CN103694961A - Multi-component mixing refrigerant for nature gas liquefaction system with pre-cooling temperature of -40 to -60 DEG C - Google Patents
Multi-component mixing refrigerant for nature gas liquefaction system with pre-cooling temperature of -40 to -60 DEG C Download PDFInfo
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- CN103694961A CN103694961A CN201310560534.5A CN201310560534A CN103694961A CN 103694961 A CN103694961 A CN 103694961A CN 201310560534 A CN201310560534 A CN 201310560534A CN 103694961 A CN103694961 A CN 103694961A
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- 239000003507 refrigerant Substances 0.000 title abstract description 69
- 238000001816 cooling Methods 0.000 title abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 149
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001294 propane Substances 0.000 claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical group CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 74
- 239000003345 natural gas Substances 0.000 claims description 67
- 238000005057 refrigeration Methods 0.000 claims description 66
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 54
- 238000000034 method Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 16
- 239000000470 constituent Substances 0.000 description 13
- 235000009508 confectionery Nutrition 0.000 description 10
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Images
Classifications
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
- F25J1/008—Hydrocarbons
- F25J1/0092—Mixtures of hydrocarbons comprising possibly also minor amounts of nitrogen
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0022—Hydrocarbons, e.g. natural 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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
- F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
- F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
- F25J1/0055—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream originating from an incorporated cascade
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0211—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
- F25J1/0214—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using a multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a dual level refrigeration cascade with at least one MCR cycle
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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
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
- F25J1/0235—Heat exchange integration
- F25J1/0237—Heat exchange integration integrating refrigeration provided for liquefaction and purification/treatment of the gas to be liquefied, e.g. heavy hydrocarbon removal from natural gas
- F25J1/0239—Purification or treatment step being integrated between two refrigeration cycles of a refrigeration cascade, i.e. first cycle providing feed gas cooling and second cycle providing overhead gas cooling
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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
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/64—Separating heavy hydrocarbons, e.g. NGL, LPG, C4+ hydrocarbons or heavy condensates in general
Abstract
The invention relates to a multi-component mixing refrigerant for a nature gas liquefaction system with a pre-cooling temperature of -40 to -60 DEG C. The multi-component mixing refrigerant comprises four sets of substances, wherein the sum of the molar concentrations of the four sets of the substances is 100%, the first set of the substance is nitrogen gas, the second set of the substance is methane (CH4, R50), the third set of the substance is ethane (C2H6, R170) or ethylene (C2H4, R1150), the fourth set of the substance is propane (C3H8, R290) or propylene (C3H6, R1270), the molar concentration of the first set of the substance is 2-8%, the molar concentration of the second set of the substance is 22-46%, the molar concentration of the fourth set of the substance is 3-25%, and the molar concentration of the third set of the substance is the balance. The multi-component mixing refrigerant has characteristics of high thermodynamic efficiency, safety and environmental protection, and can be provided for achieving nature gas liquefaction in an efficiency and energy-saving manner.
Description
Technical field
The invention belongs to Refrigeration & Cryogenic Technique field, particularly a kind of Diversity refrigeration agent that is applicable to the natural gas liquefaction system that precooling temperature is-40 to-60 ℃.
Background technology
Natural gas liquefaction flow process can be divided into Cascade, mix refrigerant liquefaction flow path according to refrigeration modes and with the liquefaction flow path three basic forms of it of decompressor.Wherein mix refrigerant liquefaction flow path is to contain C1～C5 and N
2mix refrigerant etc. various ingredients is working medium, carries out the cold that condensation step by step, evaporation, throttling expansion obtain differing temps level, progressively cooling and final natural gas liquids.According to having or not precooling link, mix refrigerant liquefaction flow path can be divided into again without precooling mix refrigerant liquefaction flow path and the mix refrigerant liquefaction flow path that has precooling.The principal feature of mix refrigerant liquefaction flow path is: 1) unit equipment is few, and Process flow is comparatively simple, invests moderate; 2) mix refrigerant component can some or all ofly be extracted and supplement from Sweet natural gas itself; 3) proportioning of mix refrigerant is very crucial, and for guaranteeing the lower energy consumption level of flow process, mix refrigerant proportioning is wanted rationally.
Compared to directly utilize mix refrigerant liquefaction flow path main refrigerant to circulate to realize to treat natural gas liquids by normal temperature cooling to precooling temperature, by being set, precooling link realizes this process of cooling, can significantly reduce liquefaction flow path than power consumption, this is mainly in the lower cooling and cold warm area of mistake, to provide cold because main refrigerant is preferably.General precooling link is relatively independent refrigeration cycle, and as the most common propane refrigeration circulation etc., precooling link can will treat that natural gas liquids is precooled to precooling temperature by normal temperature by precooling working medium.Simultaneously because precooling link can be shared a part of cooling load, at total liquefying refrigerating, load under constant prerequisite, main refrigerant circulation refrigeration duty can be minimized, main refrigerant flow measures to reduce, and then reduce the dimensional requirement to main refrigerant compressor and main heat exchanger, therefore when pursuing larger single line LNG output, it is more necessary that the setting of precooling link just seems.The selection of Pre-cooling Mode or precooling working medium mainly contains following several: propane pre-cooling, HFC precooling, MR precooling and Sweet natural gas expansion precooling.
Propane is to be applied at present precooling working medium the most common in mix refrigerant liquefaction flow path.Propane itself can obtain in natural gas _ raw material gas, and normal boiling point is-42.1 ℃, and under normal temperature, (25 ℃) saturation vapour pressure is 0.952MPa, and the hot physical property of propane has determined that it is suitable as the refrigeration cycle working medium of Sweet natural gas precooling warm area very much.Even if it should be noted that in compact cascade type natural gas liquefaction flow process, also large mainly with propane the working medium as first step refrigeration cycle.Visible propane is that ideal precooling working medium is selected, and in propane pre-cooling mix refrigerant (C3-MR) natural gas liquefaction flow process, the temperature of propane pre-cooling is-35 ℃ of left and right conventionally.
Fluorocarbon (HFC) also can be used as precooling working medium.The occasion being restricted at many hydrocarbon polymers (as propane), HFC class refrigeration agent (as R410A) will be that good precooling working medium is selected.HFC class refrigeration agent is of a great variety, and alternative strong, HFC class refrigeration agent has had ripe application experience for many years in refrigeration and low temperature field, thereby makes it as mix refrigerant natural gas liquefaction flow process precooling working medium, become possibility.Take R410A as example, under normal pressure, (0.101MPa) bubble point and dew-point temperature are respectively-51.44 ℃ and-51.36 ℃, under normal temperature, bubbling pressure and dew-point pressure are respectively 1.6522MPa and 1.6574MPa, and suitable hot physical property has guaranteed to provide good precooling effect.R410A is very extensive in the application of refrigerating field, usings it as precooling working medium, easy to operation, and has more the feature of environmental protection and security, and R410A is A1 in ASHRAE safety classification.Compared to propane, adopt R410A as precooling working medium, precooling temperature can further reduce, and reaches-50 ℃ of left and right simultaneously.
The mixing medium (Mixed Refrigerant, MR) that methane (C1), ethane/ethylene (C2), propane (C3) is major components of take also can be used as mix refrigerant natural gas liquefaction system precooling working medium.Depending on concrete applicable cases, in precooling MR, also can contain even pentane (C5) constituent element of butane (C4).With major cycle, MR is the same, and the MR proportioning that is used as precooling also needs through well-designed, so that the temperature difference of cold and hot logistics reaches minimum in precooling process, reduces the irreversible loss in precooling process, and then reduces precooling link power consumption.Because precooling MR component proportion can regulate, thereby can make precooling link more flexible.In general precooling MR, each component all can be taken from raw natural gas, and can reach the precooling temperature lower than propane pre-cooling, and this Pre-cooling Mode is extensive successful Application in LNG device (Dual Mixed Refrigerant, DMR).
It is also a kind of Pre-cooling Mode that has power savings advantages that the cold energy that utilizes high-pressure natural gas expansion to produce is treated coldly natural gas liquids in advance.Especially in natural valve Zhan Huo voltage regulating station, have stable pressure regulation load, in pressure regulation process, will there is considerable cold energy to produce, introducing in this course decompressor replaces throttling valve as voltage regulation component, natural gas temperature after expanding will reach very low level, as when normal-temperature natural-gas is expanded to 1Mpa by 3.7Mpa, can reach-50 ℃ of following precooling temperatures.Concrete liquefaction flow path scheme can be referring to public technologies such as patent ZL201110455516.1.
Along with the Sweet natural gas especially fast development of LNG industry, with the mix refrigerant liquefaction flow path of precooling, be day by day subject to inclining of the attention of scientific research and industrial application bad, this is mainly because the liquefaction that can significantly reduce whole liquefaction flow path by precooling link than power consumption, increases single line LNG liquefaction output simultaneously.Pre-cooling Mode itself is also developed the various ways such as HFC precooling, MR precooling and Sweet natural gas expansion precooling by the most traditional propane pre-cooling, precooling temperature is also progressively expanded to cold zone more by-35 ℃, this to further reduction liquefaction than power consumption and to increase single line LNG output all significant.
The major cycle mix refrigerant that is applied to precooling mix refrigerant natural gas liquefaction flow process requires and system structure design according to Pre-cooling Mode, liquefaction warm area, conventionally require to be formed by least 3 kinds of constituent elements, mix refrigerant shows as typical non-azeotropic feature, in cooling and liquefaction process, carry out condensation, evaporation, throttling expansion step by step, obtain the refrigerating duty of differing temps level, to reach the progressively object of cooling and natural gas liquids.The screening principle of each constituent element of mix refrigerant can be considered from the following aspects:
First, guarantee that mix refrigerant can reach in rational pressure range is enough to the low temperature that makes natural gas liquefaction required; Secondly, be to guarantee in liquefaction cycle in each thermal processing that irreversible loss drops to minimum, and then improve the thermodynamic(al) efficiency of liquefaction cycle, reduce liquefaction flow path power consumption levels; Again, each constituent element will have good physics, chemical stability and security; Finally, consider that natural gas liquefaction device is distributed in remote districts mostly, communications and transportation inconvenience, refrigeration agent constituent element source and economy are also important considerations, can in raw natural gas, the separated constituent element obtaining be upper choosings.
At present by some mandates or apply for a patent the mix refrigerant relating to for natural gas liquefaction flow process and form and concentration proportioning.Wherein: the Chinese patent that application number is 200810115133.8 relates to gas liquefying process for mixed refrigerant and mix refrigerant, its component is nitrogen, methane, ethene, propane, is applicable to Sweet natural gas (or coal-seam gas) liquefaction.
Separately by some mandates or apply for a patent design mix refrigerant form and concentration proportioning, wherein: the cold zone that has patent ZL97115295.0 to relate to 70-120K mixed work medium for throttling refrigeration agent, particularly relate to and be suitable for 70K-120K warm area throttling refrigeration circulation use, by 6 groups of working medium, mixed, comprising nitrogen, methane, ethane, ethene, propane, propylene etc., also comprise the HFC such as tetrafluoromethane, HCFC class working medium.Publication number is that the patent of CN1462861A relates to the method that makes industrial gasses be cooled to cryogenic temperature and obtain liquefying from envrionment temperature, and patent comprises five groups of working medium, contains the HFC class working medium such as tetrafluoromethane, trifluoromethane.Publication number is that the patent of CN10271922A proposes the Diversity refrigeration agent that is applicable to-130～-180 ℃ of deep cooling warm areas forming with five groups of materials, wherein comprises HFC class refrigeration agent.The patent of ZL03121466.5 has related to and has been applicable to 200～240K, i.e. the multicomponent mixed work medium throttling refrigerant of approximately-33～-73 ℃, and refrigeration agent comprises 4 groups of materials, mainly fluorine-containing material, consists of.ZL03121423.1 relates to the multicomponent mixture working medium throttling refrigerant that is mainly applicable to 120～150K deep cooling warm area.The patent of number of patent application 201010608844.6 relates to the mix refrigerant of-80～-100 ℃ of deep cooling warm areas.The patent of number of patent application 201210127046.0 relates to the mix refrigerant of-90～-140 ℃ of cryogenic temperatures.The patent of number of patent application 20120207993 relates to-130～--the Diversity refrigeration agent of 180 ℃ of deep cooling warm areas.But these mix refrigerants all exist that thermodynamic(al) efficiency is not high, the shortcoming of inadequate safety and environmental protection, can not realize the energy-efficient liquefaction to Sweet natural gas.
Summary of the invention
The object of the present invention is to provide a kind of Diversity refrigeration agent that is applicable to the natural gas liquefaction system that precooling temperature is-40 to-60 ℃, this Diversity refrigeration agent thermodynamic(al) efficiency is high, safety and environmental protection, and the liquefaction of the realization that mix refrigerant can be energy-efficient to Sweet natural gas.
In order to reach above-mentioned purpose, the present invention adopts technical scheme to comprise following four groups of materials, and the volumetric molar concentration sum of following four groups of materials is 100%:
First group of material is nitrogen;
Second group of material is methane;
The 3rd group of material is ethane or ethene;
The 4th group of material is propane or propylene;
Wherein, the volumetric molar concentration of first group of material is 2%～8%; The volumetric molar concentration of second group of material is 22%～46%; The volumetric molar concentration of the 4th group of material is 3%～25%; The volumetric molar concentration of the 3rd group of material is surplus.
The 3rd group of described material is ethane, and the 4th group of material is propane or propylene, and the volumetric molar concentration of second group of material is 25%～46%; The volumetric molar concentration of the 4th group of material is 3%～15%.
The volumetric molar concentration of second group of described material is that the volumetric molar concentration of the 25%～35%, four group of material is 7%～15%.
The volumetric molar concentration of second group of described material is that the volumetric molar concentration of the 29%～39%, four group of material is 5%～12%.
The volumetric molar concentration of second group of described material is that the volumetric molar concentration of the 36%～46%, four group of material is 3%～10%.
The 3rd group of described material is ethene, and the 4th group of material is propane or propylene, and the volumetric molar concentration of second group of material is 22%～36%; The volumetric molar concentration of the 4th group of material is 4%～25%.
The volumetric molar concentration of second group of described material is 22%～32%; The volumetric molar concentration of the 4th group of material is 15%～25%.
The volumetric molar concentration of second group of described material is 24%～34%; The volumetric molar concentration of the 4th group of material is 8%～22%.
The volumetric molar concentration of second group of described material is 26%～36%; The volumetric molar concentration of the 4th group of material is 4%～18%.
The present invention considers the high heating power of mix refrigerant and learns efficiency, the factors such as environmental protection and source and transport economic specific property, the Diversity refrigeration agent that is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-40 to-60 ℃ is provided, this Diversity refrigeration agent thermodynamic(al) efficiency is high, and in mix refrigerant, each constituent element is can be directly separated and purify and obtain in raw natural gas, therefore, safety and environmental protection, can be applied to the mix refrigerant natural gas liquefaction system that precooling temperature is-40 to-60 ℃ as major cycle refrigeration working medium, the liquefaction of energy-efficient realization to Sweet natural gas.
Accompanying drawing explanation
Fig. 1 is the Process flow that has precooling mix refrigerant natural gas liquefaction system;
Fig. 2 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 1;
Fig. 3 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 2;
Fig. 4 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 3;
Fig. 5 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 4;
Fig. 6 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 5;
Fig. 7 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 6;
Fig. 8 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 7;
Fig. 9 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 8;
Figure 10 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 9;
Figure 11 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 10;
Figure 12 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 11;
Figure 13 is main heat exchanger and cross cold heat exchanger section hot and cold stream temperature and the relation curve of cooling load in embodiment 12;
Wherein: 1A: a stage compressor, 2A: one-level water cooler, 3A: two stage compressor, 4A: secondary coolers, 5A: mix refrigerant gas-liquid separator, 6A: main heat exchanger, 7A: first throttle device, 8A: mixing tank, 9A: cross cold heat exchanger, 10A: the second throttling set, 1B: heavy hydrocarbon separator, 2B: the 3rd throttling set, 3B: natural gas liquids gas-liquid separator, 1C: precool heat exchanger device.
Embodiment
The Diversity refrigeration agent that is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-40 to-60 ℃ provided by the invention, is comprised of following four groups of materials, and these four groups of materials are respectively:
First group of material is nitrogen (N
2);
Second group of material is methane (CH
4, R50);
The 3rd group of material is ethane (C
2h
6, R170) or ethene (C
2h
4, R1150);
The 4th group of material is propane (C
3h
8, R290) or propylene (C
3h
6, R1270);
The volumetric molar concentration sum of the mixture that described four groups of materials form is 100%.
Of the present inventionly be applicable to the Diversity refrigeration agent that precooling temperature is the mix refrigerant natural gas liquefaction system of-40 to-60 ℃, at different precooling warm areas and respectively organize under material various combination, the corresponding concrete volumetric molar concentration of respectively organizing material is as shown in table 1:
Different precooling warm areas of table 1 and respectively organize under material various combination the corresponding concrete volumetric molar concentration of respectively organizing material
Referring to Fig. 1, the mix refrigerant natural gas liquefaction system that the precooling temperature that Diversity refrigeration agent of the present invention adapts to is-40 to-60 ℃ comprises precool heat exchanger device 1C, main heat exchanger 6A and crosses cold heat exchanger 9A, on precool heat exchanger device 1C, be provided with precooling working medium entrance and precooling sender property outlet for the turnover of precooling working medium, be also provided with and purify raw natural gas entrance and purify the outlet of raw natural gas entrance; Purifying the outlet of raw natural gas entrance is connected with heavy hydrocarbon separator 1B, and the outlet of the heavy hydrocarbon of heavy hydrocarbon separator 1B is connected with the external world, the gas outlet of de-heavy hydrocarbon is connected with natural gas liquids gas-liquid separator 3B through main heat exchanger 6A and mistake cold heat exchanger 9A and the 3rd throttling set 2B successively.
Precool heat exchanger device 1C is successively through a stage compressor 1A, one-level water cooler 2A, two stage compressor 3A and secondary coolers 4A return to precool heat exchanger device 1C, and then be connected with mix refrigerant gas-liquid separator 5A, and the pneumatic outlet of mix refrigerant gas-liquid separator 5A successively main heat exchanger 6A and first throttle device 7A is connected with the first entrance of mixing tank 8A, liquid exit is connected with mistake cold heat exchanger 9A through main heat exchanger 6A, cross cold heat exchanger 9A and returned to cold heat exchanger 9A through the second throttling set 10A, be connected with the second entrance of mixing tank 8A again, the outlet of mixing tank 8A is connected with precool heat exchanger device 1C through main heat exchanger 6A.
Precooling temperature shown in Fig. 1 is that the Diversity refrigerant circulation process of mix refrigerant natural gas liquefaction system of-40 to-60 ℃ is as follows: Diversity refrigeration agent is successively through the two stages of compression of a stage compressor 1A and two stage compressor 3A, make Diversity refrigerant compression to certain pressure, and after a stage compressor 1A compression, pass through the Diversity refrigeration agent after the cooling one-level compression of one-level water cooler 2A, rear by the Diversity refrigeration agent after the cooling two-stage compression of secondary coolers in two stage compressor 3A compression.Diversity refrigeration agent through two stages of compression becomes high pressure Diversity refrigeration agent, high pressure Diversity refrigeration agent flows into precool heat exchanger device 1C and carries out precooling, be condensed into biphase gas and liquid flow, biphase gas and liquid flow enters mix refrigerant gas-liquid separator 5A and is separated into gas phase and liquid phase two portions; Wherein, it is cold by first throttle device 7A decompression throttling refrigeration that liquid phase part enters the further mistake of main heat exchanger 6A, then flows into mixing tank 8A; Gas phase part enters main heat exchanger 6A and crosses cold heat exchanger 9A cooling and excessively cold successively, then through the second throttling set 10A decompression throttling refrigeration, then backflows in cold heat exchanger 9A, for crossing cold heat exchanger 9A, provides cold, then flows into mixing tank 8A.Two strands of Diversity refrigerant fluids that flow out from cross cold heat exchanger 9A and first throttle device 7A backflow into main heat exchanger 6A after fully mixing in mixing tank 8A, for main heat exchanger, 6A provides cold, then flow back to precool heat exchanger device 1C, after part precooling cold is provided, enter one-level compressor 1A, complete the circulation of Diversity refrigeration agent.
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further details.
One, embodiment 1-4 prepares the Diversity refrigeration agent that the present invention is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-40 ℃, the inner minimum heat transfer temperature difference of interchanger is 2K, envrionment temperature is 33 ℃, and each constituent element concentration of Diversity refrigeration agent and performance are in Table 2:
Table 2 embodiment 1-4 is applicable to the Diversity refrigeration agent of the natural gas liquefaction system that precooling temperature is-40 ℃
As seen from Table 2, when precooling temperature is-40 ℃, use the major cycle of Diversity refrigeration agent less than power consumption, use the liquefaction flow path energy-efficient performance of mix refrigerant good.
Two, embodiment 5-8 prepares the Diversity refrigeration agent that the present invention is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-50 ℃, the inner minimum heat transfer temperature difference of interchanger is 2K, envrionment temperature is 33 ℃, and each constituent element concentration of Diversity refrigeration agent and performance are in Table 2:
Table 3 embodiment 5-8 is applicable to the Diversity refrigeration agent of the natural gas liquefaction system that precooling temperature is-50 ℃
As seen from Table 3, when precooling temperature is-50 ℃, use the major cycle of Diversity refrigeration agent less than power consumption, use the liquefaction flow path energy-efficient performance of mix refrigerant good.
Three, embodiment 9-12 prepares the Diversity refrigeration agent that the present invention is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-60 ℃, the inner minimum heat transfer temperature difference of interchanger is 2K, envrionment temperature is 33 ℃, and each constituent element concentration of Diversity refrigeration agent and performance are in Table 4:
Table 4 embodiment 9-12 is applicable to the Diversity refrigeration agent of the natural gas liquefaction system that precooling temperature is-60 ℃
As seen from Table 4, when precooling temperature is-60 ℃, use the major cycle of mix refrigerant less than power consumption, use the liquefaction flow path energy-efficient performance of mix refrigerant good.
In addition, from Fig. 2-13, can find out, in the working process of embodiment 1-12, heat transfer temperature difference is less, and heat exchange is comparatively even, and folder point has a narrow range of temperature, and heat exchange property is good, and mix refrigerant meets the requirement of energy-conserving and environment-protective, can realize the liquefaction to Sweet natural gas energy-efficiently; Wherein, the T in Fig. 2-13
hotrepresent hot-fluid temperature curve, T
coldrepresent cold flow point curve.
Four, embodiment 13-16 prepares the Diversity refrigeration agent that the present invention is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-40 ℃, the inner minimum heat transfer temperature difference of interchanger is 2K, envrionment temperature is 33 ℃, and each constituent element concentration of Diversity refrigeration agent and performance are in Table 5:
Table 5 embodiment 13-16 is applicable to the Diversity refrigeration agent of the natural gas liquefaction system that precooling temperature is-40 ℃
Five, embodiment 17-20 prepares the Diversity refrigeration agent that the present invention is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-50 ℃, the inner minimum heat transfer temperature difference of interchanger is 2K, envrionment temperature is 33 ℃, and each constituent element concentration of Diversity refrigeration agent and performance are in Table 6:
Table 6 embodiment 17-20 is applicable to the Diversity refrigeration agent of the natural gas liquefaction system that precooling temperature is-50 ℃
Six, embodiment 21-24 prepares the Diversity refrigeration agent that the present invention is applicable to the mix refrigerant natural gas liquefaction system that precooling temperature is-60 ℃, the inner minimum heat transfer temperature difference of interchanger is 2K, envrionment temperature is 33 ℃, and each constituent element concentration of Diversity refrigeration agent and performance are in Table 4:
Table 7 embodiment 21-24 is applicable to the Diversity refrigeration agent of the natural gas liquefaction system that precooling temperature is-60 ℃
Claims (9)
1. be applicable to the Diversity refrigeration agent that precooling temperature is the natural gas liquefaction system of-40 to-60 ℃, it is characterized in that, comprise following four groups of materials, and the volumetric molar concentration sum of following four groups of materials is 100%:
First group of material is nitrogen;
Second group of material is methane;
The 3rd group of material is ethane or ethene;
The 4th group of material is propane or propylene;
Wherein, the volumetric molar concentration of first group of material is 2%～8%; The volumetric molar concentration of second group of material is 22%～46%; The volumetric molar concentration of the 4th group of material is 3%～25%; The volumetric molar concentration of the 3rd group of material is surplus.
2. be according to claim 1ly applicable to the Diversity refrigeration agent that precooling temperature is the natural gas liquefaction system of-40 to-60 ℃, it is characterized in that: the 3rd group of described material is ethane, the 4th group of material is propane or propylene, and the volumetric molar concentration of second group of material is 25%～46%; The volumetric molar concentration of the 4th group of material is 3%～15%.
3. be according to claim 2ly applicable to the Diversity refrigeration agent that precooling temperature is the natural gas liquefaction system of-40 to-60 ℃, it is characterized in that: the volumetric molar concentration of second group of described material is that the volumetric molar concentration of the 25%～35%, four group of material is 7%～15%.
4. be according to claim 2ly applicable to the Diversity refrigeration agent that precooling temperature is the natural gas liquefaction system of-40 to-60 ℃, it is characterized in that: the volumetric molar concentration of second group of described material is that the volumetric molar concentration of the 29%～39%, four group of material is 5%～12%.
5. be according to claim 2ly applicable to the Diversity refrigeration agent that precooling temperature is the natural gas liquefaction system of-40 to-60 ℃, it is characterized in that: the volumetric molar concentration of second group of described material is that the volumetric molar concentration of the 36%～46%, four group of material is 3%～10%.
6. be according to claim 1ly applicable to the Diversity refrigeration agent that precooling temperature is the natural gas liquefaction system of-40 to-60 ℃, it is characterized in that: the 3rd group of described material is ethene, the 4th group of material is propane or propylene, and the volumetric molar concentration of second group of material is 22%～36%; The volumetric molar concentration of the 4th group of material is 4%～25%.
7. the Diversity refrigeration agent that is applicable to the natural gas liquefaction system that precooling temperature is-40 to-60 ℃ according to claim 6, is characterized in that: the volumetric molar concentration of second group of described material is 22%～32%; The volumetric molar concentration of the 4th group of material is 15%～25%.
8. the Diversity refrigeration agent that is applicable to the natural gas liquefaction system that precooling temperature is-40 to-60 ℃ according to claim 6, is characterized in that: the volumetric molar concentration of second group of described material is 24%～34%; The volumetric molar concentration of the 4th group of material is 8%～22%.
9. the Diversity refrigeration agent that is applicable to the natural gas liquefaction system that precooling temperature is-40 to-60 ℃ according to claim 6, is characterized in that: the volumetric molar concentration of second group of described material is 26%～36%; The volumetric molar concentration of the 4th group of material is 4%～18%.
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|---|---|---|---|
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|---|---|---|---|
| CN201310560534.5A CN103694961A (en) | 2013-11-12 | 2013-11-12 | Multi-component mixing refrigerant for nature gas liquefaction system with pre-cooling temperature of -40 to -60 DEG C |
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| CN107556969A (en) * | 2016-06-30 | 2018-01-09 | 中石化洛阳工程有限公司 | A kind of working medium to be generated electricity for cold energy of liquefied natural gas organic Rankine bottoming cycle |
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| CN109631492A (en) * | 2018-12-13 | 2019-04-16 | 西安石油大学 | It is a kind of to use the cascade natural gas liquefaction device of azeotrope and method |
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| CN112444099A (en) * | 2019-09-03 | 2021-03-05 | 中国石油化工股份有限公司 | Natural gas liquefaction equipment |
| CN116606632A (en) * | 2023-07-19 | 2023-08-18 | 中科美菱低温科技股份有限公司 | Refrigerant and method for producing the same |
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