CN102620524A - Cascade type natural gas pressurized liquefaction process with sublimation removal of CO2 - Google Patents
Cascade type natural gas pressurized liquefaction process with sublimation removal of CO2 Download PDFInfo
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- CN102620524A CN102620524A CN2012101114176A CN201210111417A CN102620524A CN 102620524 A CN102620524 A CN 102620524A CN 2012101114176 A CN2012101114176 A CN 2012101114176A CN 201210111417 A CN201210111417 A CN 201210111417A CN 102620524 A CN102620524 A CN 102620524A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 239000003345 natural gas Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 87
- 238000000859 sublimation Methods 0.000 title abstract 3
- 230000008022 sublimation Effects 0.000 title abstract 3
- 239000007789 gas Substances 0.000 claims abstract description 44
- 238000001816 cooling Methods 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 14
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 13
- 238000005057 refrigeration Methods 0.000 claims description 43
- 239000012530 fluid Substances 0.000 claims description 31
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 230000006835 compression Effects 0.000 claims description 25
- 238000007906 compression Methods 0.000 claims description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000003949 liquefied natural gas Substances 0.000 claims description 19
- 238000001465 metallisation Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 15
- 239000001294 propane Substances 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 8
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 239000007792 gaseous phase Substances 0.000 claims description 5
- 238000005243 fluidization Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000007781 pre-processing Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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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
- F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
- F25J1/008—Hydrocarbons
- F25J1/0085—Ethane; Ethylene
-
- 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
- F25J1/0087—Propane; Propylene
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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
- F25J1/0203—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 single-component refrigerant [SCR] fluid in a closed vapor compression cycle
- F25J1/0205—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 single-component refrigerant [SCR] fluid in a closed vapor compression cycle as a dual level SCR refrigeration 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
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0244—Operation; Control and regulation; Instrumentation
- F25J1/0254—Operation; Control and regulation; Instrumentation controlling particular process parameter, e.g. pressure, temperature
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/20—Processes or apparatus using other separation and/or other processing means using solidification of components
-
- 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
- F25J2220/66—Separating acid gases, e.g. CO2, SO2, H2S or RSH
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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
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/08—Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
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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
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/30—Compression of the feed stream
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
The invention relates to a cascade type natural gas pressurized liquefaction process with sublimation removal of CO2. Natural gas is kept at a gas state and precooled in a precooler, and is fed into a crystallizer and kept on cooling, so that solid dry ice can be separated out by sublimation and the CO2 content is reduced to 0.5%; and then, natural gas is fed into a cryogenic compressor for pressurization, fed into a liquefier for liquefaction under a high pressure, and fed into a storage tank for storage. The cold quantity required by a liquefaction process is provided by an independent two-stage cascade refrigerating cycle. Compared with the prior art, the process provided by the utility model not only dispenses with CO2 pretreatment equipment which occupies a large area in the conventional natural gas liquefaction process, but also simplifies the traditional three-stage cascade refrigerating cycle to two-stage refrigerating cycle, so as to greatly reduce the cost of investment for natural gas liquefaction on an offshore platform which has high manufacturing cost. Meanwhile, the natural gas liquefaction at a high temperature also reduces the energy consumption of the refrigerating cycle.
Description
Technical field
The present invention relates to the purification and the liquefaction process of natural gas, be a kind of in gas deliquescence process low temperature remove the liquefaction process of carbon dioxide, particularly a kind of in the natural band of gas hydraulic fluid of tandem type process, sublimating removes the liquefaction process of carbon dioxide.Belong to chemical industry and cryogenic technique field.
Background technology
Exploration practices proves, the petroleum resources that in the numerous sedimentary basin in Chinese marine site, is richly stored with, and the marine gas reserves of verifying at present is about 1/3 of national gas reserves.The development and use of marine natural gas not only can provide a kind of clean energy resource of high heating value, can reduce the degree of dependence to petroleum resources simultaneously, have important environmental protection and energy strategy safety meaning.For ease of the trade that transports of natural gas, often with its liquefaction.Need carry out purified treatment before the traditional natural gas liquefaction, wherein take off CO
2Generally will reach the standard of 50～100ppm, this preprocessing process not only floor space is big, and energy consumption is many.
Natural band of gas hydraulic fluidization technology (PLNG technology) is meant and under the about 1～2MPa of higher pressure, makes natural gas liquefaction obtain the technology of liquefied natural gas with pressure (LNG) product.Corresponding condensing temperature is about-100～-120 ℃, and higher condensing temperature has not only reduced required cold that provides and required heat exchange area, has reduced energy consumption, and has increased CO among the LNG greatly
2Solubility (CO
2Molar solubility is less than 0.01% in normal pressure LNG, and under the PLNG condition, can increase to 1～3%).The increase of solubility has reduced purification process to removing CO
2Requirement, for the PLNG flow process, consider safe clearance, it is generally acknowledged that reaching 0.5% standard gets final product.Initial PLNG flow process mainly is to CO
2The natural gas that content is lower proposes, however because CO
2The increment that solubility with temperature in PLNG raises has its limit, and the PLNG flow process is for CO
2It is just powerless that content is higher than 0.5% natural gas, and it is used and therefore receives very big restriction.How to expand the PLNG flow process to CO
2The scope of application of content becomes problem demanding prompt solution.
In the whole bag of tricks, adopt the CO in the method separation removal natural gas of sublimating
2Make its molar fraction reduce to 0.5%, both kept common PLNG flow process and need not ad hoc CO
2The problems such as obstruction that are easy to cause appear in the advantage of pre-processing device when having avoided solid-liquid in some method two identical again, be CO
2Molar fraction be higher than 0.5% natural gas adopt the PLNG technology to provide maybe.
Sublimate and remove CO in the natural gas
2Technology, mainly be to utilize CO
2The higher phase-change characteristic that is prone to sublimate of three phase point temperature offers the cold of natural gas in conjunction with band hydraulic fluid flow process, makes CO in the natural gas
2The frosting of under lower temperature, sublimating, thus realize CO
2Gas solid separation with natural gas.For avoiding occurring liquefaction phenomenon in the process of sublimating, must guarantee CO in the natural gas
2The frosting temperature be higher than the dew-point temperature of natural gas, for meeting this requirement CO in the natural gas under 1.4～1.6MPa pressure
2Molar fraction must not be higher than 30%.Sublimate and remove CO in the natural gas
2Method, on the one hand, can remove CO in the natural gas
2Content, make CO in the natural gas
2Content reach the requirement of liquefaction flow path; On the other hand, can also obtain solid dry ice as byproduct.
Tandem type natural gas liquefaction flow process generally by three grades independently cooling cycle system form.Typical tandem type cooling cycle system is made up of propane, ethene (or ethane), the cold circulatory system overlapping of methane three tier structure, and the circulation of first order propane refrigeration provides cold for natural gas, ethene and methane; Second level ethylene refrigeration circulation provides cold for natural gas and methane; Third level methane refrigeration cycle is that natural gas provides cold.Because the cascade type liquefaction flow process adopted most widely used high efficiency vapor compression type refrigerating system in the refrigerating industry, and the classification of refrigeration warm area is thinner, can mate well with the thermic load that liquefaction process falls in natural gas, thereby energy consumption is low; Utilize the evaporation of cold-producing medium liquid phase that cold is provided, refrigerant flow is little; And cold-producing medium is pure material, no proportioning problem.But cascade type liquefaction flow process unit is many, complicated this shortcoming of flow process has limited applying of it greatly, less employing in the natural gas liquid chemical industry at present.But,, can omit the refrigeration system of minimum temperature one-level under higher temperature if adopt cascade type liquefaction to circulate because natural gas liquefies for band hydraulic fluid natural gas flow process.This makes the key equipment quantity of whole device significantly reduce, and the flow process complexity obviously reduces, and also becomes a kind of flow process form that the circulation of band hydraulic fluid is fit to employing.
In the prior art; Application number is 03802427.6, name is called the patent of invention of " producing the method and apparatus of liquefied natural gas through removing freezable solids ", adopts cooler and the eddy-current technique processed by special material to remove the freezable components such as carbon dioxide in the natural gas feed stream continuously.But the material of the cooler in this patent is required to be one of metal oxide, pottery, monocrystalline or sapphire, and is too special and expensive, is difficult to apply; And in container center rather than the technology that on wall, forms, in engineering practice, be difficult to realize as the solid phase of this patent core.The patent No. is 5819555, name is called that " feed stream removes CO through gas solid separation
2A kind of method " United States Patent (USP), proposed relevant sublimating and removed CO
2Technology, but do not relate to natural gas liquefaction process, and can't guarantee that natural gas do not separate out solid CO in follow-up liquefaction process
2
Summary of the invention
The object of the invention is exactly to provide a kind of to CO for the defective that overcomes above-mentioned prior art existence
2The natural gas design that content is higher for CO
2Molar fraction is less than 0.5% natural gas, and the PLNG flow process can be tolerated whole CO
2And do not separate out solid, thereby can directly remove the very big CO of occupation of land
2Pre-processing device is implemented natural gas liquefaction for the extremely limited offshore platform in place possibility is provided.For CO
2Molar fraction is utilized CO more than or equal to 0.5% natural gas
2The characteristic of sublimating, the cold that provides through band hydraulic fluid process is with the CO in the natural gas
2Sublimating removes, and adopts band hydraulic fluidization technology liquefied natural gas, thereby realizes removing CO
2The purpose of pretreatment unit, minimizing floor space.
The object of the invention can be realized through following technical scheme:
A kind of band is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, sublimate in the process of natural gas liquefaction and remove CO
2, producing LNG product with pressure then, CO has been cancelled in the innovative design on flow process
2Pretreatment unit, and guaranteed not have CO in the follow-up liquefaction process
2Crystal is separated out; Adopt two-stage cascade formula refrigeration system for the natural gas liquefaction flow process cold to be provided simultaneously, more traditional three-stage cascade formula kind of refrigeration cycle has been saved the one-level refrigeration system, has simplified flow process, has reduced equipment investment, specifically may further comprise the steps:
1) with CO
2The raw natural gas of molar fraction between 0.5%～30% introduced the pressure conditioning equipment, with its pressure regulation to 1.4～1.6MPa;
2) natural gas after the step 1) pressure regulation is introduced forecooler precooling cooling;
3) through step 2) natural gas after the precooling introduces the crystallizer cooling, and sublimate and isolate solid dry ice wherein;
4) isolate CO through step 3)
2After natural gas introduce the cryogenic compressor pressurization;
5) natural gas after the step 4) compression is introduced liquefier, liquefies behind the absorption cold;
6) introducing of the liquefied natural gas product after step 5) band hydraulic fluidization natural gas storage tank stores and gets final product;
Wherein, Step 2), natural gas cooling liquefaction process institute chilling requirement overlaps independently by one that two-stage cascade formula refrigeration system provides 3), 5); For low temperature level kind of refrigeration cycle, at first cold-producing medium is introduced first compressor (7) multi-stage compression, introduce first cooler (8) cooling then; Introduce forecooler (2) cooling again; Then introduce first throttle valve (9) throttling cooling again, introduce liquefier (5), crystallizer (3), forecooler (2) then more successively, for these three equipment are got back to compressor (7) after the cold rewarming is provided; For high temperature level kind of refrigeration cycle; At first cold-producing medium is introduced second compressor (10) multi-stage compression, introduce second cooler (11) cooling then, introduce second choke valve (12) throttling cooling again; Then introduce forecooler (2) again for after it provides the cold rewarming, get back to second compressor (10).
The pressure of the raw natural gas described in the step 1) omits step 1) when 1.4～1.6MPa.
Step 2) natural gas is not less than CO in the natural gas in the outlet temperature at forecooler in
2The frosting temperature.
Crystallizer described in the step 3) is the cooling of collection natural gas, CO
2Sublimating, to reclaim function be the equipment of one for crystallization, dry ice, the CO of natural gas in the gaseous phase outlet of crystallizer
2Molar fraction is 0.5%.
Compressor described in the step 4) can bear-110 ℃ of low temperature, and the gas pressure at compressor outlet place is 1.8～2.2MPa, and the rising of pressure has guaranteed not have CO in the follow-up liquefaction process
2Crystal is separated out.
Liquefier described in the step 5) makes entering natural gas liquefaction wherein under 1.8～2.2MPa pressure.
The pressure that obtains in the step 5) be the liquid of 1.8～2.2MPa without the throttling step-down, directly introduce LNG tank and store as product, liquefied natural gas product pressure is higher than the conventional gas liquefaction flow path.
The minimum operating pressure of the natural gas storage tank described in the step 6) is 1.8～2.2MPa.
Described cascaded refrigeration systems is made up of low temperature level Vapor Compression Refrigeration Cycle system and high temperature level Vapor Compression Refrigeration Cycle system two-stage.
The cold-producing medium that described low temperature level Vapor Compression Refrigeration Cycle system adopts is an ethene, and the cold-producing medium that described high temperature level Vapor Compression Refrigeration Cycle system adopts is a propane.
The cold that described high temperature level Vapor Compression Refrigeration Cycle system provides is used for cooled natural gas, and the ethene in the low temperature level Vapor Compression Refrigeration Cycle system is carried out precooling.
Compared with prior art, the present invention can save CO
2Pre-processing device and one-level cooling cycle system reduce heat exchange area, practice thrift equipment investment, save floor space.Through the extensively analog computation of the HYSYS software of employing of petrochemical industry, confirm that the present invention can improve the natural gas liquefaction flow process greatly to CO
2Tolerance, and can reduce the specific energy consumption of liquefied natural gas significantly, and obtain dry ice as byproduct.Reducing greatly of floor space, the remarkable reduction of energy consumption is for the liquefaction of marine natural gas provides possibility.
Description of drawings
Fig. 1 sublimates for band and removes CO
2The natural band of gas hydraulic fluid of tandem type flow chart.
Among the figure, 1 is the pressure conditioning equipment, and 2 is forecooler, and 3 is crystallizer, and 4 is cryogenic compressor; 5 is liquefier, and 6 is natural gas storage tank, and 7 is first compressor, and 8 is first cooler; 9 is the first throttle valve, and 10 is second compressor, and 11 is second cooler, and 12 is second choke valve.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
A kind of band is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, embodiment is as shown in Figure 1.Propane is as high temperature level cold-producing medium, flow 0.772kmol/h; Ethene is as low temperature level cold-producing medium, flow 0.884kmol/h; Raw natural gas molar constituent 0.5%CO
2+ 99.5%CH
4, pressure 1.5MPa, 35 ℃ of temperature, flow 1kmol/h, then band is sublimated and is removed CO
2The concrete steps of the natural band of gas hydraulic fluid of tandem type metallization processes following:
1, because raw natural gas within 1.4～1.6MPa pressure limit, saves pressure conditioning equipment 1.Unstripped gas is introduced forecooler 2, from cold-producing medium propane, ethylene absorbing cold, flow out forecooler 2, temperature drops to-37 ℃;
The natural gas that 2, will pass through after step 1 precooling is introduced crystallizer 3, and from cold-producing medium ethylene absorbing cold, temperature begins to descend the CO in the gaseous natural gas
2The crystallization that begins to sublimate is separated out, the solid CO that crystallization is separated out
2From crystallizer, separate as byproduct dry ice.Along with the further reduction of temperature, more CO
2Crystallization is separated out, and remains in the CO in the gaseous natural gas
2Content reduces gradually, and till the molar content value 0.5% that reaches the permission of band hydraulic fluid flow process, the temperature of crystallizer 3 gaseous phase outlet natural gases is reduced to-109 ℃;
3, will pass through step 2 sublimates and removes CO
2The natural gas of back carbonated 0.5% is introduced cryogenic compressor 4, is pressurized to 2MPa, and temperature is elevated to-93 ℃;
The natural gas that 4, will pass through after step 3 is pressurizeed is introduced liquefier 5, carries out 100% liquefaction from cold-producing medium ethylene absorbing cold, and temperature drops to-107 ℃;
The natural gas that 5, will pass through after step 4 cooling is liquefied is introduced natural gas storage tank 6;
Above natural gas cooling liquefaction process institute chilling requirement overlaps independently by one, and two-stage cascade formula refrigeration system provides.For low temperature level kind of refrigeration cycle; At first ethylene gas is introduced first compressor (7) multi-stage compression to 1578kPa, introduce first cooler (8) then and be cooled to 35 ℃, introduce forecooler (2) again and be cooled to-37 ℃; Introduce first throttle valve (9) throttling again to 55kPa; Temperature is reduced to-114 ℃, and then introduces liquefier (5), crystallizer (3), forecooler (2) successively, for these three equipment are got back to compressor (7) after cold rewarming to 25 ℃ is provided.For high temperature level kind of refrigeration cycle; At first propane gas is introduced second compressor (10) multi-stage compression to 1220kPa; Introduce second cooler (11) then and be cooled to 35 ℃, introduce second choke valve (12) throttling again to 101kPa, temperature is reduced to-42 ℃; Then introduce forecooler (2) again and rewarming to 25 ℃ is provided behind the cold, get back to second compressor (10) for it.
Draw through analog computation, the natural band of gas hydraulic fluid of this tandem type flow process removes CO sublimating
2After liquefied rate be 100% o'clock, the specific energy consumption of LNG product is about 0.19kWh/Nm
3, compared to the about 0.35kWh/Nm of conventional tandem type natural gas liquefaction flow process
3Energy consumption, reduced about 46%.
A kind of band is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, sublimate in the process of natural gas liquefaction and remove CO
2, producing LNG product with pressure then, CO has been cancelled in the innovative design on flow process
2Pretreatment unit, and guaranteed not have CO in the follow-up liquefaction process
2Crystal is separated out; Adopt two-stage cascade formula refrigeration system for the natural gas liquefaction flow process cold to be provided simultaneously, more traditional three-stage cascade formula kind of refrigeration cycle has been saved the one-level refrigeration system, has simplified flow process, has reduced equipment investment.
Propane is as high temperature level cold-producing medium, flow 0.844kmol/h; Ethene is as low temperature level cold-producing medium, flow 1.012kmol/h; Raw natural gas molar constituent 10%CO
2+ 90%CH
4, pressure 1.5MPa, 35 ℃ of temperature, flow 1kmol/h, then band is sublimated and is removed CO
2The concrete steps of the natural band of gas hydraulic fluid of tandem type metallization processes following:
1, because raw natural gas within 1.4～1.6MPa pressure limit, saves pressure conditioning equipment 1.Unstripped gas is introduced forecooler 2, from cold-producing medium propane, ethylene absorbing cold, flow out forecooler 2, temperature drops to-37 ℃;
The natural gas that 2, will pass through after step 1 precooling is introduced crystallizer 3, and from cold-producing medium ethylene absorbing cold, temperature begins to descend the CO in the gaseous natural gas
2The crystallization that begins to sublimate is separated out, the solid CO that crystallization is separated out
2From crystallizer, separate as byproduct dry ice.Along with the further reduction of temperature, more CO
2Crystallization is separated out, and remains in the CO in the gaseous natural gas
2Content reduces gradually, and till the molar content value 0.5% that reaches the permission of band hydraulic fluid flow process, the temperature of crystallizer 3 gaseous phase outlet natural gases is reduced to-109 ℃;
3, will pass through step 2 sublimates and removes CO
2The natural gas of back carbonated 0.5% is introduced cryogenic compressor 4, is pressurized to 2MPa, and temperature is elevated to-93 ℃;
The natural gas that 4, will pass through after step 3 is pressurizeed is introduced liquefier 5, carries out 100% liquefaction from cold-producing medium ethylene absorbing cold, and temperature drops to-107 ℃;
The natural gas that 5, will pass through after step 4 cooling is liquefied is introduced natural gas storage tank 6;
Above natural gas cooling liquefaction process institute chilling requirement overlaps independently by one, and two-stage cascade formula refrigeration system provides.For low temperature level kind of refrigeration cycle; At first ethylene gas is introduced first compressor (7) multi-stage compression to 1578kPa, introduce first cooler (8) then and be cooled to 35 ℃, introduce forecooler (2) again and be cooled to-37 ℃; Introduce first throttle valve (9) throttling again to 55kPa; Temperature is reduced to-114 ℃, and then introduces liquefier (5), crystallizer (3), forecooler (2) successively, for these three equipment are got back to compressor (7) after cold rewarming to 24 ℃ is provided.For high temperature level kind of refrigeration cycle; At first propane gas is introduced second compressor (10) multi-stage compression to 1220kPa; Introduce second cooler (11) then and be cooled to 35 ℃, introduce second choke valve (12) throttling again to 101kPa, temperature is reduced to-42 ℃; Then introduce forecooler (2) again and rewarming to 24 ℃ is provided behind the cold, get back to second compressor (10) for it.
Draw through analog computation, the natural band of gas hydraulic fluid of this tandem type flow process removes CO sublimating
2After liquefied rate be 100% o'clock, the specific energy consumption of LNG product is about 0.23kWh/Nm
3, compared to the about 0.35kWh/Nm of conventional tandem type natural gas liquefaction flow process
3Energy consumption, reduced approximately 34%, and can obtain the solid CO of nearly 0.1kmol/h
2Product.
A kind of band is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, sublimate in the process of natural gas liquefaction and remove CO
2, producing LNG product with pressure then, CO has been cancelled in the innovative design on flow process
2Pretreatment unit, and guaranteed not have CO in the follow-up liquefaction process
2Crystal is separated out; Adopt two-stage cascade formula refrigeration system for the natural gas liquefaction flow process cold to be provided simultaneously, more traditional three-stage cascade formula kind of refrigeration cycle has been saved the one-level refrigeration system, has simplified flow process, has reduced equipment investment.
Propane is as high temperature level cold-producing medium, flow 1.054kmol/h; Ethene is as low temperature level cold-producing medium, flow 1.141kmol/h; Raw natural gas molar constituent 30%CO
2+ 70%CH
4, pressure 1.5MPa, 35 ℃ of temperature, flow 1kmol/h, then band is sublimated and is removed CO
2The concrete steps of the natural band of gas hydraulic fluid of tandem type metallization processes following:
1, because raw natural gas within 1.4～1.6MPa pressure limit, saves pressure conditioning equipment 1.Unstripped gas is introduced forecooler 2, from cold-producing medium propane, ethylene absorbing cold, flow out forecooler 2, temperature drops to-37 ℃;
The natural gas that 2, will pass through after step 1 precooling is introduced crystallizer 3, and from cold-producing medium ethylene absorbing cold, temperature begins to descend the CO in the gaseous natural gas
2The crystallization that begins to sublimate is separated out, the solid CO that crystallization is separated out
2From crystallizer, separate as byproduct dry ice.Along with the further reduction of temperature, more CO
2Crystallization is separated out, and remains in the CO in the gaseous natural gas
2Content reduces gradually, and till the molar content value 0.5% that reaches the permission of band hydraulic fluid flow process, the temperature of crystallizer 3 gaseous phase outlet natural gases is reduced to-109 ℃;
3, will pass through step 2 sublimates and removes CO
2The natural gas of back carbonated 0.5% is introduced cryogenic compressor 4, is pressurized to 2MPa, and temperature is elevated to-93 ℃;
The natural gas that 4, will pass through after step 3 is pressurizeed is introduced liquefier 5, carries out 100% liquefaction from cold-producing medium ethylene absorbing cold, and temperature drops to-107 ℃;
The natural gas that 5, will pass through after step 4 cooling is liquefied is introduced natural gas storage tank 6;
Above natural gas cooling liquefaction process institute chilling requirement overlaps independently by one, and two-stage cascade formula refrigeration system provides.For low temperature level kind of refrigeration cycle; At first ethylene gas is introduced first compressor (7) multi-stage compression to 1578kPa, introduce first cooler (8) then and be cooled to 35 ℃, introduce forecooler (2) again and be cooled to-37 ℃; Introduce first throttle valve (9) throttling again to 55kPa; Temperature is reduced to-114 ℃, and then introduces liquefier (5), crystallizer (3), forecooler (2) successively, for these three equipment are got back to compressor (7) after cold rewarming to 19 ℃ is provided.For high temperature level kind of refrigeration cycle; At first propane gas is introduced second compressor (10) multi-stage compression to 1220kPa; Introduce second cooler (11) then and be cooled to 35 ℃, introduce second choke valve (12) throttling again to 101kPa, temperature is reduced to-42 ℃; Then introduce forecooler (2) again and rewarming to 19 ℃ is provided behind the cold, get back to second compressor (10) for it.
Draw through analog computation, the natural band of gas hydraulic fluid of this tandem type flow process removes CO sublimating
2After liquefied rate be 100% o'clock, the specific energy consumption of LNG product is about 0.35kWh/Nm
3, compared to the about 0.35kWh/Nm of conventional tandem type natural gas liquefaction flow process
3Energy consumption, energy consumption does not have increase, and can obtain the solid CO of nearly 0.3kmol/h
2Product.
Claims (11)
1. a band is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that this technology may further comprise the steps:
1) with CO
2The raw natural gas of molar fraction between 0.5%～30% introduced pressure conditioning equipment (1), with its pressure regulation to 1.4～1.6MPa;
2) natural gas after the step 1) pressure regulation is introduced forecooler (2) precooling cooling;
3) through step 2) natural gas after the precooling introduces crystallizer (3) cooling, and sublimate and isolate solid dry ice wherein;
4) isolate CO through step 3)
2After natural gas introduce cryogenic compressor (4) pressurization;
5) natural gas after the step 4) compression is introduced liquefier (5), liquefies behind the absorption cold;
6) the introducing natural gas storage tank of the liquefied natural gas product after step 5) band hydraulic fluidization (6) stores and gets final product;
Wherein, Step 2), natural gas cooling liquefaction process institute chilling requirement overlaps independently by one that two-stage cascade formula refrigeration system provides 3), 5); For low temperature level kind of refrigeration cycle, at first cold-producing medium is introduced first compressor (7) multi-stage compression, introduce first cooler (8) cooling then; Introduce forecooler (2) cooling again; Then introduce first throttle valve (9) throttling cooling again, introduce liquefier (5), crystallizer (3), forecooler (2) then more successively, for these three equipment are got back to compressor (7) after the cold rewarming is provided; For high temperature level kind of refrigeration cycle; At first cold-producing medium is introduced second compressor (10) multi-stage compression, introduce second cooler (11) cooling then, introduce second choke valve (12) throttling cooling again; Then introduce forecooler (2) again for after it provides the cold rewarming, get back to second compressor (10).
2. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the pressure of the raw natural gas described in the step 1) omits step 1) when 1.4～1.6MPa.
3. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that step 2) in natural gas be not less than CO in the natural gas in outlet temperature at forecooler
2The frosting temperature.
4. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the crystallizer described in the step 3) (3) is collection natural gas cooling, CO
2Sublimating, to reclaim function be the equipment of one for crystallization, dry ice, the CO of natural gas in the gaseous phase outlet of crystallizer (3)
2Molar fraction is 0.5%.
5. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the compressor described in the step 4) (4) can bear-11O ℃ low temperature, the gas pressure in compressor (4) exit is 1.8～2.2MPa.
6. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the liquefier described in the step 5) (5) makes entering natural gas liquefaction wherein under 1.8～2.2MPa pressure.
7. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes; It is characterized in that; The pressure that obtains in the step 5) be the liquid of 1.8～2.2MPa without the throttling step-down, directly introduce LNG tank (6) and store as product, liquefied natural gas product pressure is higher than the conventional gas liquefaction flow path.
8. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the minimum operating pressure of the natural gas storage tank described in the step 6) (6) is 1.8～2.2MPa.
9. a kind of band according to claim 1 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that described cascaded refrigeration systems is made up of low temperature level Vapor Compression Refrigeration Cycle system and high temperature level Vapor Compression Refrigeration Cycle system two-stage.
10. a kind of band according to claim 8 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the cold-producing medium that described low temperature level Vapor Compression Refrigeration Cycle system adopts is an ethene, the cold-producing medium that described high temperature level Vapor Compression Refrigeration Cycle system adopts is a propane.
11. a kind of band according to claim 8 is sublimated and is removed CO
2The natural band of gas hydraulic fluid of tandem type metallization processes, it is characterized in that the cold that described high temperature level Vapor Compression Refrigeration Cycle system provides is used for cooled natural gas, and the ethene in the low temperature level Vapor Compression Refrigeration Cycle system is carried out precooling.
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