KR102794639B1 - Method and apparatus for separating synthesis gas by cryogenic distillation - Google Patents
Method and apparatus for separating synthesis gas by cryogenic distillation Download PDFInfo
- Publication number
- KR102794639B1 KR102794639B1 KR1020207028610A KR20207028610A KR102794639B1 KR 102794639 B1 KR102794639 B1 KR 102794639B1 KR 1020207028610 A KR1020207028610 A KR 1020207028610A KR 20207028610 A KR20207028610 A KR 20207028610A KR 102794639 B1 KR102794639 B1 KR 102794639B1
- Authority
- KR
- South Korea
- Prior art keywords
- tower
- gas
- recovered
- liquid
- strip
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead 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
- 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
-
- 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
-
- 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
- F25J2205/24—Processes or apparatus using other separation and/or other processing means using regenerators, cold accumulators or reversible heat exchangers
-
- 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
- F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
-
- 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
- F25J2235/60—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being (a mixture of) hydrocarbons
-
- 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
-
- 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
- F25J2270/04—Internal refrigeration with work-producing gas expansion loop
-
- 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
- F25J2270/24—Quasi-closed internal or closed external carbon monoxide refrigeration cycle
-
- 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
- F25J2270/88—Quasi-closed internal refrigeration or heat pump cycle, if not otherwise provided
-
- 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
- F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
- F25J2270/902—Details about the refrigeration cycle used, e.g. composition of refrigerant, arrangement of compressors or cascade, make up sources, use of reflux exchangers etc.
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
본 발명은 수소 및 일산화탄소를 포함하는 합성 가스를 극저온 증류에 의해 분리시키기 위한 방법에 관한 것으로서, 이에 따라, 합성 가스(1, 5)는 세척되어 극저온으로 냉각되며, 냉각된 합성 가스는 수소 감손 액체(33)를 생성하기 위해 제1 수단(15)에 의해 분리되고, 수소 감손 액체는 스트립탑(25)의 상부 부분으로 유입되며, 수소 농축 가스(27)는 스트립탑의 헤드에서 배출되고, 적어도 부분적으로 응축되어, 스트립탑의 상부 부분으로 다시 이송된다.The present invention relates to a method for separating a synthesis gas containing hydrogen and carbon monoxide by cryogenic distillation, whereby a synthesis gas (1, 5) is washed and cooled to a cryogenic temperature, the cooled synthesis gas is separated by a first means (15) to produce a hydrogen-depleted liquid (33), the hydrogen-depleted liquid is introduced into the upper part of a strip column (25), and a hydrogen-enriched gas (27) is discharged from the head of the strip column, is at least partially condensed and is conveyed back to the upper part of the strip column.
Description
본 발명은 극저온 증류(cryogenic distillation)에 의한 합성 가스의 분리를 위한 공정 및 장치에 관한 것이다.The present invention relates to a process and apparatus for separating synthesis gas by cryogenic distillation.
합성 가스는 주 성분으로서, 수소, 메탄 및 일산화탄소를 포함한다. 이는 또한 질소를 포함할 수 있다.Syngas contains hydrogen, methane and carbon monoxide as its main components. It may also contain nitrogen.
합성 가스를 이의 다양한 성분으로 분리시키기 위해, EP 0 465 366에 설명된 메탄 스크러빙(scrubbing) 유형의 공정을 사용하는 것이 알려져 있다. 이러한 공정은 특히, CO/CH4 탑(column)의 하부에서 회수된 메탄이 풍부한 유체의 일부를 스크러빙 유체로서 사용하는 것을 기반으로 하며, 이 경우 이러한 유체의 다른 일부는 메탄 퍼지(purge)의 형태로 회수된다.In order to separate synthesis gas into its various components, it is known to use processes of the methane scrubbing type as described in EP 0 465 366. These processes are based in particular on using a part of the methane-rich fluid recovered from the bottom of a CO/CH 4 column as scrubbing fluid, another part of this fluid being recovered in the form of a methane purge.
제1 탑은 CO 및 메탄이 풍부한 일부를 하부에서 회수하고, 수소가 풍부한 일부를 상부에서 회수하기 위해, 메탄 스크러빙을 수행한다.Tower 1 performs methane scrubbing to recover the CO and methane-rich portion from the bottom and the hydrogen-rich portion from the top.
제2 탑 또는 스트립탑(stripping column)(플래시 탑)은 제1 탑의 액체 일부에 함유된 몇 퍼센트의 수소를 배출시키기 위해 사용된다.A second column or stripping column (flash column) is used to remove a few percent of the hydrogen contained in the liquid portion of the first column.
또한, 메탄 스크러브탑(scrubbing column)에서 가스의 연속적인 냉각을 수행하는 것이 특허 FR 2 807 505 A1 또는 FR 2 807 504 A1에서 알려져 있다.Furthermore, it is known from patents FR 2 807 505 A1 or FR 2 807 504 A1 to carry out continuous cooling of the gas in a methane scrubbing column.
이는 스크러빙이 발열성이고 저온에서 더 효율적임에 따라, 가급적 극저온에 더 가까울수록, 제1 탑의 메탄 스크러빙의 효율을 개선할 수 있게 하기 때문이다.This is because scrubbing is exothermic and more efficient at lower temperatures, allowing for improved efficiency of methane scrubbing in the first tower the closer it is to cryogenic temperatures.
청구항 제1항의 전제부에 따른 공정은 WO 2013/178901 및 EP 317 851에서 알려져 있다. 종래기술의 이러한 공정에 따라, 스트립탑으로부터의 오버헤드 가스(overhead gas)는, 탑에 존재하는 전용 교환기를 사용하여 또는 메탄 스크러브탑과 결합된 보조 탑을 사용하여 냉각된다.A process according to the preamble of claim 1 is known from WO 2013/178901 and EP 317 851. According to this prior art process, the overhead gas from a strip tower is cooled either by means of a dedicated exchanger present in the tower or by means of an auxiliary tower combined with a methane scrub tower.
본 발명은 중간 가스 냉각과 함께 기존의 스크러브탑 설비를 사용함으로써, 성능 품질을 개선할 수 있게 한다.The present invention enables improved performance quality by using existing scrub top equipment together with intermediate gas cooling.
본 발명의 청구 대상 중에서,Among the claims of the present invention,
· 합성 가스 분리 장치에서 CO 회수 효율을 개선하거나,· Improve CO recovery efficiency in a synthesis gas separation unit, or
· 스트립탑의 특정 배치에 의해 동일한 CO 효율로 자본 비용을 최적화하는 것이 바람직하다.· It is desirable to optimize capital cost with the same CO efficiency by specific arrangement of strip towers.
본 발명의 방안은, 스트립탑의 상부 부분에서 회수된 가스를 메탄 스크러브탑의 적어도 하나의 중간 가스가 냉각되는 교환기에서 냉각 및 적어도 부분적으로 응축시키고, 이로부터 적어도 부분적으로 응축된 가스의 적어도 일부를 스트립탑의 상부 부분으로 복귀시키는 것이다. 스트립탑은 상부 부분, 및 상부 부분 아래의 하부 부분을 포함한다.The present invention provides a method of cooling and at least partially condensing gas recovered from an upper portion of a strip tower in an exchanger in which at least one intermediate gas of a methane scrub tower is cooled, and at least a portion of the at least partially condensed gas is returned to the upper portion of the strip tower. The strip tower comprises an upper portion and a lower portion below the upper portion.
냉각 시에, 상부 부분으로부터 회수된 이러한 가스는 상당한 양의 CO 및 메탄을 응축시킨다. 액체 일부는 스트립탑 상부 환류(reflux)로서 복귀함으로써, CO 및 메탄의 수율을 증가시킬 것이다. 이를 통해, EP 0 317 851 A2의 첨탑(minaret)을 부분적으로 대체할 수 있고, 한계 비용에 대한 수율을 회복할 수 있다. (아래 참조)When cooled, these gases recovered from the upper part condense significant amounts of CO and methane. A portion of the liquid will be returned as strip top reflux, thereby increasing the yield of CO and methane. This will allow the minaret of EP 0 317 851 A2 to be partially replaced, restoring the yield for marginal costs. (see below)
이는 또한 작업을 더 용이하게 할 수 있게 한다. 일반적으로, 스트립탑이 불충분하게 조정되는 경우, 적지 않은 양의 CO가 탑 상부에 남는다. 따라서, 이러한 냉각을 통해, 장치의 작업을 원활하게 할 수 있고, 사이클 압축기의 유량을 다소 증가시킴으로써 CO 수율의 어느 정도의 손실을 보정할 수 있다.This also makes the operation easier. Normally, if the strip tower is not adjusted enough, a considerable amount of CO remains at the top of the tower. Therefore, through this cooling, the operation of the device can be made smoother, and some loss in CO yield can be compensated by slightly increasing the flow rate of the cycle compressor.
스트립탑으로부터의 오버헤드 가스를 응축시키기 위해, 존재하는 탑에 따라, 상이한 유체가 사용될 수 있다.To condense the overhead gas from the strip tower, different fluids may be used, depending on the tower present.
후속적으로, 본 발명이 EP 0 317 851-A2에 설명된 바와 같은 스트립탑 첨탑과 조합되는 경우, 첨탑에서 상승하는 오버헤드 가스가 더 저온으로 스크러빙 구역에 유입될 것이다. 따라서, 첨탑의 메탄 스크러빙은 모두 보다 효과적일 것이다.Subsequently, if the present invention is combined with a strip top spire as described in EP 0 317 851-A2, the overhead gas rising from the spire will enter the scrubbing zone at a lower temperature. Therefore, the methane scrubbing of the spire will be altogether more effective.
CO 수율은 첨탑의 경우에 비해, 약 0.5% 내지 1%만큼 증가될 수 있다.The CO yield can be increased by about 0.5% to 1% compared to the spire case.
예를 들어, 스트립탑으로부터의 이러한 오버헤드 가스는 예를 들어, 액체 CO와 같은, 콜드 박스(cold box)로부터의 다른 유체와의 역류 방향으로 냉각될 수 있다.For example, these overhead gases from the strip tower can be cooled countercurrently with another fluid from the cold box, such as liquid CO.
FR 2 807 505-A1에 설명된 장치에 따라, 메탄 스크러빙의 맥락에서, 가급적 최저 온도로 작동하기 위해, 액체 CO 수용부(capacity)가 메탄 스크러브탑 상부에 설치된다는 점을 유의하는 것이 유리하다. 따라서, CO 회수 수율을 증가시키기 위해, 수용부로부터 비롯되는 액체 CO를 가열하는 역할을 하는 교환기에 스트립탑으로부터 비롯되는 가스를 추가하는 것으로 충분할 것이다. 스트립탑으로부터의 이러한 오버헤드 가스는 합성 가스 유량의 일부(2 내지 3%)만을 나타내는 반면에, 정상 시간으로 처리된 가스는 대략적으로 전체 수소 유량(즉, 유량의 70%)을 나타낸다. 따라서, 이러한 스트립탑 오버헤드 유체를 교환기에 추가하는 것은 자본 비용의 측면에서 미미한 것이며, 수율을 개선할 수 있게 한다.According to the device described in FR 2 807 505-A1, in the context of methane scrubbing, it is advantageous to note that the liquid CO capacity is installed above the methane scrub tower in order to operate at the lowest possible temperatures. Therefore, in order to increase the CO recovery yield, it may be sufficient to add gas from the strip tower to the exchanger, which serves to heat the liquid CO coming from the receiver. This overhead gas from the strip tower represents only a part of the synthesis gas flow (2 to 3%), whereas the gas treated in normal time represents roughly the entire hydrogen flow (i.e. 70% of the flow). Therefore, adding this strip tower overhead fluid to the exchanger is insignificant in terms of capital costs and allows for an improvement in the yield.
본 발명의 청구 대상에 따라, 극저온 증류에 의한 합성 가스의 분리를 위한 공정이 제공되며, 합성 가스는 수소, 일산화탄소 및 메탄, 그리고 가능하면 질소를 포함하고,According to the subject matter of the present invention, a process for the separation of synthesis gas by cryogenic distillation is provided, wherein the synthesis gas comprises hydrogen, carbon monoxide and methane, and possibly nitrogen,
i) 합성 가스는 정제되어 극저온으로 냉각되며,i) The synthesis gas is purified and cooled to cryogenic temperatures;
ii) 냉각된 합성 가스는 수소 감손 액체를 생성하기 위한 제1 수단에 의해 분리되고, 제1 수단에 의해 수행되는 분리는, 오버헤드 응축기를 갖는 일산화탄소와 메탄의 분리를 위한 탑으로부터 회수된 메탄 농축 액체의 적어도 일부를 통해 스크러브탑에서 스크러빙하는 단계를 포함하며, 응축기는 일산화탄소 사이클에 의해 냉각되고,ii) the cooled synthesis gas is separated by a first means for producing a hydrogen-depleted liquid, the separation performed by the first means comprising the step of scrubbing in a scrub tower through at least a portion of a methane-enriched liquid recovered from a tower for separation of carbon monoxide and methane having an overhead condenser, the condenser being cooled by the carbon monoxide cycle,
iii) 수소 감손 액체는 스트립탑의 상부 부분으로 유입되며, 스트립탑은 하부 부분을 더 포함하고,iii) The hydrogen-depleted liquid is introduced into the upper part of the strip tower, which further includes a lower part;
iv) 수소 농축 가스는 스트립탑의 상부에서 회수되며,iv) Hydrogen enriched gas is recovered from the top of the strip tower;
v) 스트립탑의 하부에서 액체가 회수되어 분리탑으로 이송되고, 일산화탄소 농축 및 메탄 감손 가스는 분리탑의 상부에서 회수되며, 일산화탄소 감손 및 메탄 농축 액체는 분리탑의 하부에서 회수되고, 일산화탄소 농축 가스는 생성물을 형성하기 위해 단계 i)의 합성 가스와의 열교환에 의해 가열되며,v) The liquid is recovered from the bottom of the stripping column and transferred to the separation column, the carbon monoxide-enriched and methane-depleted gas is recovered from the top of the separation column, the carbon monoxide-depleted and methane-enriched liquid is recovered from the bottom of the separation column, and the carbon monoxide-enriched gas is heated by heat exchange with the synthesis gas of step i) to form a product,
vi) 스트립탑의 상부 부분에서 회수된 가스는 적어도 부분적으로 응축되어 스트립탑의 상부 부분으로 적어도 부분적으로 복귀되고, 스트립탑의 상부 부분에서 회수된 가스는, 스크러브탑으로부터 회수된 적어도 하나의 가스를 냉각시키는 역할도 하는 열교환기에서 적어도 부분적으로 응축되며, 열교환기는 냉매를 가열하는 역할도 하는 것을 특징으로 한다.vi) the gas recovered from the upper portion of the strip tower is at least partially condensed and at least partially returned to the upper portion of the strip tower, and the gas recovered from the upper portion of the strip tower is at least partially condensed in a heat exchanger which also serves to cool at least one gas recovered from the scrub tower, wherein the heat exchanger also serves to heat the refrigerant.
다른 선택적인 양태에 따라,Depending on other optional aspects,
- 스트립탑의 상부 부분에서 회수된 가스는 일산화탄소 사이클 액체의 적어도 일부와 접촉되어 응축된다;- The gas recovered from the upper part of the strip tower is condensed by contacting at least a portion of the carbon monoxide cycle liquid;
- 합성 가스는 질소를 포함하며, 스트립탑으로부터 회수된 액체, 또는 이러한 액체로부터 유도된 유체는 탈질소탑(denitrogenation column)에서 분리되고, 탈질소탑의 액체는 스트립탑으로부터의 오버헤드 가스를 적어도 부분적으로 응축시키는 역할을 한다;- The synthesis gas contains nitrogen, and the liquid recovered from the stripping column, or a fluid derived from such a liquid, is separated in a denitrification column, the liquid of the denitrification column serving to at least partially condense the overhead gas from the stripping column;
- 스트립탑의 상부 부분에서 회수된 가스는, 분리탑으로부터 회수되어 가열되고 선택적으로 적어도 부분적으로 기화되는 일산화탄소 농축 액체와의 열교환에 의해 적어도 부분적으로 응축된다;- The gas recovered from the upper part of the strip tower is at least partially condensed by heat exchange with a carbon monoxide enriched liquid recovered from the separation tower, heated and optionally at least partially vaporized;
- 일산화탄소 농축 액체는, 분리탑의 증류 구역으로부터 또는 분리탑의 상부를 형성하는 수용부로부터 회수된다;- The carbon monoxide concentrated liquid is recovered from the distillation zone of the separation tower or from the receiving compartment forming the upper part of the separation tower;
- 스트립탑의 상부 부분으로부터 회수된 가스는, 스트립탑의 임의의 열 및 물질 전달 수단보다 높은 레벨로 회수된 스트립탑으로부터의 오버헤드 가스이다;- The gas recovered from the upper portion of the strip tower is overhead gas from the strip tower recovered at a level higher than any heat and mass transfer means of the strip tower;
- 스트립탑의 상부 부분으로부터 회수된 가스는, 스트립탑의 상부 아래의 적어도 하나의 이론단(theoretical plate)에서 회수되며, 분리탑으로부터 회수된 메탄 농축 액체의 일부는 가스의 회수를 위한 레벨보다 높은 스트립탑의 레벨로 이송된다;- The gas recovered from the upper part of the strip tower is recovered in at least one theoretical plate below the upper part of the strip tower, and a portion of the methane-enriched liquid recovered from the separation tower is transferred to a level of the strip tower higher than the level for gas recovery;
- 제1 수단에 의해 수행되는 분리는 메탄 농축 액체로 스크러빙하는 단계를 포함하지 않는다;- The separation performed by the first means does not include the step of scrubbing with a methane-enriched liquid;
- 공정은, 분리탑으로부터 비롯되는 일산화탄소 농축 가스를 사용하는 사이클에 의해 저온으로 유지된다;- The process is maintained at a low temperature by a cycle using carbon monoxide enriched gas coming from the separation tower;
- 수소 감손 액체는 1 몰% 내지 3 몰%의 수소를 포함한다;- The hydrogen-depleted liquid contains 1 mol% to 3 mol% hydrogen;
- 냉매는 일산화탄소로 농축된다;- The refrigerant is concentrated with carbon monoxide;
- 냉매는, 선택적으로 분리탑으로부터 비롯되어 제2 열교환기에서 기화되는 일산화탄소 농축 액체이다;- The refrigerant is a carbon monoxide enriched liquid, optionally derived from the separation tower and vaporized in the second heat exchanger;
- 제2 열교환기는 냉매에 의해서만 가열된다.- The second heat exchanger is heated only by the refrigerant.
본 발명의 다른 청구 대상에 따라, 극저온 증류에 의한 합성 가스의 분리를 위한 장치가 제공되며, 합성 가스는 수소, 일산화탄소, 메탄, 및 선택적으로 질소를 포함하고, 장치는, 열교환기; 메탄 스크러브탑인 제1 분리 수단; 스트립탑, 및 선택적으로, 일산화탄소와 메탄의 분리를 위한 탑; 합성 가스를 정제하기 위한 수단; 열교환기에서 극저온으로 냉각되도록 정제된 가스를 이송하기 위한 수단; 수소 감손 액체를 생성하기 위해, 냉각된 합성 가스를 제1 수단에 이송하기 위한 수단; 수소 감손 액체를 스트립탑의 상부 부분으로 유입시키기 위한 수단으로서, 스트립탑은 하부 부분을 더 포함하는, 수단; 스트립탑의 상부에서 수소 농축 가스를 회수하기 위한 수단; 스트립탑의 하부에서 액체를 회수하기 위한 수단; 제2 열교환기; 스트립탑의 상부 부분에서 회수된 가스를 그곳으로 이송하기 위한 수단, 및 제2 열교환기에서 적어도 부분적으로 응축된 가스의 적어도 일부를 스트립탑의 상부 부분에 이송하기 위한 수단; 일산화탄소와 메탄의 분리를 위한 탑에 스트립탑 하부 액체를 이송하기 위한 수단; 일산화탄소 농축 및 메탄 감손 가스를 분리탑의 상부에서 회수하기 위한 수단; 일산화탄소 감손 및 메탄 농축 액체를 분리탑의 하부에서 회수하기 위한 수단; 및 생성물을 형성하기 위해 합성 가스와의 열교환에 의해 열교환기에서 가열되도록, 일산화탄소 농축 가스를 이송하기 위한 수단을 포함하며, 장치는, 스크러브탑으로부터 회수된 적어도 하나의 가스를 제2 열교환기에서 냉각되도록 이송하기 위한 수단; 및 적어도 하나의 냉매를 제2 열교환기에서 가열되도록 이송하기 위한 수단을 포함하는 것을 특징으로 한다.In accordance with another object of the present invention, there is provided an apparatus for separating synthesis gas by cryogenic distillation, the synthesis gas comprising hydrogen, carbon monoxide, methane, and optionally nitrogen, the apparatus comprising: a heat exchanger; a first separation means, which is a methane scrub tower; a strip tower, and optionally, a tower for separating carbon monoxide and methane; means for purifying the synthesis gas; means for conveying the purified gas to be cryogenically cooled in the heat exchanger; means for conveying the cooled synthesis gas to the first means, to produce a hydrogen-depleted liquid; means for introducing the hydrogen-depleted liquid into an upper portion of the strip tower, the strip tower further comprising a lower portion; means for recovering a hydrogen-enriched gas from the upper portion of the strip tower; means for recovering a liquid from the lower portion of the strip tower; a second heat exchanger; means for conveying thereto gas recovered from the upper portion of the strip tower, and means for conveying at least a portion of the gas at least partially condensed in the second heat exchanger to the upper portion of the strip tower; A device comprising: means for conveying a strip tower bottom liquid to a tower for separation of carbon monoxide and methane; means for recovering a carbon monoxide enriched and methane depleted gas from an upper portion of the separation tower; means for recovering a carbon monoxide depleted and methane enriched liquid from a lower portion of the separation tower; and means for conveying the carbon monoxide enriched gas to be heated in a heat exchanger by heat exchange with a synthesis gas to form a product, wherein the device is characterized by comprising means for conveying at least one gas recovered from the scrub tower to be cooled in a second heat exchanger; and means for conveying at least one refrigerant to be heated in the second heat exchanger.
장치는,The device is,
- 스트립탑의 상부 부분에서 가스를 회수하고, 일산화탄소 사이클 액체의 적어도 일부와 접촉되어 응축되도록 이를 이송하기 위한 수단;- Means for recovering gas from the upper portion of the strip tower and conveying it so as to contact and condense it with at least a portion of the carbon monoxide cycle liquid;
- 합성 가스가 질소를 포함하는 경우, 스트립탑으로부터 회수된 액체 또는 이러한 액체로부터 유도된 유체를 분리시키기 위한 탈질소탑;- A denitrification tower for separating the liquid recovered from the strip tower or the fluid derived from such liquid, when the synthesis gas contains nitrogen;
- 스트립탑으로부터의 오버헤드 가스를 적어도 부분적으로 응축시키는 역할을 하도록, 스트립탑으로부터 회수된 액체를 이송하기 위한 수단;- Means for conveying liquid recovered from the strip tower so as to at least partially condense the overhead gas from the strip tower;
- 분리탑으로부터 회수되어 가열되고 선택적으로 적어도 부분적으로 기화되는 일산화탄소 농축 액체와 스트립탑의 상부 부분에서 회수된 가스 사이의 열교환을 가능하게 하기 위한 수단;- Means for enabling heat exchange between the carbon monoxide enriched liquid recovered from the separation tower, heated and optionally at least partially vaporized, and the gas recovered in the upper part of the strip tower;
- 분리탑의 증류 구역으로부터인 또는 분리탑의 상부를 형성하는 수용부로부터인 일산화탄소 농축 액체를 회수하기 위한 수단;- Means for recovering carbon monoxide enriched liquid from the distillation zone of the separation tower or from the receiving compartment forming the upper part of the separation tower;
- 스트립탑의 임의의 열 및 물질 전달 수단보다 높은 레벨로 회수된 스트립탑으로부터의 오버헤드 가스로서 스트립탑의 상부 부분으로부터 회수된 가스를 회수하기 위한 수단;- Means for recovering gas recovered from the upper portion of the strip tower as overhead gas from the strip tower recovered at a level higher than any heat and mass transfer means of the strip tower;
- 스트립탑의 상부 아래의 적어도 하나의 이론단에서 스트립탑의 상부 부분으로부터 회수된 가스를 회수하기 위한 수단;- Means for recovering gas recovered from the upper part of the strip tower in at least one theoretical plate below the upper part of the strip tower;
- 분리탑으로부터 회수된 메탄 농축 액체의 일부를 가스의 회수를 위한 레벨보다 높은 스트립탑의 레벨로 이송하기 위한 수단;- Means for transporting a portion of the methane enriched liquid recovered from the separation tower to a level of the strip tower higher than the level for gas recovery;
- 분리탑으로부터 비롯되는 일산화탄소 농축 가스를 사용하는 사이클을 포함하는 공정을 저온으로 유지시키기 위한 수단을 더 포함할 수 있으며,- may further include means for maintaining the process at a low temperature, including a cycle using carbon monoxide enriched gas from the separation tower;
- 제2 열교환기는 간접 열교환기이다.- The second heat exchanger is an indirect heat exchanger.
본 발명은 본 발명에 따른 공정을 예시적으로 각각 나타내는 도면을 참조하여 더 상세히 설명될 것이다.The present invention will be described in more detail with reference to the drawings, each illustrating by way of example a process according to the present invention.
도 1은 상 분리기(9), 메탄 스크러브탑(15), 스트립탑(25), 및 예를 들어, 탑들을 위한 구조화된 충전물을 수용하고, 극저온으로 작동할 수 있는, 일산화탄소와 메탄의 분리를 위한 탑(45)을 사용하는 공정을 도시한다.Figure 1 illustrates a process using a phase separator (9), a methane scrub tower (15), a strip tower (25), and a tower (45) for the separation of carbon monoxide and methane, which can accommodate structured packing for the towers and can operate at cryogenic temperatures.
일산화탄소, 메탄 및 일산화탄소를 포함하는 합성 가스(1)는 열교환기(7)에 도달하기 전에 정제 장치(3)에서 물 및/또는 이산화탄소가 정제되며, 열교환기(7)에서 극저온으로 냉각되어 부분적으로 응축된다.Synthesis gas (1) containing carbon monoxide, methane and carbon monoxide is purified of water and/or carbon dioxide in a purification device (3) before reaching the heat exchanger (7), and is partially condensed by being cooled to a cryogenic temperature in the heat exchanger (7).
수소 농축 가스(11) 및 수소 감손 액체(13)를 형성하기 위해, 상 분리기(9)에서 2개의 상이 분리된다. 교환기에서 가열되는 수소 농축 가스(19)를 생성하는 메탄 스크러브탑(15)의 하부로 가스(11)가 이송된다. 이러한 가스(19)의 일부는 정제 장치(3)를 재생시키는 역할을 한다.To form a hydrogen-enriched gas (11) and a hydrogen-depleted liquid (13), two phases are separated in a phase separator (9). The gas (11) is conveyed to the bottom of a methane scrub tower (15) where it produces a hydrogen-enriched gas (19) that is heated in an exchanger. A portion of this gas (19) serves to regenerate the purification unit (3).
탑(15)으로부터 회수된 적어도 하나의 중간 가스(21A, 21B, 21C)는 공정의 유체(이 경우, 액체(51))와의 간접 열교환에 의해 열교환기(23)에서 냉각된다.At least one intermediate gas (21A, 21B, 21C) recovered from the tower (15) is cooled in a heat exchanger (23) by indirect heat exchange with a process fluid (in this case, liquid (51)).
탑(15)으로부터의 하부 액체(17)는 분리기(9)로부터의 액체(13)와 합류되고, 1 몰% 내지 3 몰%의 수소를 함유하는 혼합물(91)이 스트립탑(25)의 상부로 이송된다. 스트립탑으로부터의 오버헤드 가스(27)가 열교환기(23)에서 적어도 부분적으로 응축된다. 적어도 부분적으로 응축된 가스의 적어도 일부(31)는 환류 액체를 제공하기 위해 스트립탑(25)의 상부에 복귀된다. 나머지(29)는 합성 가스(5)와 접촉되어 열교환기(7)에서 가열될 수 있다.The bottom liquid (17) from the top (15) is combined with the liquid (13) from the separator (9), and a mixture (91) containing 1 mol % to 3 mol % hydrogen is conveyed to the top of the strip tower (25). The overhead gas (27) from the strip tower is at least partially condensed in the heat exchanger (23). At least a portion (31) of the at least partially condensed gas is returned to the top of the strip tower (25) to provide a reflux liquid. The remainder (29) can be contacted with the synthesis gas (5) and heated in the heat exchanger (7).
열교환기(23)에서 냉각되도록 남겨진 냉매 가스(27)는 그 내부에서 적어도 부분적인 응축을 받을 것이다. 부분적인 응축의 경우, 액체 및 가스가 생성된다. 생성된 액체의 일부는 다른 파이프(31)를 통과하거나, 그렇지 않으면 냉각될 냉매 가스가 비롯되는 파이프(27)를 통해 복귀하여, 탑(25)에 합류되는 것이 가능하다. 이러한 두 번째 경우에는, 파이프(31)가 필요하지 않다.The refrigerant gas (27) left to be cooled in the heat exchanger (23) will undergo at least a partial condensation therein. In the case of a partial condensation, liquid and gas are produced. It is possible that a part of the produced liquid passes through another pipe (31) or else returns through the pipe (27) from which the refrigerant gas to be cooled comes and joins the tower (25). In this second case, the pipe (31) is not necessary.
스트립탑(25)의 하부에서 획득된 액체(33)는 교환기(7)에서 냉각되어 분리탑(45)으로 이송된다. 동일한 액체의 다른 부분(35)은 하부 리보일러(reboiler)(37)에서 기화되어 스트립탑의 하부에 복귀된다.The liquid (33) obtained from the bottom of the strip tower (25) is cooled in the exchanger (7) and transferred to the separation tower (45). Another portion (35) of the same liquid is vaporized in the bottom reboiler (37) and returned to the bottom of the strip tower.
분리탑은 증류에 의한 분리를 위한 다수의 구역, 및 선택적으로 수용부(99)를 포함한다. 이는 하부 액체(75)를 가열하는 역할을 하는 하부 리보일러(73)를 가지며, 형성된 가스는 하부로 복귀된다. 메탄 농축 하부 액체(77)는 2개로 분할된다. 일부(83)는 연료를 형성하기 위해 교환기(7)에서 기화된다. 나머지(85)는 펌프(87)에 의해 가압되어 스크러브탑(15)의 상부로 이송된다.The separation tower comprises a number of zones for separation by distillation, and optionally a receiving section (99). It has a bottom reboiler (73) which serves to heat the bottom liquid (75), the formed gas being returned to the bottom. The methane-enriched bottom liquid (77) is split into two. A portion (83) is vaporized in the exchanger (7) to form fuel. The remainder (85) is pressurized by a pump (87) and conveyed to the top of the scrub tower (15).
탑으로부터의 일산화탄소 농축 오버헤드 가스(43)는 일산화탄소 농축 가스(57)를 생성하는 생성물 압축기(57)로 이송된다. 일산화탄소 농축 가스의 일부(61)는 냉각되어 2개로 분할된다. 일부(65)는 저온을 제공하기 위해 터빈(67)에서 팽창된다. 팽창된 가스(89)는 압축기(57)의 흡입구로 복귀된다. 나머지 가스(69)는 교환기(7)에서 계속 냉각되고, 리보일러(73 및 37)를 가열하는 역할을 한다(흐름(93 및 73)). 따라서, 리보일링을 위해 사용되었던 가스가 부분적으로 응축되어, 분리탑(45)의 상부의 수용부(99)에 흐름(97)으로서 공급된다. 수용부(99)로부터의 가스(41)는 압축기(57)에 공급된다. 수용부(99)로부터의 액체(47)는 상 분리기(49)로 이송되고, 분리기로부터의 액체(51)는, 스트립탑으로부터의 오버헤드 가스(27) 뿐만 아니라 중간 가스(21A, 21B, 21C)를 냉각시키기 위한 열교환기(23)의 냉매 역할을 한다. 따라서, 액체(51)가 기화되어 상 분리기(49)로 복귀되며, 이로부터의 가스(53)가 압축기(57)에 공급된다.The carbon monoxide enriched overhead gas (43) from the tower is conveyed to the product compressor (57) which produces carbon monoxide enriched gas (57). A portion (61) of the carbon monoxide enriched gas is cooled and split into two. A portion (65) is expanded in the turbine (67) to provide a low temperature. The expanded gas (89) is returned to the suction of the compressor (57). The remaining gas (69) continues to be cooled in the exchanger (7) and serves to heat the reboilers (73 and 37) (streams (93 and 73)). Thus, the gas used for reboilment is partially condensed and supplied as stream (97) to the receiver (99) at the top of the separation tower (45). The gas (41) from the receiver (99) is supplied to the compressor (57). The liquid (47) from the receiving unit (99) is transferred to the phase separator (49), and the liquid (51) from the separator acts as a refrigerant in the heat exchanger (23) to cool the overhead gas (27) from the strip tower as well as the intermediate gases (21A, 21B, 21C). Accordingly, the liquid (51) is vaporized and returned to the phase separator (49), and the gas (53) therefrom is supplied to the compressor (57).
분리탑의 분리 구역으로부터 회수된 액체는 공정의 액체(47) 또는 다른 액체를 대체할 수 있다.The liquid recovered from the separation section of the separation tower can replace the process liquid (47) or another liquid.
도 2에 도시된 공정의 대안적인 형태에 따라, 스트립탑은 메탄 스크러빙 구역을 포함하며, 펌프(87)에 의해 가압된 액체(85)의 일부는 스트립탑(25)의 상부로 이송되고, 다른 일부는 도 1에서와 같이, 스크러브탑(15)의 상부로 이송된다.According to an alternative form of the process illustrated in FIG. 2, the strip tower comprises a methane scrubbing section, and a portion of the pressurized liquid (85) by the pump (87) is conveyed to the top of the strip tower (25), and another portion is conveyed to the top of the scrub tower (15), as in FIG. 1.
이 경우, 스트립탑(25)으로부터 회수된 가스(27)는 탑의 상부 아래의 적어도 하나의 이론적 플래토(theoretical plateau)에서 획득된다.In this case, the gas (27) recovered from the strip tower (25) is obtained from at least one theoretical plateau below the top of the tower.
교환기(23)에서 적어도 부분적으로 응축된 가스는 회수 지점 옆의 스트립탑으로 복귀하고, 스트립탑의 상부 부분(스크러빙 구역(25A))에서 상승하는 가스는 수소로 더 농축됨으로써, 필요한 이론단수를 감소시킬 수 있게 한다.The gas, at least partially condensed in the exchanger (23), is returned to the strip tower next to the recovery point, and the gas rising from the upper part of the strip tower (scrubbing section (25A)) is further concentrated with hydrogen, thereby reducing the required number of theoretical plates.
도 3에 도시된 바와 같이, 본 발명은 공정이 메탄 스크러브탑을 사용하지 않는 경우에도 적용된다. 이 경우, 제1 분리는 간단히 분리기(9)에서의 부분적인 응축에 의해 수행된다. 가스(11)가 가열되고, 수소 감손 액체(13)는 스트립탑(25)으로 이송된다. 후자는 요건에 따라, 도 2에서와 같은 메탄 스크러빙 구역을 포함할 수 있거나 포함하지 않을 수 있다.As illustrated in Figure 3, the present invention also applies when the process does not use a methane scrub tower. In this case, the first separation is simply carried out by partial condensation in the separator (9). The gas (11) is heated and the hydrogen-depleted liquid (13) is conveyed to a strip tower (25). The latter may or may not include a methane scrubbing section, as in Figure 2, depending on the requirements.
이 경우에는, 메탄 스크러빙 구역(25A)이 존재하므로, 도 2에서와 같이, 스트립탑으로부터 회수된 가스(27)가 중간 레벨로 획득된다.In this case, since a methane scrubbing zone (25A) exists, the gas (27) recovered from the strip tower is obtained at an intermediate level, as in Fig. 2.
따라서, 모든 가압된 메탄은 스트립탑(25)의 상부로 이송된다.Therefore, all the pressurized methane is transported to the top of the strip tower (25).
스크러브탑(15)이 없는 경우, 열교환기(23)가 단순화되고, 단지 2개의 유체(냉각될 가스(27) 및 가열될 액체(51)) 사이의 열교환만을 가능하게 한다.In the absence of a scrub top (15), the heat exchanger (23) is simplified and only allows heat exchange between two fluids (the gas to be cooled (27) and the liquid to be heated (51)).
구역(25A)이 없는 경우, 가스(27)는 탑(25)의 상부에서 획득된다.In the absence of zone (25A), gas (27) is obtained from the top of the tower (25).
Claims (15)
상기 합성 가스는 수소, 일산화탄소 및 메탄, 그리고 가능하면 질소를 포함하고,
i) 상기 합성 가스(1, 5)는 정제되어 극저온으로 냉각되며,
ii) 상기 냉각된 합성 가스는 수소 감손 액체(91)를 생성하기 위한 제1 수단(9, 15)에 의해 분리되고, 상기 제1 수단에 의해 수행되는 상기 분리는, 오버헤드 응축기를 갖는 일산화탄소와 메탄의 분리를 위한 탑으로부터 회수된 메탄 농축 액체의 적어도 일부를 통해 스크러브탑(15)에서 스크러빙하는 단계를 포함하며, 상기 응축기는 일산화탄소 사이클에 의해 냉각되고,
iii) 상기 수소 감손 액체는 스트립탑(25)의 상부 부분으로 유입되며, 상기 스트립탑(25)은 하부 부분을 더 포함하고,
iv) 수소 농축 가스(27, 29)가 상기 스트립탑의 상부에서 회수되며,
v) 상기 스트립탑의 하부에서 액체(33)가 회수되어 분리탑(45)으로 이송되고, 일산화탄소 농축 및 메탄 감손 가스(43)가 상기 분리탑의 상부에서 회수되며, 일산화탄소 감손 및 메탄 농축 액체(77)가 상기 분리탑의 하부에서 회수되고, 상기 일산화탄소 농축 가스는, 생성물(29)을 형성하기 위해 단계 i)의 상기 합성 가스와의 열교환에 의해 가열되며,
vi) 상기 스트립탑의 상부 부분에서 회수된 가스(27)는 적어도 부분적으로 응축되어 상기 스트립탑의 상부 부분으로 적어도 부분적으로 복귀되고,
상기 스트립탑의 상부 부분에서 회수된 상기 가스는, 상기 스크러브탑으로부터 회수된 적어도 하나의 가스(210, 211)를 냉각시키는 역할도 하는 열교환기(23)에서 적어도 부분적으로 응축되며, 상기 열교환기는 냉매를 가열하는 역할도 하는 것을 특징으로 하는,
극저온 증류에 의한 합성 가스의 분리를 위한 공정.A process for separating synthesis gas by cryogenic distillation,
The above synthesis gas contains hydrogen, carbon monoxide and methane, and possibly nitrogen,
i) The above synthesis gas (1, 5) is purified and cooled to a cryogenic temperature,
ii) the cooled synthesis gas is separated by a first means (9, 15) for producing a hydrogen-depleted liquid (91), the separation performed by the first means comprising the step of scrubbing in a scrub tower (15) at least a portion of a methane-enriched liquid recovered from a tower for separation of carbon monoxide and methane having an overhead condenser, the condenser being cooled by a carbon monoxide cycle,
iii) The hydrogen-depleted liquid is introduced into the upper part of the strip tower (25), and the strip tower (25) further includes a lower part,
iv) Hydrogen enriched gas (27, 29) is recovered from the top of the strip tower,
v) Liquid (33) is recovered from the bottom of the strip tower and transferred to a separation tower (45), carbon monoxide-enriched and methane-depleted gas (43) is recovered from the top of the separation tower, carbon monoxide-depleted and methane-enriched liquid (77) is recovered from the bottom of the separation tower, and the carbon monoxide-enriched gas is heated by heat exchange with the synthesis gas of step i) to form a product (29).
vi) The gas (27) recovered from the upper part of the strip tower is at least partially condensed and at least partially returned to the upper part of the strip tower,
The gas recovered from the upper part of the strip tower is at least partially condensed in a heat exchanger (23) which also serves to cool at least one gas (210, 211) recovered from the scrub tower, characterized in that the heat exchanger also serves to heat the refrigerant.
Process for separation of synthesis gas by cryogenic distillation.
상기 스트립탑의 상부 부분에서 회수된 상기 가스(27)는 상기 일산화탄소 사이클 액체의 적어도 일부(51)와 접촉되어 응축되는, 공정.In the first paragraph,
A process in which the gas (27) recovered from the upper portion of the strip tower is condensed by contacting at least a portion (51) of the carbon monoxide cycle liquid.
상기 합성 가스(1, 5)는 질소를 포함하며,
상기 스트립탑(25)으로부터 회수된 상기 액체, 또는 이러한 액체로부터 유도된 유체는 탈질소탑(55)에서 분리되고, 이의 상기 액체는 상기 스트립탑의 상부 부분에서 회수된 가스를 적어도 부분적으로 응축시키는 역할을 하는, 공정.In paragraph 1 or 2,
The above synthesis gas (1, 5) contains nitrogen,
A process wherein the liquid recovered from the strip tower (25), or a fluid derived from such liquid, is separated in a denitrification tower (55), the liquid serving to at least partially condense the gas recovered in the upper portion of the strip tower.
상기 스트립탑의 상부 부분에서 회수된 상기 가스(27)는, 상기 분리탑(45)으로부터 회수되어 가열되고 선택적으로 적어도 부분적으로 기화되는 일산화탄소 농축 액체와의 열교환에 의해 적어도 부분적으로 응축되는, 공정.In paragraph 1 or 2,
A process wherein the gas (27) recovered from the upper portion of the strip tower is at least partially condensed by heat exchange with a carbon monoxide enriched liquid recovered from the separation tower (45), heated and optionally at least partially vaporized.
상기 일산화탄소 농축 액체(47)는, 상기 분리탑(45)의 증류 구역으로부터 또는 상기 분리탑의 상부를 형성하는 수용부로부터 회수되는, 공정.In paragraph 4,
The above carbon monoxide concentrated liquid (47) is recovered from the distillation zone of the separation tower (45) or from the receiving portion forming the upper portion of the separation tower.
상기 스트립탑의 상부 부분으로부터 회수된 상기 가스(27)는, 상기 스트립탑의 임의의 열 및 물질 전달 수단보다 높은 레벨로 회수된 상기 스트립탑으로부터의 오버헤드 가스인, 공정.In paragraph 1 or 2,
The gas (27) recovered from the upper portion of the strip tower is an overhead gas from the strip tower recovered at a level higher than any heat and mass transfer means of the strip tower.
상기 스트립탑의 상부 부분으로부터 회수된 상기 가스는 상기 스트립탑의 상부 아래의 적어도 하나의 이론단에서 회수되며,
상기 분리탑으로부터 회수된 상기 메탄 농축 액체의 일부는 상기 가스의 회수를 위한 레벨보다 높은 상기 스트립탑의 레벨로 이송되는, 공정.In paragraph 1 or 2,
The gas recovered from the upper portion of the strip tower is recovered from at least one theoretical plate below the upper portion of the strip tower,
A process wherein a portion of the methane enriched liquid recovered from the separation tower is transferred to a level of the strip tower higher than the level for recovery of the gas.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1852439A FR3079288B1 (en) | 2018-03-21 | 2018-03-21 | METHOD AND APPARATUS FOR SEPARATING SYNTHESIS GAS BY CRYOGENIC DISTILLATION |
| FR1852439 | 2018-03-21 | ||
| PCT/FR2019/050624 WO2019180374A1 (en) | 2018-03-21 | 2019-03-20 | Method and appliance for separating a synthesis gas by cryogenic distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20200135805A KR20200135805A (en) | 2020-12-03 |
| KR102794639B1 true KR102794639B1 (en) | 2025-04-16 |
Family
ID=77417440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020207028610A Active KR102794639B1 (en) | 2018-03-21 | 2019-03-20 | Method and apparatus for separating synthesis gas by cryogenic distillation |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20210055047A1 (en) |
| EP (1) | EP3769022B1 (en) |
| KR (1) | KR102794639B1 (en) |
| CN (1) | CN111886465B (en) |
| SG (1) | SG11202008918SA (en) |
| WO (1) | WO2019180374A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102826876B1 (en) | 2022-04-18 | 2025-06-30 | (주)원익머트리얼즈 | Method for purifying low-purity carbon monoxide and apparatus therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007502398A (en) | 2003-05-19 | 2007-02-08 | レール・リキード−ソシエテ・アノニム・ア・ディレクトワール・エ・コンセイユ・ドゥ・スールベイランス・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method and apparatus for providing a fluid mixture containing at least 10% carbon monoxide |
| CN104769376A (en) | 2012-05-31 | 2015-07-08 | 乔治洛德方法研究和开发液化空气有限公司 | Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and/or nitrogen |
| WO2017212136A1 (en) | 2016-06-06 | 2017-12-14 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and facility for combined production of a mixture of hydrogen and nitrogen as well as carbon monoxide by cryogenic distillation and scrubbing |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6800551A (en) * | 1968-01-12 | 1969-07-15 | ||
| DE2912761A1 (en) * | 1979-03-30 | 1980-10-09 | Linde Ag | METHOD FOR DISASSEMBLING A GAS MIXTURE |
| DE3736354A1 (en) * | 1987-10-27 | 1989-05-11 | Linde Ag | PROCESS FOR H (DOWN ARROW) 2 (DOWN ARROW) / CO-DISASSEMBLY BY PARTIAL CONDENSATION AT DEEP TEMPERATURE |
| DE3739724A1 (en) * | 1987-11-24 | 1989-06-08 | Linde Ag | METHOD AND DEVICE FOR DISASSEMBLING A GAS MIXTURE |
| FR2655137B1 (en) * | 1989-11-28 | 1992-10-16 | Air Liquide | AIR DISTILLATION PROCESS AND INSTALLATION WITH ARGON PRODUCTION. |
| FR2664263B1 (en) | 1990-07-04 | 1992-09-18 | Air Liquide | PROCESS AND PLANT FOR THE SIMULTANEOUS PRODUCTION OF METHANE AND CARBON MONOXIDE. |
| DE4210637A1 (en) * | 1992-03-31 | 1993-10-07 | Linde Ag | Process for the production of high-purity hydrogen and high-purity carbon monoxide |
| FR2728663B1 (en) * | 1994-12-23 | 1997-01-24 | Air Liquide | PROCESS FOR SEPARATING A GASEOUS MIXTURE BY CRYOGENIC DISTILLATION |
| FR2807504B1 (en) | 2000-04-07 | 2002-06-14 | Air Liquide | COLUMN FOR CRYOGENIC SEPARATION OF GASEOUS MIXTURES AND METHOD FOR CRYOGENIC SEPARATION OF A HYDROGEN AND CO-CONTAINING MIXTURE USING THE SAME |
| FR2807505B1 (en) * | 2000-04-07 | 2002-06-14 | Air Liquide | LIQUID-GAS DISPENSER FOR MATERIAL AND / OR HEAT EXCHANGE COLUMN, AND COLUMN USING SUCH A DISPENSER |
| FR2916264A1 (en) * | 2006-12-21 | 2008-11-21 | Air Liquide | Mixture separating method, involves separating mixture using carbon monoxide cycle, where cycle assures cooling of methane at washing column, over-cooling of washing column and/or condensation at top of denitrification column |
| EP2149769A1 (en) * | 2008-07-31 | 2010-02-03 | BP Alternative Energy International Limited | Separation of carbon dioxide and hydrogen |
| CN101659316A (en) * | 2009-09-15 | 2010-03-03 | 王德荣 | Marine inert gases system |
| CN102435045A (en) * | 2011-12-14 | 2012-05-02 | 杭州中泰深冷技术股份有限公司 | Liquid nitrogen washing and purifying synthesis gas and cryogenic separation and LNG recovery device thereof |
| DE102012004047A1 (en) * | 2012-03-02 | 2013-09-05 | Linde Ag | Method for producing e.g. gas product, involves carrying out decomposition in carbon dioxide product, and returning residual gas into carbon monoxide methane separation unit such that lossless methane process operation is performed |
| CN104445272B (en) * | 2014-11-28 | 2016-04-27 | 王文领 | A kind of conversion gas phlegma comprehensive reutilization method containing ammonia, carbonic acid gas |
-
2019
- 2019-03-20 EP EP19716467.6A patent/EP3769022B1/en active Active
- 2019-03-20 SG SG11202008918SA patent/SG11202008918SA/en unknown
- 2019-03-20 CN CN201980020597.7A patent/CN111886465B/en active Active
- 2019-03-20 WO PCT/FR2019/050624 patent/WO2019180374A1/en not_active Ceased
- 2019-03-20 US US16/982,846 patent/US20210055047A1/en not_active Abandoned
- 2019-03-20 KR KR1020207028610A patent/KR102794639B1/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007502398A (en) | 2003-05-19 | 2007-02-08 | レール・リキード−ソシエテ・アノニム・ア・ディレクトワール・エ・コンセイユ・ドゥ・スールベイランス・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method and apparatus for providing a fluid mixture containing at least 10% carbon monoxide |
| CN104769376A (en) | 2012-05-31 | 2015-07-08 | 乔治洛德方法研究和开发液化空气有限公司 | Device and method for cryogenically separating a mixture of carbon monoxide and methane plus hydrogen and/or nitrogen |
| WO2017212136A1 (en) | 2016-06-06 | 2017-12-14 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and facility for combined production of a mixture of hydrogen and nitrogen as well as carbon monoxide by cryogenic distillation and scrubbing |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3769022B1 (en) | 2024-11-06 |
| US20210055047A1 (en) | 2021-02-25 |
| WO2019180374A1 (en) | 2019-09-26 |
| CN111886465B (en) | 2022-06-24 |
| KR20200135805A (en) | 2020-12-03 |
| SG11202008918SA (en) | 2020-10-29 |
| CN111886465A (en) | 2020-11-03 |
| EP3769022A1 (en) | 2021-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4747858A (en) | Process for removal of carbon dioxide from mixtures containing carbon dioxide and methane | |
| US6767388B2 (en) | Process for dehydrating and fractionating a low-pressure natural gas | |
| US8628601B2 (en) | Carbon dioxide purification | |
| US5452581A (en) | Olefin recovery method | |
| US4548618A (en) | Process and apparatus for the separation of a mixture of gases | |
| JPS58195778A (en) | Manufacture of carbon monoxide | |
| US6266976B1 (en) | Cryogenic H2 and carbon monoxide production with an impure carbon monoxide expander | |
| US4629484A (en) | Process for separating hydrogen and methane from an ethylene rich stream | |
| US6173585B1 (en) | Process for the production of carbon monoxide | |
| EP0023838B1 (en) | Separation of gas mixtures | |
| US7036337B2 (en) | Recovery of hydrogen from refinery and petrochemical light ends streams | |
| US4338107A (en) | Wash system gas separation | |
| US6793714B2 (en) | Process for dehydrating and stripping a wet natural gas | |
| US6578377B1 (en) | Recovery of hydrogen and carbon monoxide from mixtures including methane and hydrocarbons heavier than methane | |
| KR102794639B1 (en) | Method and apparatus for separating synthesis gas by cryogenic distillation | |
| AU2012207039A1 (en) | Method and device for scrubbing medium regeneration in gas scrubbers | |
| CN110779276B (en) | For CH 4 Method and device for producing a mixture of carbon monoxide, hydrogen and methane by cryogenic separation | |
| CN1221102A (en) | Ultra high purity nitrogen and oxygen generator unit | |
| US20230295527A1 (en) | Process and plant for removing carbon dioxide and water from synthesis gas | |
| US6318119B1 (en) | High-pressure gas fractionating process and system | |
| JP3730362B2 (en) | Method for separating hydrogen and methane from gaseous hydrocarbons | |
| KR20130040764A (en) | Hydrocarbon Gas Treatment Method | |
| CN116496820A (en) | Recovery method and recovery system for refinery dry gas | |
| WO2009016625A2 (en) | Method and system for the separation of a mixture containing carbon dioxide, hydrocarbon, and hydrogen | |
| CN112143537A (en) | Method and apparatus for the cryogenic separation of syngas for the production of CH4 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PA0105 | International application |
Patent event date: 20201006 Patent event code: PA01051R01D Comment text: International Patent Application |
|
| PG1501 | Laying open of application | ||
| A201 | Request for examination | ||
| PA0201 | Request for examination |
Patent event code: PA02012R01D Patent event date: 20220222 Comment text: Request for Examination of Application |
|
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20240807 Patent event code: PE09021S01D |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 20250402 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20250408 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 20250409 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration |