CN110114626A - Method and apparatus for passing through partial condensation cryogenic separation synthesis gas - Google Patents
Method and apparatus for passing through partial condensation cryogenic separation synthesis gas Download PDFInfo
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- CN110114626A CN110114626A CN201780074179.7A CN201780074179A CN110114626A CN 110114626 A CN110114626 A CN 110114626A CN 201780074179 A CN201780074179 A CN 201780074179A CN 110114626 A CN110114626 A CN 110114626A
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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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- 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
- F25J3/0233—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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- 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
- F25J3/0261—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
- 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
- F25J3/0271—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 H2/CO mixtures, i.e. of synthesis 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
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/40—Features relating to the provision of boil-up in the bottom of a 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
- F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
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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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
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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
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
- F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
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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
- F25J2270/02—Internal 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
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/34—Details about subcooling of liquids
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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
- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/40—Vertical layout or arrangement of cold equipments within in the cold box, e.g. columns, condensers, heat exchangers etc.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Separation By Low-Temperature Treatments (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
For separating the synthesis gas (1 containing hydrogen and carbon monoxide, 5) in method, the synthesis gas is cooling in heat exchanger (E), partial condensation and the liquid (11) for being sent to the gas (7) and hydrogen-depleted gas in the first phase separator (9) with generation rich in hydrogen, at least part of the liquid of the hydrogen-depleted gas is sent to the top of stripping columns (13), at least part of the bottom liquid (17) of the stripping columns is at least partly vaporized into the heat exchanger, and the product rich in carbon monoxide is obtained from least part of the bottom liquid of the stripping columns.
Description
The present invention relates to the methods and apparatus for passing through partial condensation cryogenic separation synthesis gas.
Unit for producing carbon monoxide and hydrogen can be divided into two parts:
-Synthesis gas(mainly contain H2、CO、CH4、CO2, Ar and N2Mixture)Generation.For producing synthesis gas
In various commercial routes, the route based on coal gasification is seemingly growing, especially the country in the deposit rich in coal, example
Such as China.For individually or in low H2CO is produced under/CO output ratio, the technique of partial oxidation natural gas can also prove
It is advantageous.Another route is steam reforming.
-The purification of synthesis gas.It was found that following:
For being washed with liquid solvent to remove the unit for the most of sour gas being present in synthesis gas,
Unit for being purified on adsorbent bed,
For producing the unit of CO separated by low temperature " ice chest " approach.
By air flow bed or fluidized bed coal gasification production synthesis gas, ice chest process is partial condensation.For inciting somebody to action
Product from distillation is sent to production MEG (monoethylene glycol), TDI/MDI (toluene di-isocyanate(TDI) and/or methylenediphenyl two
Isocyanates) or PC (polycarbonate) application, need to include for separating the CH in ice chest4Column.Such as in FR 2 780
Described in 391, separation energy is provided by recycle compressor.Cooling syngas is to prevent in the pressure for being equivalent to compressor inlet pressure
The evaporation of low pressure recycle under power.The CO/CH4Column top condensation can be by the evaporative contribution of the circulation.
The present invention uses the ice chest of the partial condensation with synthesis gas, and wherein cooling syngas is to prevent being equivalent to for example
Required for application as producing monoethylene glycol, polycarbonate or toluene di-isocyanate(TDI), methylenediphenyl diisocyanates
It is evaporated under the pressure of the CO pressure directly generated under pressure from stripping column bottom, the pressure is usually between 5 and 9 bars.
It therefore, there is no need to compressor or CO be compressed in CO consumer by pump.
The cooling of synthesis gas of the invention is lower than in state of the art (warmer temperature), this causes than existing skill
The CO yield obtained in art level is lower.In some cases, such as when the gas that will be enriched in hydrogen is sent to methanol production list
When in member, the carbon monoxide also upgrading in methanol production unit that is present in the gas rich in hydrogen.
CO/CH4It is contributed back up through a part in liquid of the column top injection from stripping column bottom column top.
Theme according to the present invention, provides a kind of method for separating synthetic gas, which contains hydrogen, an oxygen
Change carbon and optionally methane and/or nitrogen and/or argon gas, in the method:
I) synthesis gas is cooled down in a heat exchanger, partial condensation and be sent in the first phase separator with generate be rich in
The gas of hydrogen and the liquid of hydrogen-depleted gas,
Ii after) depressurizing in valve, the liquid of the hydrogen-depleted gas is at least partly sent to the pressure between 6 and 20 bars of absolute values
The top of the stripping columns of lower operation,
Iii the gas rich in hydrogen is reheated in the heat exchanger without decompression or separation), and is not recycled
Into the synthesis gas,
Iv) at least part of the bottom liquid from the stripping columns is at least partly evaporated in the heat exchanger, and
And optionally reheat until the heat exchanger hot end to form gas,
V) top gas from the stripping columns is reheated in the heat exchanger without decompression or separation, and no longer
It is recycled in the synthesis gas,
And
Vi) gas rich in carbon monoxide is obtained from least part of the bottom liquid from the stripping columns, and is made
At least part of the liquid or the gas is used not pressurize before to it as final product.
Final product is discharged from the process to be sent to the product of client.
According to other optional aspects:
By at least part of the bottom liquid from the stripping columns, all the liquid is sent in the heat exchanger really
To evaporate it in the heat exchanger, without pressurizeing to it,
The synthesis gas is separated in the single phase separation device of the stripping columns upstream,
The stripping columns are equipped with the column of plate or filler,
First phase separator and any other phase separator if applicable had not both contained filler or had not contained
Plate,
The synthesis gas contains methane, and by a part of the bottom liquid from the stripping columns be sent in splitter with
The gas rich in carbon monoxide and the liquid rich in methane are generated, at least part of the bottom liquid is that the splitter is contributed
Whole condensation energy that column top needs,
All gases rich in carbon monoxide are reheated in the heat exchanger to serve as product,
The gas rich in carbon monoxide from the splitter is added in the heat exchanger again without decompression or separation
Heat, and be not recycled in the synthesis gas,
An oxygen of at least carbon monoxide of 20mol%, even at least 25mol% really should be contained rich in gas of hydrogen
Change carbon,
The gas rich in hydrogen is sent in the unit for being used to produce methanol as unstripped gas,
It is rich in the gas of carbon monoxide at most 80%, really even up to 75% yield production,
This method does not include the stage of compression fluid other than the optionally synthesis gas of the upstream stage i),
The synthesis gas reheats the bottom of the stripping columns, and if applicable, reheats on first phase separator
The bottom of the splitter of trip,
It is depressurized in the turbine in this method without stream,
Without providing the cryogenic liquid stream from external source for this method,
All liq from the stripping column bottom is used as process product knot after evaporating and optionally reheating
Beam, without as liquid pressing or as the liquid compression of evaporation.
According to another aspect of the present invention, it provides a kind of for separating containing hydrogen, carbon monoxide and optionally first
The equipment of the synthesis gas of alkane and nitrogen and/or argon gas, the equipment include heat exchanger, the first phase separator, stripping columns,
Have the device for staying in the heat exchanger cooling synthesis gas for conveying, for by the synthesis gas of the partial condensation be sent to this
To generate the device rich in the gas of hydrogen and the liquid of hydrogen-depleted gas in one phase separator, for being reheated in the heat exchanger
The gas rich in hydrogen is discharged to from the equipment afterwards and is not made its decompression, is isolated or follows it again together with synthesis gas
The device of ring, the device at the top for the liquid of the hydrogen-depleted gas to be at least partly sent to the stripping columns after depressurizing in valve, is used
Top gas is discharged to from the stripping columns of the equipment after reheating in the heat exchanger and is not made its decompression, is isolated
Or the device for recycling it together with synthesis gas, at least partly evaporation and optionally is stayed in the heat exchanger for conveying
Ground needs to be reheated until the hot end of the heat exchanger is to form at least one of the bottom liquid from the stripping columns of gas
The device divided, and for obtaining as final product from least part of the bottom liquid from the stripping columns rich in one
These devices are not connect by the device of the gas of carbonoxide with pump or compressor.
According to other optional aspects, which includes:
For whole bottom liquids from the stripping columns being sent in the heat exchanger to make it in the heat exchanger
The device of middle evaporation, and there is no pressurizing device between the stripping column bottom and the heat exchanger,
An oxidation is rich in for a part of the bottom liquid from the stripping columns to be sent in the splitter to generate
The device of the gas of carbon and the liquid rich in methane,
For generating the splitter of the gas rich in carbon monoxide and the liquid rich in methane,
It reheats for conveying to have to stay in the heat exchanger to serve as all gases rich in carbon monoxide of product
Device,
For the gas that should be rich in hydrogen to be sent to the device for being used to produce the unit of methanol as unstripped gas,
In addition to optionally in the synthesic gas compressor of the heat exchanger upstream other than, not be used for compression fluid device,
Reboiler is contained in the stripping column bottom,
Reboiler is contained in the separation column bottom,
For the synthesis gas is sent to the stripping columns reboiler and, if applicable, be sent in first phase point
The device of the reboiler of splitter from device upstream,
The equipment does not include carbon monoxide cycle,
The equipment includes the device for will be discharged as all gases rich in carbon monoxide of final product.
Optionally, which does not include turbine.
The present invention will be described in more detail with reference to the accompanying drawings, these attached drawings indicate according to the method for the present invention.
In Fig. 1, partial condensation stage is the stripping stages in the column 13 operated between 6 and 20 bars of absolute values later.
It will be containing hydrogen and carbon monoxide and there are also the synthesis gas 1 of optionally methane and/or nitrogen and/or argon gas in clean unit 3
Middle purification is to remove water and/or methanol and/or carbon monoxide.The gas 5 of formation is partly cooled down simultaneously in heat exchanger E
And it is used subsequently to the liquid 23 of the bottom reboiler 21 of heating stripping columns 13.So cooling gas is further cooled down until heat
The cold end of exchanger E is partly condensed, and is sent to phase separator 9, and separation is formed by liquid in the phase separator
Be formed by gas.The stripping columns operate under the pressure between 6 and 20 bars of absolute values.
The gas 7 that will be enriched in hydrogen is discharged from the top of the phase separator, and is sent to without decompression or separation for giving birth to
The unit for producing methanol reacts carbon monoxide and hydrogen to form methanol by catalysis in the unit.Make the liquid of hydrogen-depleted gas
11 depressurize and are sent to the top of stripping columns 13.In exchanger E again by the gas 15 formed at the top of stripping columns 13
Heating, without depressurizing or separating.Liquid 17 is set to depressurize and evaporate in heat exchanger E produced to be formed in valve
CO, without pressurizeing.
According to the alternative form of Fig. 1 shown in figure 2, conveying have stay in it is cooling from the stripping in heat exchanger E
It is discharged in cold end, depressurizes in valve 19, and separate in the second phase separator 27 by the liquid 17 of column bottom.It is handed in heat
The liquid 31 from the phase separator is reheated in parallel operation E, and combine with the gas 29 from the phase separator 27 it with
Form the carbon monoxide 33 produced by the equipment.
In this Fig. 2, the synthesis gas 5 of the heated reboiler 21 carried out since the medium temperature of exchanger E is not shown
Cooling with simplify the figure.The cooling of gas 5 is carried out in a manner of identical with Fig. 1.
In the case where synthesis gas contains methane, by Fig. 1 from stripping columns 13 containing methane and carbon monoxide
Bottom liquid 17 is sent to CO/CH4In splitter 37, while by being located at CO/CH4The room 39 of column top.Bottom liquid is evaporated wherein
A part of body 17 and as gas 43 from the room be discharged.Residue 45 is discharged from the room and is divided into two parts.In valve
In make part 49 depressurize and be sent to CO/CH as charging4The top of column 37.CO/CH as a result,4The reflux at 37 top of column is by column
A part 49 that the liquid 17 from 13 bottom of stripping columns is injected at top is contributed.
Depressurize residue 47 in valve to generate the stream of partial condensation.Separate section condenses in phase separator 55
Stream, and is mixed to form stream 53 for liquid phase 59 and gas phase 57, is again heated to the medium temperature of heat exchanger E, and as into
Material returns to CO/CH4In column 37.From CO/CH4The bottom discharge of column 37 is rich in the liquid 42 of methane, and then in heat exchanger
It is evaporated in E.Carbon monoxide 41 is used as gaseous products from CO/CH4The top of column 37 is discharged and reheats in heat exchanger E.
The product of distillation can be sent to production MEG (monoethylene glycol), TDI/MDI (toluene di-isocyanate(TDI) and/or methylene
Base diphenyl diisocyanate) or PC (polycarbonate).
The substitute for the Fig. 3 being shown in FIG. 4 is not used in CO/CH4The room 39 at 37 top of column.Bottom from stripping columns 13
Portion's liquid 17 is divided into two parts.It regard part 61 as CO/CH4The overhead-liquid of column conveys.Depressurize residue 63 in valve,
Separation is formed by the stream of part evaporation in phase separator 65, and liquid phase 69 and gas phase 67 are mixed, and is again heated to heat exchange
The medium temperature of device E, and CO/CH is returned to as stream 71 as charging4In column 37.From CO/CH4The bottom of column 37 is discharged rich
Liquid 42 containing methane, and evaporated in heat exchanger E.Carbon monoxide 41 is used as gaseous products from CO/CH4It arranges at the top of column
It reheats out and in heat exchanger E.
The synthesis gas 5 of Fig. 3 and 4 is cooling reheated in condenser/reboiler 21 before feeding phase separator 9 first
Bottom liquid from stripping columns and then in condenser/reboiler 81 reheat come from CO/CH4The bottom liquid of column.
It can be by two condenser/reboilers of synthesis gas parallel feed.
In all examples, cooled down by means of the evaporation of the liquid rich in carbon monoxide from the stripping column bottom
Synthesis gas to be separated, and the gaseous products that will be enriched in carbon monoxide (evaporate it in the bottom liquid CO from the stripping columns
Afterwards or in CO/CH4It is direct at column outlet) without compression as product convey.
The yield of carbon monoxide is typically about from 60% to 75%, and for state of the art, yield is 75%-
90%.
The invention enables being possible to carry out without CO compressor, and pass through in use in the first phase separator exit portion
To produce methanol, (it needs H to the gas rich in hydrogen for dividing condensation to generate2And CO) in the case where the loss of yield be not unfavorable
's.Compared with the 10-15mol% in state of the art, the CO content in this gas can be at least 20mol%, really very
To at least 25mol%.This CO upgrading in the production of methanol.
Compared with state of the art, the CO purity in our inventions is identical.For all these figures, can will steam
The product evaporated is sent to production MEG (monoethylene glycol), TDI/MDI (toluene di-isocyanate(TDI) and/or methylenediphenyl diisocyanate
Ester) or PC (polycarbonate).
This method is without using any turbine and preferably without using any of the cooling of the cryogenic liquid from external source
Contribution.In each figure, by the cooling of synthesis gas partial condensation by at least partly evaporation tribute of the bottom liquid from stripping columns
It offers.This evaporation carries out under single pressure.
Claims (15)
1. one kind be used for separating synthetic gas (1,5) method, the synthesis gas contain hydrogen, carbon monoxide and optionally methane and/
Or nitrogen and/or argon gas, in the method:
I) synthesis gas is cooling in heat exchanger (E), it partial condensation and is sent in the first phase separator (9) to generate richness
The gas (7) of hydrogen and the liquid (11) of hydrogen-depleted gas,
Ii after) being depressurized in valve, the liquid of the hydrogen-depleted gas is at least partly sent under the pressure between 6 and 20 bars of absolute values and is grasped
The top of the stripping columns (13) of work,
Iii the gas rich in hydrogen is reheated in the heat exchanger without decompression or separation), and is not recycled to this
In synthesis gas,
Iv) at least part of the bottom liquid (17,59,69) from the stripping columns is at least partly steamed in the heat exchanger
Hair, and optionally reheat until the heat exchanger hot end to form gas,
V) top gas (15) from the stripping columns is reheated in the heat exchanger without decompression or separation, and no longer
It is recycled in the synthesis gas,
And
Vi) gas (17,29,33,41) rich in carbon monoxide is obtained from least part of the bottom liquid from the stripping columns
, and use at least part of the liquid or the gas as not pressurizeing to it before final product.
2. the method for claim 1, wherein by least one from the bottom liquid (17) of the stripping columns (13)
Divide, be even all sent in the heat exchanger (E) to evaporate it in the heat exchanger, without adding to it really
Pressure.
3. the method for claim 1, wherein the synthesis gas contains methane, and will come from the bottom of the stripping columns (13)
At least part (61,63) of portion's liquid (17) is sent in splitter (37) to generate the gas (41) and richness that are rich in carbon monoxide
Liquid (42) containing methane, at least part of the bottom liquid are that the splitter contributes the whole condensations needed in column top
Energy.
4. method as claimed in claim 1,2 or 3, wherein reheated in the heat exchanger (E) all rich in carbon monoxide
Gas (17,29,33,41) to serve as product.
5. the method as described in one of preceding claims, wherein the gas (15) of hydrogen should be rich in containing at least 20mol%'s
Carbon monoxide, the really even at least carbon monoxide of 25mol%.
6. method as claimed in claim 5, wherein being sent to the gas (15) rich in hydrogen as unstripped gas for producing
In the unit of methanol.
7. the method as described in one of preceding claims, wherein produced at most 80%, really even up to 75% yield
Gas (17,29,33,41) rich in carbon monoxide.
8. the method as described in one of preceding claims, in addition to not wrapped except the optionally synthesis gas (1,5) of the upstream stage i)
Include the stage of compression fluid.
9. the method as described in one of preceding claims, wherein the synthesis gas (1,5) reheats the bottom of the stripping columns (13)
Portion, and if applicable, reheat the bottom of the splitter (37) of the first phase separator (9) upstream.
10. the method as described in one of preceding claims, wherein depressurized in the turbine in this method without stream.
11. the method as described in one of preceding claims does not use carbon monoxide cycle to provide cooling.
12. a kind of synthesis gas for separating containing hydrogen, carbon monoxide and optionally methane and/and/or nitrogen and/or argon gas
Equipment, the equipment include heat exchanger (E), the first phase separator (9), stripping columns (13), for convey stay in the heat friendship
The device of cooling synthesis gas in parallel operation, for the synthesis gas of the partial condensation to be sent in first phase separator to generate richness
The device of the liquid (11) of the gas (7) and hydrogen-depleted gas of hydrogen, for this to be rich in hydrogen after reheating in the heat exchanger
The device that the gas of gas is discharged from the equipment and does not make its decompression, is isolated or recycles it together with synthesis gas, is used
The liquid of the hydrogen-depleted gas is at least partly sent to the device at the top of the stripping columns after depressurizing in valve, in the heat exchange
In device reheat after by top gas (15) from the stripping columns of the equipment be discharged and do not make its decompression, be isolated or by its with
The device that synthesis gas recycles together at least partly evaporates and optionally needs again for conveying to stay in the heat exchanger
Heating forms at least part (59,69) of the bottom liquid from the stripping columns of gas up to the hot end of the heat exchanger
Device, and for obtaining being rich in as final product from least part of the bottom liquid (17) from the stripping columns
These devices, do not connect by the device of the gas (17,29,33,41) of carbon monoxide with pump or compressor.
13. equipment as claimed in claim 12 does not include carbon monoxide cycle.
14. equipment as described in claim 12 or 13, comprising for all rich in carbon monoxide of final product will to be used as
The device of gas (17,29,33,41) discharge.
15. the equipment as described in one of claim 12 to 14, comprising splitter (37) and for the stripping columns will to be come from
(13) a part (53) of bottom liquid (17) be sent in the splitter so as to generate be rich in carbon monoxide gas (41) and
The device of liquid (42) rich in methane.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1660209A FR3057942B1 (en) | 2016-10-21 | 2016-10-21 | METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A SYNTHESIS GAS BY PARTIAL CONDENSATION |
| FR1660209 | 2016-10-21 | ||
| FR1660482A FR3058207B1 (en) | 2016-10-28 | 2016-10-28 | PROCESS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE |
| FR1660482 | 2016-10-28 | ||
| CN2016212577565 | 2016-11-22 | ||
| CN201621257756.5U CN206831923U (en) | 2016-11-22 | 2016-11-22 | Equipment for separating the mixture containing hydrogen and carbon monoxide |
| PCT/FR2017/052879 WO2018073543A1 (en) | 2016-10-21 | 2017-10-19 | Method and equipment for cryogenically separating a synthesis gas by partial condensation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110114626A true CN110114626A (en) | 2019-08-09 |
| CN110114626B CN110114626B (en) | 2021-04-27 |
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| CN201780074179.7A Active CN110114626B (en) | 2016-10-21 | 2017-10-19 | Process and apparatus for the cryogenic separation of synthesis gas by partial condensation |
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| Country | Link |
|---|---|
| CN (1) | CN110114626B (en) |
| FR (1) | FR3057942B1 (en) |
| WO (1) | WO2018073543A1 (en) |
Citations (5)
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| CN1907849A (en) * | 2005-05-10 | 2007-02-07 | 林德股份公司 | Process and device for the recovery of products from synthesis gas |
| FR2930332A1 (en) * | 2008-04-18 | 2009-10-23 | Air Liquide | METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE |
| US20150233633A1 (en) * | 2014-02-17 | 2015-08-20 | Black & Veatch Corporation | Lng recovery from syngas using a mixed refrigerant |
| CN104870921A (en) * | 2012-08-02 | 2015-08-26 | 林德股份公司 | Method for the cryogenic separation of methane from synthesis gas, more particularly oxogas |
| CN105716370A (en) * | 2016-04-07 | 2016-06-29 | 开封空分集团有限公司 | System and method of preparing hydrogen rich gas and carbon monoxide from synthesis gas |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2780391B1 (en) | 1998-06-26 | 2000-10-20 | Air Liquide | PROCESS FOR PRODUCING CARBON MONOXIDE |
| FR2942869A1 (en) * | 2009-03-06 | 2010-09-10 | Air Liquide | Cryogenic separation method for mixture of carbon monoxide, hydrogen and nitrogen, involves constituting nitrogenless flow with final product at range or pressure higher than range set during pressurization in pump or compressor |
| FR2991442B1 (en) * | 2012-05-31 | 2018-12-07 | L'air Liquide,Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | APPARATUS AND METHOD FOR CRYOGENIC SEPARATION OF A MIXTURE OF CARBON MONOXIDE AND METHANE AND HYDROGEN AND / OR NITROGEN |
-
2016
- 2016-10-21 FR FR1660209A patent/FR3057942B1/en active Active
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2017
- 2017-10-19 WO PCT/FR2017/052879 patent/WO2018073543A1/en active Application Filing
- 2017-10-19 CN CN201780074179.7A patent/CN110114626B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907849A (en) * | 2005-05-10 | 2007-02-07 | 林德股份公司 | Process and device for the recovery of products from synthesis gas |
| FR2930332A1 (en) * | 2008-04-18 | 2009-10-23 | Air Liquide | METHOD AND APPARATUS FOR CRYOGENIC SEPARATION OF A MIXTURE OF HYDROGEN AND CARBON MONOXIDE |
| CN104870921A (en) * | 2012-08-02 | 2015-08-26 | 林德股份公司 | Method for the cryogenic separation of methane from synthesis gas, more particularly oxogas |
| US20150233633A1 (en) * | 2014-02-17 | 2015-08-20 | Black & Veatch Corporation | Lng recovery from syngas using a mixed refrigerant |
| CN105716370A (en) * | 2016-04-07 | 2016-06-29 | 开封空分集团有限公司 | System and method of preparing hydrogen rich gas and carbon monoxide from synthesis gas |
Also Published As
| Publication number | Publication date |
|---|---|
| FR3057942A1 (en) | 2018-04-27 |
| WO2018073543A1 (en) | 2018-04-26 |
| CN110114626B (en) | 2021-04-27 |
| FR3057942B1 (en) | 2019-12-27 |
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