、CH4、O2And the gaseous mixture of a small amount of other gaseous impurities；Described device includes being provided with first
Overhead condensation evaporator (K1), the second overhead condensation evaporator (K2), the 3rd overhead condensation evaporator (K3) and the first tower reactor are again
Boiling device (B1), the second tower reactor reboiler (B2), the dehydrogenation tower (C1) of the 3rd tower reactor reboiler (B3), deoxidation-methane tower (C2) and
Denitrification column (C3) continuous rectification equipment；
Also include to realize N2Circulation loop and energy transfer process and the recycle compressor (CP1) that sets, main heat exchanger (EH1),
Turbo-expander (TP1), first throttle valve (V1), second throttle (V2), the 3rd choke valve (V3), return tank (SP1) and
Carbonoxide canned motor pump (BP1)；
Wherein, after recycle compressor (CP1) is pressurized and is cooled to normal temperature, medium pressure nitrogen gas 201 is changed low-pressure nitrogen 220 into master
Cooling in hot device (EH1), wherein, enter deoxidation-methane tower in the middle part extraction section medium pressure nitrogen gas 202 of main heat exchanger (EH1)
(C2) cooling in the second tower reactor reboiler (B2), so that the liquid portion evaporation in the tower reactor of deoxidation-methane tower (C2) is de-
Rectifying in oxygen-methane tower (C2), and lift the methane concentration in tower reactor liquid, carbon monoxide content reduce；In after cooling
Pressure nitrogen 204 is again introduced into cooling in the 3rd tower reactor reboiler (B3) of denitrification column (C3), so that in the tower reactor of denitrification column (C3)
Liquid portion evaporation rectifying in denitrification column (C3), and reduce carbonomonoxide concentration lifting, nitrogen content in tower reactor liquid
To obtain qualified carbon monoxide fluid product；Middle hydraulic fluid nitrogen 205 after cooling and the cold end in main heat exchanger (EH1) out by
After the middle hydraulic fluid nitrogen 203 for liquefying and being subcooled converges, the second overhead condensation that pressure liquid nitrogen 207 enters deoxidation-methane tower (C2) steams
As the low-temperature receiver of the second overhead condensation evaporator (K2) in hair device (K2), pressure liquid nitrogen 211 more than needed is divided into two strands of pressure liquid nitrogen
212 and pressure liquid nitrogen 213 throttled to normal pressure through choke valve and respectively enter the first overhead condensation evaporator of dehydrogenation tower (C1)
(K1) and in the 3rd overhead condensation evaporator (K3) of denitrification column (C3), as the first overhead condensation evaporator (K1) and the 3rd tower
The low-temperature receiver on top condenser/evaporator (K3)；The pressure nitrogen gas 208 evaporated in deoxidation-methane tower (C2) tower condenser/evaporator are changed into master
Pressure nitrogen gas 209 are extracted out after the re-heat of part from the middle part of main heat exchanger (EH1), in hot device (EH1) into nitrogen gas turbine expanding machine
(TP1) expansion produces the cold damage of cold supplementary device, the overhead condensation evaporator (K1) of low-pressure nitrogen 210 and first after expansion in
And the 3rd evaporation in overhead condensation evaporator (K3) low-pressure nitrogen 218 and the mixed low-pressure nitrogen 219 of low-pressure nitrogen 217,
Into main heat exchanger (EH1) low-pressure nitrogen passage re-heat to normal temperature obtain low-pressure nitrogen 220 after, into recycle compressor
(CP1) recycled in.
2. device according to claim 1, it is characterised in that hydrogen making and high-purity CO method in said device
Including：
Step 1：By the synthesis air cooling, it is then fed into being cooled down again in first tower reactor reboiler (B1) of dehydrogenation tower (C1)
Afterwards, rectifying in dehydrogenation tower (C1) is entered through first throttle valve (V1) decompression, wherein, the thick hydrogen obtained in tower top enters the first tower top
Condenser/evaporator (K1) exchanges heat with liquid nitrogen so that being mixed in most of carbon monoxide therein, nitrogen condensation turns into liquid and flow back
To lower top of tower, and uncooled hydrogen through main heat exchanger (EH1) re-heat to normal temperature as output of products；
Step 2：The synthesis gas-liquid containing a small amount of hydrogen in the first tower reactor reboiler of dehydrogenation tower (C1) (B1) is back to through
Two choke valves (V2) decompression after import deoxidation-methane tower (C2) in, wherein, tower top obtain containing micro amount of oxygen and be substantially free of first
The carbon monoxide of alkane, nitrogen, the mixture of Microamounts of Hydrogen, exchange heat into the second overhead condensation evaporator (K2) with liquid nitrogen, part
Mixture is condensed into phegma of the liquid as deoxidation-methane tower (C2), and portion gas mixture is led through the 3rd choke valve (V3)
Enter rectifying in denitrification column (C3)；The liquid rich in methane that extraction part is isolated in tower reactor is after main heat exchanger (EH1) re-heat
Used as fuel gas；
Step 3：Gaseous mixture rectifying in denitrification column (C3) after the throttling of the 3rd choke valve (V3), wherein, the 3rd tower reactor is again
The carbon monoxide liquid containing micro amount of oxygen and nitrogen in boiling device (B3) imports master and changes after being pressurized through carbon monoxide screens pump (BP1)
Re-heat is used as output of products in hot device (EH1)；The nitrogen containing micro CO is obtained in tower top to be steamed into the 3rd overhead condensation
With liquid nitrogen heat exchange in hair device (K3), part nitrogen mixture is condensed into phegma of the liquid as denitrification column (C3), remaining nitrogen
Used as the regeneration source of the gas of purified synthesis gas device after into main heat exchanger (EH1) re-heat.
3. device according to claim 2, it is characterised in that in the step 3, the carbon monoxide liquid is through carbon monoxide
Canned motor pump (BP1) supercharging refers to be forced into higher than discharge pressure needed for product gas.
4. device according to claim 1, it is characterised in that the second tower reactor of the entrance deoxidation-methane tower (C2) is boiled again
Medium pressure nitrogen gas in device (B2) and the medium pressure nitrogen gas in the 3rd tower reactor reboiler (B3) for entering denitrification column (C3) are sequential series
Connection, converges by expenditure and pressure after progressively cooling down with liquid nitrogen 203.
5. device according to claim 1, it is characterised in that described device also includes dehydrogenation tower (C1), deoxidation-methane tower
(C2), denitrification column (C3), the first overhead condensation evaporator (K1), the second overhead condensation evaporator (K2), the 3rd overhead condensation steam
Hair device (K3), the first tower reactor reboiler (B1), the second tower reactor reboiler (B2), the 3rd tower reactor reboiler (B3), main heat exchanger
(EH1) pipeline and valve, being connected between turbo-expander (TP1) and carbon monoxide screens pump (BP1).
6. device according to claim 1, it is characterised in that the pressure in the tower reactor reboiler of the entrance deoxidation-methane tower
Power nitrogen 202 separates one nitrogen and is boiled again with the 3rd tower reactor of denitrification column before the 3rd tower reactor reboiler (B3) for entering denitrification column
Nitrogen mixing after device (B3) cooling, change separates the flow of one nitrogen to change the 3rd tower reactor reboiler (B3) of denitrification column
Load.
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| CN105462640B (en) * | 2015-12-03 | 2018-06-29 | 合肥通用机械研究院 | A kind of deep cooling hydrocarbon material denitrogenation tower top condensing unit |
| CN105692552B (en) * | 2016-01-28 | 2018-02-02 | 上海化工研究院有限公司 | A kind of rectification process of energy-efficient high-purity CO and hydrogen |
| CN106379899A (en) * | 2016-08-30 | 2017-02-08 | 成都赛普瑞兴科技有限公司 | Method for preparing carbon monoxide and hydrogen from synthetic gas |
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| CN107473223B (en) * | 2017-08-15 | 2020-04-03 | 成都深冷液化设备股份有限公司 | CO cryogenic separation system adopting nitrogen circulation and method thereof |
| CN107758619A (en) * | 2017-10-18 | 2018-03-06 | 浙江海天气体有限公司 | Nitrogen hydrogen ammonia gaseous mixture purifying plant |
| CN108441273B (en) * | 2018-04-02 | 2019-12-24 | 东北大学 | Oxygen-containing low-concentration combustible gas deoxidation method and deoxidation system |
| CN111847453B (en) * | 2020-07-30 | 2022-03-18 | 上海化工研究院有限公司 | Device and process for preparing ultra-pure carbon monoxide |
| CN112758892B (en) * | 2021-01-05 | 2021-12-17 | 西南化工研究设计院有限公司 | Pressure swing adsorption hydrogen purification system and method thereof |
| FR3120431B1 (en) * | 2021-03-05 | 2023-03-31 | Air Liquide | Purification of carbon monoxide by cryogenic distillation |
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Effective date of registration: 20210625 Address after: 201800 rooms 202 and 204, building 3, 150 Heyu Road, Jiading District, Shanghai Patentee after: SHANGHAI QIYUAN GAS DEVELOPMENT Co.,Ltd. Address before: 201800 150 Heyu Road, Jiading District, Shanghai Patentee before: SHANGHAI QIYUAN AIR SEPARATE TECHNOLOGY DEVELOPMENT Co.,Ltd. |