CN102620524B - 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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- CN102620524B CN102620524B CN201210111417.6A CN201210111417A CN102620524B CN 102620524 B CN102620524 B CN 102620524B CN 201210111417 A CN201210111417 A CN 201210111417A CN 102620524 B CN102620524 B CN 102620524B
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- natural gas
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- sublimated
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 284
- 239000003345 natural gas Substances 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000000859 sublimation Methods 0.000 title abstract 3
- 230000008022 sublimation Effects 0.000 title abstract 3
- 238000001816 cooling Methods 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007789 gas Substances 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
- 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 20
- 239000001294 propane Substances 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 11
- 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
- 230000033228 biological regulation Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 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
- 230000007423 decrease Effects 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
- 239000012071 phase 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
- 230000007547 defect 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
- 239000003507 refrigerant Substances 0.000 description 1
- 230000000717 retained effect Effects 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
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
- F25J1/0002—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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 purification and the liquefaction process of natural gas, be a kind of in gas deliquescence process the liquefaction process, particularly a kind of liquefaction process of the carbon dioxide removal of sublimating in tandem type natural gas liquefaction process with pressure of low temperature carbon dioxide removal.Belong to chemical industry and cryogenic technique field.
Background technology
Exploration practices proves, the petroleum resources that is richly stored with in the numerous sedimentary basin of China Seas, and the offshore natural gas reserves of verifying are at present about 1/3 of national gas reserves.The exploitation of offshore 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 the safe meaning of important environmental protection and energy strategy.For ease of the trade that transports of natural gas, often by its liquefaction.Before traditional natural gas liquefaction, need to carry out purified treatment, wherein de-CO
2the standard that generally will reach 50～100ppm, this preprocessing process not only floor space is large, and energy consumption is many.
Natural gas liquefaction technology with pressure (PLNG technology) refers at higher pressure and approximately under 1～2MPa, makes natural gas liquefaction obtain the technology of liquefied natural gas with pressure (LNG) product.Corresponding condensing temperature is about-100～-120 DEG C, and the required cold providing and required heat exchange area have not only been provided higher condensing temperature, have reduced energy consumption, and have greatly increased CO in LNG
2solubility (CO
2in normal pressure LNG, molar solubility is less than 0.01%, and can increase to 1～3% under PLNG condition).The increase of solubility has reduced purification process to removing CO
2requirement, for PLNG flow process, consider safe clearance, it is generally acknowledged the standard that reaches 0.5%.Initial PLNG flow process is mainly for CO
2the natural gas that content is lower proposes, but due to CO
2the increment that solubility with temperature in PLNG raises has its limit, and PLNG flow process is for CO
2content is just helpless higher than 0.5% natural gas, and therefore its application is extremely restricted.How to expand 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 be down to 0.5%, both retained common PLNG flow process without ad hoc CO
2the advantage of pre-processing device has avoided again solid-liquid two-phase in some method to occur being easy to the problems such as the obstruction that causes simultaneously, is CO
2molar fraction provides by PLNG technology higher than 0.5% Gas Exploitation may.
Sublimate and remove CO in natural gas
2technology, be mainly to utilize CO
2the higher phase-change characteristic of easily sublimating of three phase point temperature, offers the cold of natural gas in conjunction with liquefaction flow path with pressure, make the CO in natural gas
2the frosting of sublimating at lower temperature, thus realize CO
2gas solid separation with natural gas.For avoiding occurring must ensureing CO in natural gas by liquefaction phenomenon in the process of sublimating
2frosting temperature higher than the dew-point temperature of natural gas, for meeting this requirement, CO in natural gas under 1.4～1.6MPa pressure
2molar fraction must not be higher than 30%.Sublimate and remove CO in natural gas
2method, on the one hand, can remove CO in natural gas
2content, make CO in 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; Ethylene refrigeration circulation in the second level provides cold for natural gas and methane; Third level methane refrigeration cycle provides cold for natural gas.Because Cascade has adopted most widely used high efficiency vapor compression type refrigerating system in refrigerating industry, and refrigeration warm area classification is thinner, and the thermic load that can fall liquefaction process with natural gas is mated well, 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, without proportioning problem.But Cascade unit is many, complicated this shortcoming of flow process has limited applying of it greatly, less employing in natural gas liquid chemical industry at present.But for liquefied natural gas flow process with pressure, because natural gas liquefies under higher temperature, if adopt cascade type liquefaction circulation can omit the refrigeration system of minimum temperature one-level.This greatly reduces the key equipment quantity of whole device, and flow process complexity obviously reduces, and also becomes liquefaction cycle with pressure and is applicable to a kind of Process flow adopting.
In prior art, application number is 03802427.6, name is called the patent of invention of " method and apparatus of producing liquefied natural gas by removing freezable solids ", adopts the cooler be made up of special material and eddy-current technique to remove continuously the freezable components such as carbon dioxide in natural gas feed stream.But the material of the cooler in this patent is required to be one of metal oxide, pottery, monocrystalline or sapphire, too special and expensive, be difficult to apply; And the technology forming in container center instead of on wall as the solid phase of this patent core is difficult to realize in engineering practice.The patent No. is 5819555, name is called that " feed stream removes CO by 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 cannot ensure that natural gas do not separate out solid CO in follow-up liquefaction process
2.
Summary of the invention
Object of the present invention is exactly to provide a kind of for CO in order to overcome the defect that above-mentioned prior art exists
2the natural gas design that content is higher, for CO
2the natural gas that molar fraction is less than 0.5%, PLNG flow process can be tolerated whole CO
2and do not separate out solid, thereby can directly remove the CO that occupation of land is very large
2pre-processing device, implements natural gas liquefaction for the extremely limited offshore platform in place possibility is provided.For CO
2molar fraction is more than or equal to 0.5% natural gas, utilizes CO
2the characteristic of sublimating, the cold providing by liquefaction process with pressure is by the CO in natural gas
2sublimate and remove, adopt liquefaction technology liquefied natural gas with pressure, remove CO thereby realize
2the object of pretreatment unit, minimizing floor space.
Object of the present invention can be achieved through the following technical solutions:
A kind of band is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, in the process of natural gas liquefaction, sublimate and remove CO
2, then producing LNG product with pressure, CO has been cancelled in the innovative design in flow process
2pretreatment unit, and ensured in follow-up liquefaction process without CO
2crystal is separated out; Adopt two-stage cascade formula refrigeration system to provide cold for natural gas liquefaction flow process, more traditional three-stage cascade formula kind of refrigeration cycle has been saved one-level refrigeration system, has simplified flow process, has reduced equipment investment, specifically comprises the following steps simultaneously:
1) by CO
2the raw natural gas of molar fraction between 0.5%～30% introduced pressure conditioning equipment, by its pressure regulation to 1.4～1.6MPa;
2) through step 1) natural gas after pressure regulation introduces forecooler precooling cooling;
3) through step 2) natural gas after precooling introduces crystallizer cooling, and sublimate and isolate solid dry ice wherein;
4) through step 3) isolate CO
2after natural gas introduce cryogenic compressor pressurization;
5) through step 4) natural gas after compression introduces liquefier, and absorb after cold and liquefy;
6) through step 5) liquefied natural gas product after liquefaction with pressure introduces natural gas storage tank and stores;
Wherein, step 2), 3), 5) in, natural gas cooling liquefaction process institute chilling requirement is provided by a set of independently two-stage cascade formula refrigeration system, for low temperature level kind of refrigeration cycle, first cold-producing medium is introduced to the first compressor (7) multi-stage compression, then introduce the first cooler (8) cooling, introduce again forecooler (2) cooling, then introduce again first throttle valve (9) throttling cooling, then introduce successively again liquefier (5), crystallizer (3), forecooler (2), for these three equipment are got back to compressor (7) after cold rewarming is provided, for high temperature level kind of refrigeration cycle, first cold-producing medium is introduced to the second compressor (10) multi-stage compression, then introduce the second cooler (11) cooling, introduce again the second choke valve (12) throttling cooling, then introducing forecooler (2) provides after cold rewarming for it again, gets back to the second compressor (10).
Step 1) described in the pressure of raw natural gas in the time of 1.4～1.6MPa, omit step 1).
Step 2) in natural gas at CO in the outlet temperature of forecooler is not less than natural gas
2frosting temperature.
Step 3) described in crystallizer be collection natural gas cooling, CO
2the equipment that function is integrated, the CO of natural gas in the gaseous phase outlet of crystallizer are reclaimed in sublimate crystallization, dry ice
2molar fraction is 0.5%.
Step 4) described in compressor can bear-110 DEG C of low temperature, the gas pressure at compressor outlet place is 1.8～2.2MPa, the rising of pressure has ensured in follow-up liquefaction process without CO
2crystal is separated out.
Step 5) described in liquefier under 1.8～2.2MPa pressure, make to enter natural gas liquefaction wherein.
Step 5) in the pressure that the obtains liquid that is 1.8～2.2MPa without reducing pressure by regulating flow, directly introduce LNG tank as product and store, liquefied natural gas product pressure is higher than conventional gas liquefaction flow path.
Step 6) described in the minimum operating pressure of natural gas storage tank be 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 ethene, and the cold-producing medium that described high temperature level Vapor Compression Refrigeration Cycle system adopts is propane.
The cold that described high temperature level Vapor Compression Refrigeration Cycle system provides is for cooled natural gas, and the ethene in low temperature level Vapor Compression Refrigeration Cycle system is carried out to precooling.
Compared with prior art, the present invention can save CO
2pre-processing device and one-level cooling cycle system, reduce heat exchange area, saves equipment investment, saves floor space.The analog computation of the HYSYS software extensively adopting by petrochemical industry, proved invention can improve natural gas liquefaction flow process greatly to CO
2tolerance, and can reduce significantly the specific energy consumption of liquefied natural gas, and obtain dry ice as byproduct.Greatly reducing of floor space, the remarkable reduction of energy consumption, for the liquefaction of offshore natural gas provides possibility.
Brief description of the drawings
Fig. 1 sublimates and removes CO for band
2tandem type natural gas liquefaction flow path figure with pressure.
In figure, 1 is 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 the first compressor, and 8 is the first cooler, 9 is first throttle valve, and 10 is the second compressor, and 11 is the second cooler, and 12 is the second choke valve.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
A kind of band is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, 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 DEG C of temperature, flow 1kmol/h, band is sublimated and is removed CO
2the concrete steps of tandem type natural gas liquefaction process with pressure as follows:
1, because raw natural gas is within 1.4～1.6MPa pressure limit, save pressure conditioning equipment 1.Unstripped gas is introduced to forecooler 2, absorb cold from cold-producing medium propane, ethene, flow out forecooler 2, temperature drops to-37 DEG C;
2, the natural gas after step 1 precooling is introduced to crystallizer 3, absorb cold from cold-producing medium ethene, temperature starts to decline, the CO in gaseous natural gas
2start the crystallization of sublimating, the solid CO of crystallization
2from crystallizer, separate as byproduct dry ice.Along with the further reduction of temperature, more CO
2crystallization, remains in the CO in gaseous natural gas
2content reduces gradually, until reach the molar content value 0.5% that liquefaction flow path with pressure allows, the temperature of crystallizer 3 gaseous phase outlet natural gases is reduced to-109 DEG C;
3, will sublimate and remove CO through step 2
2the natural gas of rear carbonated 0.5% is introduced cryogenic compressor 4, is pressurized to 2MPa, and temperature is elevated to-93 DEG C;
4, the natural gas after step 3 is pressurizeed is introduced to liquefier 5, absorb cold carry out 100% liquefaction from cold-producing medium ethene, temperature drops to-107 DEG C;
5, the natural gas of lowering the temperature through step 4 after liquefaction is introduced to natural gas storage tank 6;
Above natural gas cooling liquefaction process institute chilling requirement is provided by a set of independently two-stage cascade formula refrigeration system.For low temperature level kind of refrigeration cycle, first ethylene gas is introduced to the first compressor (7) multi-stage compression to 1578kPa, then introduce the first cooler (8) and be cooled to 35 DEG C, introduce again forecooler (2) and be cooled to-37 DEG C, introduce again first throttle valve (9) throttling to 55kPa, temperature is reduced to-114 DEG C, and then introduce successively liquefier (5), crystallizer (3), forecooler (2), for these three equipment are got back to compressor (7) after cold rewarming to 25 DEG C is provided.For high temperature level kind of refrigeration cycle, first propane gas is introduced to the second compressor (10) multi-stage compression to 1220kPa, then introduce the second cooler (11) and be cooled to 35 DEG C, introduce again the second choke valve (12) throttling to 101kPa, temperature is reduced to-42 DEG C, then introduce again forecooler (2) and provide rewarming to 25 DEG C after cold for it, get back to the second compressor (10).
Draw through analog computation, this tandem type natural gas liquefaction flow path with pressure removes CO sublimating
2after liquefied rate while being 100%, 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%.
Embodiment 2
A kind of band is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, in the process of natural gas liquefaction, sublimate and remove CO
2, then producing LNG product with pressure, CO has been cancelled in the innovative design in flow process
2pretreatment unit, and ensured in follow-up liquefaction process without CO
2crystal is separated out; Adopt two-stage cascade formula refrigeration system to provide cold for natural gas liquefaction flow process, more traditional three-stage cascade formula kind of refrigeration cycle has been saved one-level refrigeration system, has simplified flow process, has reduced equipment investment simultaneously.
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 DEG C of temperature, flow 1kmol/h, band is sublimated and is removed CO
2the concrete steps of tandem type natural gas liquefaction process with pressure as follows:
1, because raw natural gas is within 1.4～1.6MPa pressure limit, save pressure conditioning equipment 1.Unstripped gas is introduced to forecooler 2, absorb cold from cold-producing medium propane, ethene, flow out forecooler 2, temperature drops to-37 DEG C;
2, the natural gas after step 1 precooling is introduced to crystallizer 3, absorb cold from cold-producing medium ethene, temperature starts to decline, the CO in gaseous natural gas
2start the crystallization of sublimating, the solid CO of crystallization
2from crystallizer, separate as byproduct dry ice.Along with the further reduction of temperature, more CO
2crystallization, remains in the CO in gaseous natural gas
2content reduces gradually, until reach the molar content value 0.5% that liquefaction flow path with pressure allows, the temperature of crystallizer 3 gaseous phase outlet natural gases is reduced to-109 DEG C;
3, will sublimate and remove CO through step 2
2the natural gas of rear carbonated 0.5% is introduced cryogenic compressor 4, is pressurized to 2MPa, and temperature is elevated to-93 DEG C;
4, the natural gas after step 3 is pressurizeed is introduced to liquefier 5, absorb cold carry out 100% liquefaction from cold-producing medium ethene, temperature drops to-107 DEG C;
5, the natural gas of lowering the temperature through step 4 after liquefaction is introduced to natural gas storage tank 6;
Above natural gas cooling liquefaction process institute chilling requirement is provided by a set of independently two-stage cascade formula refrigeration system.For low temperature level kind of refrigeration cycle, first ethylene gas is introduced to the first compressor (7) multi-stage compression to 1578kPa, then introduce the first cooler (8) and be cooled to 35 DEG C, introduce again forecooler (2) and be cooled to-37 DEG C, introduce again first throttle valve (9) throttling to 55kPa, temperature is reduced to-114 DEG C, and then introduce successively liquefier (5), crystallizer (3), forecooler (2), for these three equipment are got back to compressor (7) after cold rewarming to 24 DEG C is provided.For high temperature level kind of refrigeration cycle, first propane gas is introduced to the second compressor (10) multi-stage compression to 1220kPa, then introduce the second cooler (11) and be cooled to 35 DEG C, introduce again the second choke valve (12) throttling to 101kPa, temperature is reduced to-42 DEG C, then introduce again forecooler (2) and provide rewarming to 24 DEG C after cold for it, get back to the second compressor (10).
Draw through analog computation, this tandem type natural gas liquefaction flow path with pressure removes CO sublimating
2after liquefied rate while being 100%, 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.
Embodiment 3
A kind of band is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, in the process of natural gas liquefaction, sublimate and remove CO
2, then producing LNG product with pressure, CO has been cancelled in the innovative design in flow process
2pretreatment unit, and ensured in follow-up liquefaction process without CO
2crystal is separated out; Adopt two-stage cascade formula refrigeration system to provide cold for natural gas liquefaction flow process, more traditional three-stage cascade formula kind of refrigeration cycle has been saved one-level refrigeration system, has simplified flow process, has reduced equipment investment simultaneously.
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 DEG C of temperature, flow 1kmol/h, band is sublimated and is removed CO
2the concrete steps of tandem type natural gas liquefaction process with pressure as follows:
1, because raw natural gas is within 1.4～1.6MPa pressure limit, save pressure conditioning equipment 1.Unstripped gas is introduced to forecooler 2, absorb cold from cold-producing medium propane, ethene, flow out forecooler 2, temperature drops to-37 DEG C;
2, the natural gas after step 1 precooling is introduced to crystallizer 3, absorb cold from cold-producing medium ethene, temperature starts to decline, the CO in gaseous natural gas
2start the crystallization of sublimating, the solid CO of crystallization
2from crystallizer, separate as byproduct dry ice.Along with the further reduction of temperature, more CO
2crystallization, remains in the CO in gaseous natural gas
2content reduces gradually, until reach the molar content value 0.5% that liquefaction flow path with pressure allows, the temperature of crystallizer 3 gaseous phase outlet natural gases is reduced to-109 DEG C;
3, will sublimate and remove CO through step 2
2the natural gas of rear carbonated 0.5% is introduced cryogenic compressor 4, is pressurized to 2MPa, and temperature is elevated to-93 DEG C;
4, the natural gas after step 3 is pressurizeed is introduced to liquefier 5, absorb cold carry out 100% liquefaction from cold-producing medium ethene, temperature drops to-107 DEG C;
5, the natural gas of lowering the temperature through step 4 after liquefaction is introduced to natural gas storage tank 6;
Above natural gas cooling liquefaction process institute chilling requirement is provided by a set of independently two-stage cascade formula refrigeration system.For low temperature level kind of refrigeration cycle, first ethylene gas is introduced to the first compressor (7) multi-stage compression to 1578kPa, then introduce the first cooler (8) and be cooled to 35 DEG C, introduce again forecooler (2) and be cooled to-37 DEG C, introduce again first throttle valve (9) throttling to 55kPa, temperature is reduced to-114 DEG C, and then introduce successively liquefier (5), crystallizer (3), forecooler (2), for these three equipment are got back to compressor (7) after cold rewarming to 19 DEG C is provided.For high temperature level kind of refrigeration cycle, first propane gas is introduced to the second compressor (10) multi-stage compression to 1220kPa, then introduce the second cooler (11) and be cooled to 35 DEG C, introduce again the second choke valve (12) throttling to 101kPa, temperature is reduced to-42 DEG C, then introduce again forecooler (2) and provide rewarming to 19 DEG C after cold for it, get back to the second compressor (10).
Draw through analog computation, this tandem type natural gas liquefaction flow path with pressure removes CO sublimating
2after liquefied rate while being 100%, 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 is without increase, and can obtain the solid CO of nearly 0.3kmol/h
2product.
Claims (11)
1. a band is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that, this technique comprises the following steps:
1) by CO
2the raw natural gas of molar fraction between 0.5%～30% introduced pressure conditioning equipment (1), by its pressure regulation to 1.4～1.6MPa;
2) through step 1) natural gas after pressure regulation introduces forecooler (2) precooling cooling;
3) through step 2) natural gas after precooling introduces crystallizer (3) cooling, and sublimate and isolate solid dry ice wherein;
4) through step 3) isolate CO
2after natural gas introduce cryogenic compressor (4) pressurization;
5) through step 4) natural gas after compression introduces liquefier (5), and absorb after cold and liquefy;
6) through step 5) liquefied natural gas product after liquefaction with pressure introduces natural gas storage tank (6) and stores;
Wherein, step 2), 3), 5) in, natural gas cooling liquefaction process institute chilling requirement is provided by a set of independently two-stage cascade formula refrigeration system, for low temperature level kind of refrigeration cycle, first cold-producing medium is introduced to the first compressor (7) multi-stage compression, then introduce the first cooler (8) cooling, introduce again forecooler (2) cooling, then introduce again first throttle valve (9) throttling cooling, then introduce successively again liquefier (5), crystallizer (3), forecooler (2), for these three equipment are got back to the first compressor (7) after cold rewarming is provided, for high temperature level kind of refrigeration cycle, first cold-producing medium is introduced to the second compressor (10) multi-stage compression, then introduce the second cooler (11) cooling, introduce again the second choke valve (12) throttling cooling, then introducing forecooler (2) provides after cold rewarming for it again, gets back to the second compressor (10).
2. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that step 1) described in the pressure of raw natural gas in the time of 1.4～1.6MPa, omit step 1).
3. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that step 2) in natural gas CO in the outlet temperature of forecooler is not less than natural gas
2frosting temperature.
4. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that step 3) described in crystallizer (3) be collection natural gas cooling, CO
2the equipment that function is integrated, the CO of natural gas in the gaseous phase outlet of crystallizer (3) are reclaimed in sublimate crystallization, dry ice
2molar fraction is 0.5%.
5. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that step 4) described in compressor (4) can bear-110 DEG C of 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
2tandem type natural gas liquefaction process with pressure, it is characterized in that step 5) described in liquefier (5) under 1.8～2.2MPa pressure, make to enter natural gas liquefaction wherein.
7. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that, step 5) in the pressure that the obtains liquid that is 1.8～2.2MPa without reducing pressure by regulating flow, directly introduce LNG tank (6) as product and store, liquefied natural gas product pressure is higher than conventional gas liquefaction flow path.
8. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that step 6) described in the minimum operating pressure of natural gas storage tank (6) be 1.8MPa.
9. a kind of band according to claim 1 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, 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 9 is sublimated and is removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that, the cold-producing medium that described low temperature level Vapor Compression Refrigeration Cycle system adopts is ethene, the cold-producing medium that described high temperature level Vapor Compression Refrigeration Cycle system adopts is propane.
11. a kind of bands according to claim 9 are sublimated and are removed CO
2tandem type natural gas liquefaction process with pressure, it is characterized in that, the cold that described high temperature level Vapor Compression Refrigeration Cycle system provides is for cooled natural gas, and the ethene in low temperature level Vapor Compression Refrigeration Cycle system is carried out to precooling.
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| CN110044131B (en) * | 2019-05-06 | 2020-10-27 | 郑州轻工业学院 | Multi-stage compressed propane precooling natural gas liquefaction system and liquefaction method thereof |
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