CN104769376A - Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and/or nitrogen - Google Patents

Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and/or nitrogen Download PDF

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Publication number
CN104769376A
CN104769376A CN201380027819.0A CN201380027819A CN104769376A CN 104769376 A CN104769376 A CN 104769376A CN 201380027819 A CN201380027819 A CN 201380027819A CN 104769376 A CN104769376 A CN 104769376A
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China
Prior art keywords
tower
methane
liquid
rich
carbon monoxide
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CN201380027819.0A
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Chinese (zh)
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CN104769376B (en
Inventor
P·马蒂
J-J·塔尔伯特
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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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    • 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
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    • 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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    • 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
    • F25J3/0276—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/N2 mixtures, i.e. of ammonia synthesis gas
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    • 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
    • F25J2200/30—Processes or apparatus using separation by rectification using a side column in a single pressure column system
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    • 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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    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
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    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
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    • 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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    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
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    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
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    • 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
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/42—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • 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
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
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    • 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
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    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/02—Integration in an installation for exchanging heat, e.g. for waste heat recovery
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    • F25J2270/00—Refrigeration techniques used
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    • 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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    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/42—Modularity, pre-fabrication of modules, assembling and erection, horizontal layout, i.e. plot plan, and vertical arrangement of parts of the cryogenic unit, e.g. of the cold box

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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)
  • Carbon And Carbon Compounds (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

A device for cryogenically separating a mixture (5) of methane, carbon monoxide and hydrogen comprises a first separation unit comprising a first column (19), the first separation unit being supplied with the mixture (5), a first pipe for discharging a gas enriched with hydrogen (21) from the first unit, a second pipe for discharging a liquid (23) containing methane and carbon monoxide from the first unit, a second column (27) linked to the second pipe, a third pipe linked to the tank of the second column to withdraw a liquid enriched with methane (33) and a fourth pipe linked to the head of the second column to withdraw a gas enriched with carbon monoxide (43), the first pipe being arranged under the second column, the two columns having the same main axis, such that the liquid enriched with methane (33) is produced at a higher pressure than the pressure of the tank of the second column.

Description

For equipment and the method for the mixture of cryogenic separation carbon monoxide, methane and hydrogen and/or nitrogen
Technical field
The present invention relates to a kind of for cryogenic separation carbon monoxide, methane and hydrogen and the equipment of the mixture of nitrogen and method alternatively.
Described mixture can contain:
-carbon monoxide, hydrogen, and methane and Nitrogen gas impurity (H 2/ CO ice chest);
-nitrogen and hydrogen, carbon monoxide and methane impurities (ice chest by nitrogen purge).
Background technology
The known mixture to carbon monoxide, hydrogen and methane carries out first time cryogenic separation to produce hydrogen-rich gas and mainly containing CO, CH 4the liquid mixture of (and nitrogen).This second mixture is usually at CO/CH 4be separated in tower to produce the gas (nitrogenous) being rich in carbon monoxide and the liquid being rich in methane.
The several method for carrying out first time separation can be listed.
Knownly carry out carbon monoxide, hydrogen was separated with the first time of the mixture of methane, to remove hydrogen by partial condensation, subsequently at CO/CH 4be separated mainly carrying out second time containing carbon monoxide (with nitrogen) with the second mixture of methane in tower.
It is also known that the first time of carrying out mixture in carbon monoxide or methane or nitrogen washing tower is separated with the second mixture producing carbon monoxide and methane.Then this second mixture is at CO/CH 4be separated in tower.
The equipment that an object of the present invention is the mixture being used in cryogenic separation carbon monoxide, hydrogen and methane when methane must be produced under stress is compacter.
Another object of the present invention is, reduces the maximum height of the equipment of the mixture being used for cryogenic separation carbon monoxide, hydrogen and methane in some cases.It reduce cost and the cost of transportation of equipment.
In appropriate circumstances, from CO/CH 4the liquid methane that the bottom of tower is extracted out can be pressurized to be stored subsequently and/or to be transported to client in pump, or be sent to the top of methane wash column subsequently.
Another object of the present invention is by by making CO/CH to the supply of liquid methane pump 4the height of the bottom of tower raises the liquid that the static pressure that obtains is pressurizeed.
The feature of preamble is known from EP-A-1080765.
Summary of the invention
According to a theme of the present invention, provide a kind of equipment for cryogenic separation methane, carbon monoxide and hydrogen and the mixture of nitrogen alternatively, this equipment comprises: first separative element with at least the first tower and/or phase separator, and described first separative element is supplied to described mixture, for discharging the first pipeline of the gas being rich in hydrogen and be rich in nitrogen alternatively from first module, for from the first tower or the second pipe from the liquid of phase separator discharge containing methane and carbon monoxide, be connected to the second tower of second pipe, be connected to the bottom of the second tower to extract the 3rd pipeline being rich in the liquid of methane, with the top being connected to the second tower to extract the 4th pipeline being rich in the gas of carbon monoxide or nitrogen, first tower and/or one or more phase separator are located in below the second tower, these two towers or the second tower and phase separator have identical main shaft, thus the liquid being rich in methane produces under the pressure higher than the base pressure of the second tower, second tower comprises bottom reboiler, it is characterized in that, in the appropriate case, when described equipment comprises the first tower, this equipment does not comprise for transporting the overhead gas from the first tower to heat the device of the bottom reboiler of the second tower, and wherein second pipe is the pipeline of the bottom being connected to the first tower.
According to other optional aspect, described equipment comprises:
-being connected to the pump of the 3rd pipeline, this pump is positioned to bottom than the second tower closer to ground;
-stand-by still, the top of this stand-by still is connected to pump alternatively, the bottom of this stand-by still is connected to the top of the first tower by the device for the overhead gas from the first tower being delivered to the device bottom stand-by still and being used for the bottom liquid from stand-by still to deliver to the top of the first tower, and stand-by still is close to the first tower location;
-stand-by still is positioned to make the top than the first tower bottom it overhead farther;
-stand-by still is attached to the second tower;
-first module comprises pretreater, for mixture to be delivered to the pipeline of the first tower from pretreater, stand-by still is attached to this pretreater;
-described equipment comprises the finishing column being in the second tower downstream, and stand-by still is attached to this finishing column;
-first module comprises methane wash column, and this tower is connected to the first tower to its supply mixture, this mixture is the bottom liquid from methane wash column, and the top of methane wash column is connected to described pump;
-first module comprises phase separator and for transporting the device such as supplying the mixture of the first tower from the liquid of phase separator;
-first module comprises scrubbing tower and the first tower, and wash liquid is rich in carbon monoxide, and first module also comprises the device for the bottom liquid from scrubbing tower being delivered to the first tower;
-first module comprises scrubbing tower, and wash liquid is rich in nitrogen, and described scrubbing tower forms the first tower;
-for generation of the device of the liquid methane as final products;
-first module comprises nitrogen washing tower, and second liquid contains methane and nitrogen and the second tower and produces nitrogen-rich gas.
According to another theme of the present invention, provide a kind of method for cryogenic separation methane and carbon monoxide and hydrogen and the mixture of nitrogen alternatively, wherein, utilize and be supplied at least the first tower of mixture or phase separator and carry out first of described mixture and be separated and be rich in methane and the fluid containing carbon monoxide and/or nitrogen to produce in the bottom of the first tower or phase separator, described fluid is separated in the second tower to be rich in carbon monoxide to produce and to be rich in the gas of nitrogen alternatively and to be rich in the liquid of methane, first tower or phase separator are positioned below the second tower, described two towers or described second tower and phase separator have identical main shaft, thus the liquid being rich in methane is pressurizeed by static pressure at least in part, described second tower comprises bottom reboiler, it is characterized in that, in the appropriate case, the gas-heated of described bottom reboiler by not being overhead gas from the first tower, and be rich in the fluid source of methane from the bottom of the first tower.
According to other optional aspect of the present invention:
-described bottom reboiler is heated by recyclegas, and this recyclegas is carbon monoxide;
-being reheated in interchanger from the overhead gas of the first tower, mixture is cooled in this interchanger;
-be reheated in interchanger from whole overhead gas of the first tower;
-described in be rich in the liquid of methane pressurized closer to the pump on ground partially by the bottom be positioned to than the second tower;
-described pump is on ground;
-bottom of stand-by still is sent to from the overhead gas of the first tower, the liquid being rich in methane is sent to the top of described tower, and described stand-by still is positioned to next-door neighbour first tower;
-first module comprises pretreater, for mixture to be delivered to the pipeline of the first tower from pretreater, stand-by still is attached to this pretreater;
-described equipment comprises the finishing column being in the second tower downstream, and described stand-by still is attached to described finishing column;
-first module comprises methane wash column, and the bottom liquid from scrubbing tower is sent to described first tower as mixture, and the liquid being rich in methane through pressurization is sent to scrubbing tower;
-first module comprises scrubbing tower, and this scrubbing tower is supplied to the wash liquid being rich in carbon monoxide or nitrogen, and the bottom liquid from scrubbing tower is sent to the first tower;
-described method produces the liquid methane as final products, and this product source is from the bottom of the second tower;
-first module comprises nitrogen washing tower, and second liquid contains methane and nitrogen, and the second tower produces nitrogen-rich gas.
Accompanying drawing explanation
Illustrate in greater detail the present invention below with reference to accompanying drawings.
Fig. 1 shows the methane wash method according to prior art, Fig. 2 and 3 shows according to methane wash method of the present invention, Fig. 4 shows the method for partial condensation according to prior art, Fig. 5 shows according to method for partial condensation of the present invention, Fig. 6 shows the carbon monoxide washing methods according to prior art, Fig. 7 shows according to carbon monoxide washing methods of the present invention, and Fig. 8 shows the nitrogen washing method according to prior art, and Fig. 9 shows according to nitrogen washing method of the present invention.
Detailed description of the invention
According to Fig. 1, the mixture 1 of hydrogen, carbon monoxide and methane is cleaned to remove water and carbon dioxide in unit 3.Mixture 5 through purification is cooled to be sent to phase separator 7 in main low-temperature switch 9, separated to form the gas 11 being rich in hydrogen and the liquid 13 being rich in methane in phase separator.Gas 11 is separated in methane wash column 17, and this methane wash column is supplied to the wash liquid 41 being rich in methane at top.
Mix to be formed with liquid 13 from the bottom liquid of tower 17 and be rich in CO and CH 4and the liquid 18 containing nitrogen, this liquid 18 is sent to the top of the flash column 19 with bottom reboiler 22.The gas 21 extracted at the top of tower 19 is rich in hydrogen and is reheated in interchanger 9 for escalating into the purge gas usually delivering to fuel network.
Bottom liquid 23 from tower 19 mainly contains carbon monoxide (and nitrogen) and methane, and expands in valve 25, is then sent to CO/CH 4be separated in tower 27.The gas 44 being rich in carbon monoxide is formed at the top of described tower, and the liquid 33 being rich in methane is formed in the bottom of described tower.Liquid 33 is divided into two parts, and a part 37 is reheated (or not heating) for escalating into CO/CH in main low-temperature switch 9 again 4purge gas (or being in liquid form by walking around interchanger 9) under the pressure (several bar) of tower, another part 35 is pressurized with the top supplying methane wash column 17 and for upgrading (fluid 38) (or directly upgrading in liquid form by walking around interchanger 9) in a gaseous form under stress by means of main low-temperature switch 9 alternatively by pump 36.
Carbon monoxide cycle guarantees that described equipment keeps low temperature.The carbon monoxide being derived from the top of tower 27 is reheated in interchanger 9, delivers to compressor 51 as stream 45.Part carbon monoxide is generated as the gas 53 be under pressure in the exit of this compressor.Another part 57 is cooled and is divided into two parts in interchanger 9.The part 59 being in the medium temperature of interchanger 9 expands and delivers to compressor 51 via valve 63 by pipeline 65 in turbine 61.Another part 67 continues in interchanger 9 cooled.Cooling carbon monoxide portion 69 for heating flash evaporation tower 19 bottom reboiler 22 and be condensed.Another part 71 is for heating CO/CH 4the bottom reboiler 31 of tower 27 also mixes with part 69 of condensation.Whole stream 73 expands and is sent to CO/CH in valve 75 4the overhead condenser 29 of tower, in the gasification of this place to form carbon monoxide stream 43, this carbon monoxide stream 43 and from CO/CH 4the overhead gas mixing of tower.
A part from the liquid 77 of overhead condenser 29 is sent to phase separator 79.Extract liquid 81 from phase separator 79, this liquid is sent to interchanger 21, and this interchanger makes the middle extract cooling from methane wash column, and liquid 81 gasifies in this interchanger, and the gas of gained is sent to phase separator 79.Gas 83 from phase separator 79 is sent to the entrance of compressor 51 together with gas 43.
Be to be noted that three towers 17,27,19 are all placed on the ground, which increase floor space (space requirement).In order to respond for being rich in CH to pump 36 supply 4the static pressure height needed for liquid and do not occur cavitate risk, tower 27 is raised to enough height.
According to the present invention, as shown in Figure 2, CO/CH 4tower 27 is placed in above flash column 19, and described two towers have identical main shaft.Therefore, pump 36 is arrived and under being in elevated pressures due to static pressure from the liquid 33 being rich in methane of the bottom of described tower 27 through height H.This downstream of a part as pump 36 being in the liquid under the pressure of rising or product of upstream can be used.The ground space of the described tower of ice chest requires therefore to be lowered.In addition, if the summation of the height of two towers 27 and 19 is less than the height of tower 17, then the shell length of the tower of ice chest is not changed.
In the ice chest utilizing traditional methane wash as shown in Figure 1, the liquid phase 18 from the bottom of scrubbing tower 17 is sent to flash column 19.This has the effect that elimination is still dissolved in the residual hydrogen in carbon monoxide.
Different from Fig. 1, in order to improve the recovery of carbon monoxide, flash column comprises several additional column plate at the top of tower, forms the stand-by still 20 reducing diameter relative to tower 19.In this appendix section, gas phase is washed in a counter-current configuration by liquid methane 39, thus therefrom extracts the carbon monoxide still dissolved.Liquid/vapor flowing in this section 20 is very low: all other gas flow flowing into flash column 19 is positioned at below described portion section 20.In order to ensure good contact between the distribution of good liquid/vapor and each phase, the diameter of the top portion section 20 of flash column is reduced: to be therefore called " stand-by still " (steeple).
Tower 19 is supplied to wash liquid 18 below stand-by still.Stand-by still 20 is supplied to the liquid 39 being rich in methane being derived from pump 36 at top.Send as purge gas after being reheated in interchanger 9 from the overhead gas 21 of stand-by still.
(A) in order to help it to support, stand-by still 20 is combined in flash column 19 in the length of about one meter.
In addition, due to CO/CH 4laying of tower 27 requires certain height can supply enough available net positive suction head (being labeled as NPSH) to the methane pump or each pump 36 being positioned at bottom, in fig. 2, advises CO/CH 4tower 27 is positioned the top of flash column 19 (have or do not have stand-by still 20).The vertical accumulation of these two towers 19,27 or three towers 19,20,27 is usually combined, and that defines the height dimension of the housing of tower.Then Fig. 3 shows another modification, makes housing (flash column 19 and the CO/CH that can reduce tower 4the assembly of tower 27) vertical size.
An innovation of the present invention comprises the top-heavy new definition stand-by still 20 from flash column, such as, by being attached to the side of scrubbing tower 17.This is reorientated and can carry out in other position of ice chest (such as on another tower, such as the second tower 27 or finishing column are as denitrification column), as long as stand-by still 20 keeps being positioned to have the pressure head compared with lower part higher than flash column 19.This concept makes it possible to both below reductions:
Due to reason above-mentioned (A), reduce the length of the shell compared with lower part of flash column 19;
Due to reorientating of stand-by still 20, reduce CO/CH 4the height (simultaneously guaranteeing that new height keeps compatible with described or required by multiple methane pump NPSH) of the shell of tower 27.
When the shell sizes of described " tower " is arranged to be highly " flash column 19+CO/CH 4tower 27 " height of assembly time, then this is highly reduced.
According to Fig. 4, the mixture 1 of hydrogen, carbon monoxide and methane is cleaned to remove water and carbon dioxide in unit 3.Mixture 5 through purification is cooled to be sent to phase separator 7 in main low-temperature switch 9, separated to form hydrogen-rich gas 11 and the liquid 13 being rich in methane in phase separator.This liquid 13 is sent to the top of the flash column 19 with bottom reboiler 22.The gas 21 extracted from the top of tower 101 is rich in hydrogen and heats interchanger 9 for escalating into the purge gas usually delivering to fuel network again.
Bottom liquid 23 from tower 19 is mainly sent to CO/CH containing carbon monoxide and methane 4tower 27 is separated.The gas being rich in carbon monoxide is formed at the top of described tower, and the liquid 33 being rich in methane is formed in the bottom of described tower.Liquid 35 heats to be used as fuel again in interchanger.Liquid 33 is divided into two parts, and a part 37 is reheated (or not heating) for escalating into CO/CH in main low-temperature switch 9 again 4purge gas (or being in liquid form by walking around interchanger 9) under the pressure (several bar) of tower, another part 35 is pressurized for upgrading (fluid 38) (or directly upgrading in liquid form by walking around interchanger 9) in a gaseous form under stress via main low-temperature switch 9 alternatively by pump 36.
Carbon monoxide cycle guarantees that described equipment keeps low temperature.The carbon monoxide being derived from the top of tower 27 is reheated in interchanger 9, delivers to compressor 51 as stream 45.Part carbon monoxide is generated as the gas 53 be under pressure in the exit of compressor.Another part 57 is cooled and is divided into two parts in interchanger 9.The part 59 be under the medium temperature of interchanger 9 expands and delivers to compressor 51 via valve 63 by pipeline 65 in turbine 61.Another part 67 continues in interchanger 9 cooled.Cooling carbon monoxide portion 69 for heating tower 19 bottom reboiler 22 and be condensed.Another part 71 is for heating CO/CH 4the bottom reboiler 31 of tower 27 also mixes with part 69 of condensation.Whole stream 73 expands and is sent to CO/CH in valve 75 4the overhead condenser 29 of tower, in the gasification of this place to form carbon monoxide stream 43, this carbon monoxide stream 43 will be sent to compressor 51 after interchanger 9.
It should be noted, two towers 19 and 27 are all placed on the ground.
In the invention of Fig. 5, it should be noted, different from Fig. 4, tower 27 is positioned the top of tower 19, and tower 19 self poisoning is in the top of phase separator 7.Phase separator 7 can also be placed to next-door neighbour's two towers 101,27.
According to Fig. 6, the mixture 1 of hydrogen, carbon monoxide, nitrogen and methane is cleaned to remove water and carbon dioxide in unit 3.Mixture 5 through purification is cooled to be sent to phase separator 7 in interchanger 9, separated to form the gas 11 being rich in hydrogen and the liquid 13 being rich in methane at phase separator 7 place.Gas 11 is separated in carbon monoxide scrubbing tower 601, and this carbon monoxide scrubbing tower is supplied to the wash liquid 623 being rich in carbon monoxide at top.
Bottom liquid from tower 601 mixes to form liquid 18 with liquid 13, and the liquid formed is sent to the top of the flash column 19 with bottom reboiler 22.The gas 21 extracted from the top of tower 19 is rich in hydrogen and is reheated interchanger 9 for escalating into the purge gas usually delivering to fuel network.
Bottom liquid 23 from tower 19 is mainly sent to CO/CH containing carbon monoxide and methane 4be separated in tower 27.The gas 43 being rich in carbon monoxide is formed at the top of described tower, and the liquid 33 being rich in methane is formed in the bottom of described tower.Liquid 33 is divided into two parts, and a part 37 is reheated (or not heating) for escalating into CO/CH in main low-temperature switch 9 again 4purge gas (or being in liquid form by walking around interchanger 9) under the pressure (several bar) of tower 27, another part 35 is pressurized for upgrading (fluid 38) (or directly upgrading in liquid form by walking around interchanger 9) in a gaseous form under stress via main low-temperature switch 9 alternatively by pump 36.
Carbon monoxide cycle guarantees that described equipment keeps low temperature.The carbon monoxide being derived from the top of tower 27 is reheated in interchanger 9, delivers to compressor 51 as stream 45.Part carbon monoxide is generated as the gas 53 be under pressure in the exit of compressor.Another part 57 is cooled and is divided into two parts in interchanger 9.A part 59 expands and then delivers to compressor 51 by pipeline 65 in valve 63.Another part is divided into two parts.Cooling carbon monoxide portion 69 for heating flash evaporation tower 19 bottom reboiler 22 and be condensed.Another part 71 is for heating CO/CH 4the bottom reboiler 31 of tower 27 also mixes with part 71 of condensation.Whole stream 73 expands and is sent to CO/CH in valve 4the overhead condenser 619 of tower, in the gasification of this place to form carbon monoxide stream 43.The carbon monoxide storage tank (bain) 29 at the top place of tower 27 supplies gas to be condensed to condenser 619.
When carbon monoxide contains too much nitrogen, the overhead gas 635 from tower 27 is sent to the denitrification column 603 with overhead condenser 615.Bottom liquid 613 from denitrification column 603 is vaporized and mixes to form fluid 45 with fluid 43 in overhead condenser 615, and this fluid 45 delivers to compressor 51 via interchanger 9.The overhead gas 617 being rich in nitrogen is reheated and is sent to fuel network in interchanger 9.In tower 603, wash the fluid 609 and 611 that required carbon monoxide extracts by the discharge portion at compressor 51 provide.A part for these fluids is delivered to the top of scrubbing tower 601 as stream 623.When partly or entirely removing nitrogen from produced gas, above-mentioned all situations is all applicable to install denitrification column.
It should be noted, four towers 601,19,27,603 are all placed on the ground, which increase floor space.
According to the invention of Fig. 7, CO/CH 4tower 27 is positioned above flash column 19, and the liquid stream 35 being rich in methane is pressurizeed by static pressure in the upstream of pump 36.
Fig. 8 shows nitrogen washing method, and wherein the mixture 1 of hydrogen, carbon monoxide, nitrogen and methane leaves unit 804 and be cleaned to remove water, methyl alcohol and CO in clean unit 3 2(in above-mentioned all situations, also may require any other solvent adsorbing methyl alcohol or use in the washing of upstream).Then the mixture 5 of purification is cooled in interchanger 9 delivers to phase separator 7.Mix to form stream 11 with the uncolled part 6 of gas 5 from the gas of phase separator 7.A part for stream 11 is used for heating N again 2/ CH 4the bottom reboiler 851 of tower 850, is partly condensed simultaneously.The stream of partial condensation is sent to phase separator 809.Liquid 819 from separator 809 is rich in methane and is sent to pump 36.Gas 827 from separator 809 converges with the gas 821 from separator 7, and cooled in interchanger 9, then separated in phase separator 807, the gas 814 produced is supplied to nitrogen washing tower 811 so that separated.
Tower 811 is supplied to the liquid stream 833 produced by the liquefaction of gaseous nitrogen stream 831 in interchanger 9 at top.Another part 835 of condensation nitrogen mixes with the overhead gas 829 through heating again containing hydrogen from tower 811 and is sent to CO 2/ H 2s extraction cells (such as ) 804 for heat exchange; The gas 843 formed leaves described equipment.
Bottom liquid 847 from nitrogen washing tower 811 expands, and is then sent to phase separator 845.The gas 853 produced is reheated in interchanger 9 as purge gas.Liquid 849 supplies N 2/ CH 4tower 850 reduces to form methane and is rich in the gas flow 852 of nitrogen and is rich in the liquid stream of methane.The liquid stream 35 being rich in methane is sent to pump 36, then supplies phase separator 821.Gas 825 is sent to interchanger 9 to produce the gas phase being rich in methane.Liquid 823 also can be sent to interchanger 9 to produce the phase being rich in methane of the gaseous state be under pressure, or walks around interchanger 9 and be in liquid methane under pressure as final products to produce.The phase of methane can also be rich in by the gasify liquid that obtain in the upstream of pump 36 and the gaseous state that produces under low pressure or liquid state.
In the invention of Fig. 9, N 2/ CH 4tower 850 is positioned above nitrogen washing tower 811.
It is also conceivable that by uniquely tower 27 being placed on above phase separator---top of one in the separator 7,807,809,845 above the separator 7 in the top of the separator 7 in such as Fig. 4, Fig. 6 or in Fig. 8---and raise tower 27.

Claims (15)

1. the equipment for cryogenic separation methane, carbon monoxide and hydrogen and the mixture (5) of nitrogen alternatively, this equipment comprises: have at least the first tower (19,811) and/or phase separator (7,807,809,821,845) the first separative element, described first separative element is supplied to described mixture (5,814), for discharging the first pipeline of the gas (21,829) being rich in hydrogen and be rich in nitrogen alternatively from first module, for from the first tower or the second pipe from the liquid (23,847,849) of phase separator discharge containing methane and carbon monoxide, be connected to second tower (27,850) of second pipe, be connected to the bottom of described second tower to extract the 3rd pipeline being rich in the liquid (33) of methane, with the top being connected to the second tower to extract the gas (43 being rich in carbon monoxide or nitrogen, 852) the 4th pipeline, described first tower and/or one or more phase separator are located in below the second tower, described two towers or described second tower and described phase separator have identical main shaft, therefore under the pressure higher than the pressure of the second tower bottom, produce the liquid (33) being rich in methane, second tower comprises bottom reboiler (31), it is characterized in that, in the appropriate case, described equipment does not comprise for transporting the overhead gas from the first tower to heat the device of the bottom reboiler of the second tower, and wherein second pipe is the pipeline of the bottom being connected to the first tower.
2. equipment according to claim 1, comprises the pump (36) being connected to the 3rd pipeline, and this pump is positioned to bottom than the second tower (27,850) closer to ground.
3. equipment according to claim 2, comprise stand-by still (20), the top of this stand-by still is connected to described pump (36) alternatively, the bottom of this stand-by still is connected to the first tower (19 by the device for the overhead gas from the first tower being delivered to the device bottom stand-by still and being used for the bottom liquid from stand-by still to deliver to the top of the first tower, 811) top, described stand-by still is close to described first tower location alternatively.
4. equipment according to claim 3, wherein, described stand-by still (20) is positioned to make the top of ratio the first tower (19) bottom it overhead farther.
5. the equipment according to claim 3 or 4, wherein, described stand-by still (20) is attached to described second tower (27); Or described first module comprises pretreater (17), for mixture to be delivered to the pipeline of the first tower from pretreater, described stand-by still is attached to pretreater; Or described equipment comprises the finishing column being positioned at the second tower downstream, and described stand-by still is attached to finishing column.
6. the equipment according to any one of claim 2 to 5, wherein, described first module comprises methane wash column (17), this methane wash column is attached to the first tower (19) to the first tower supply mixture, this mixture is the bottom liquid from methane wash column, and the top of described methane wash column is connected to described pump (36).
7. equipment according to any one of claim 1 to 5, wherein, described first module comprises phase separator (7) and for transporting the device such as supplying the mixture of the first tower from the liquid of phase separator.
8. equipment according to any one of claim 1 to 5, wherein, described first module comprises scrubbing tower (601), and wash liquid is rich in carbon monoxide, and described first module also comprises the device for the bottom liquid from scrubbing tower being delivered to the first tower (19).
9., according to equipment in any one of the preceding claims wherein, comprise the device for generation of the liquid methane as final products.
10. the method for cryogenic separation methane and carbon monoxide and hydrogen and the mixture of nitrogen alternatively, wherein, utilize at least the first tower (19 being supplied to described mixture, 811) or at least phase separator (7, 807, 809, 821, 845) carry out first of described mixture to be separated and to be rich in methane and fluid (23 containing carbon monoxide and nitrogen alternatively to produce, 847, 849), described fluid is at the second tower (27, 850) in separated with produce be rich in carbon monoxide and be rich in the gas (45) of nitrogen alternatively and be rich in the liquid (35 of methane, 37), first tower or phase separator are positioned below the second tower, described two towers or described second tower have identical main shaft with phase separator, thus the liquid being rich in methane is pressurizeed by static pressure at least in part, described second tower comprises bottom reboiler (31), it is characterized in that, in the appropriate case, described bottom reboiler (31) is by heating from the gas (71) outside the overhead gas of the first tower, and be rich in the fluid source of methane from the bottom of the first tower.
11. methods according to claim 10, wherein, described bottom reboiler (31) is by recyclegas (71) heating, and this recyclegas is carbon monoxide.
12. methods according to claim 10 or 11, wherein, overhead gas (21) from described first tower (19) is reheated in interchanger (9), and described mixture is cooled in described interchanger (9).
13. methods according to claim 12, wherein, the whole overhead gas (21) from described first tower are reheated in interchanger (9).
14. according to claim 10 to the method according to any one of 13, wherein, described in be rich in the liquid (35) of methane pressurized closer to the pump (36) on ground partially by the bottom be positioned to than the second tower (27).
15. methods according to claim 14, wherein, described pump (36) rest on the ground.
CN201380027819.0A 2012-05-31 2013-05-06 For cryogenic separation carbon monoxide, methane and hydrogen and/or the equipment of the mixture of nitrogen and method Active CN104769376B (en)

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PCT/FR2013/051003 WO2013178901A2 (en) 2012-05-31 2013-05-06 Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and/or nitrogen

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