CN205561413U - Gaseous cryogenic liquefying system - Google Patents
Gaseous cryogenic liquefying system Download PDFInfo
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- CN205561413U CN205561413U CN201620283647.4U CN201620283647U CN205561413U CN 205561413 U CN205561413 U CN 205561413U CN 201620283647 U CN201620283647 U CN 201620283647U CN 205561413 U CN205561413 U CN 205561413U
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- heat exchanger
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- outfan
- gas
- knockout drum
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Abstract
The utility model provides a gaseous cryogenic liquefying system, the heat transfer unit includes the one -level heat exchanger E1, second grade heat exchanger E2 and the tertiary heat exchanger E3 that concatenate in proper order, wherein one -level heat exchanger E1's input is connected with compression unit, and the output and gas -liquid separation unit connection of inflation liquefaction unit are connected to tertiary heat exchanger E3's the output and the input of inflation liquefaction unit, tertiary heat exchanger E3's refrigerant input is connected with the gas outlet end of gas -liquid separation unit, and this third grade heat exchanger E3's refrigerant output is connected with one -level heat exchanger E1's first refrigerant input, this one -level heat exchanger E1's first refrigerant output and compression unit connects, second grade heat exchanger E2's refrigerant input is connected with the finished product output of gas -liquid separation unit, perhaps is connected with one -level heat exchanger E1's output, and this second grade heat exchanger E2's refrigerant output is connected with compression unit. The utility model discloses whole technology is simple and practical more, easy sledge massing, and nos refrigerator consumes energy and the pollution of conventional refrigerant etc..
Description
Technical field
This utility model relates to gas liquefaction field, is specifically related to a kind of gas cryogenic liquefying system.
Background technology
Equipment is few, liquid of driving out is fast because producing flexibly, moving for high-pressure spray liquefaction process based on nozzles with injector
Advantage, is used widely, but in tradition in conventional gas, rare gas and mini gas liquefaction field
In technique, the liquefaction of process gas cooling except utilize high pressure feed flow into nozzles with injector and wherein high speed swollen
Swollen, it is thus achieved that outside low temperature, also need to introduce refrigeration machine and provide cold, refrigerator system equipment for system heat exchange unit
Relatively big, increase equipment investment and floor space, be unfavorable for sledge massing, it addition, conventional chiller coolant
Relatively big to environmental disruption, part coolant is the most disabled in developed country, if using other coolant instead, then freezes
Poor effect or price are high.
Utility model content
This utility model is for the deficiencies in the prior art, it is proposed that one removes refrigeration machine in tradition liquefaction system
System, the process stream after utilization processes provides cold as coolant for heat exchange unit, is greatly reduced equipment
Volume, makes integral device structure simpler, it is simple to a kind of gas cryogenic liquefying system of skid, specifically
Technical scheme is as follows:
A kind of gas cryogenic liquefying system, is provided with compression unit, heat exchange unit, expansion liquefaction unit gentle
Liquid separative element, wherein said heat exchange unit includes first-class heat exchanger E1, the secondary heat exchanger E2 being sequentially connected in series
Outfan with three grades of heat exchanger E3, the input of wherein said first-class heat exchanger E1 and described compression unit
Connecting, the outfan of described three grades of heat exchanger E3 is connected with the input of described expansion liquefaction unit, described swollen
The outfan of swollen liquefaction unit is connected with described gas-liquid separation unit;
The coolant input of described three grades of heat exchanger E3 is connected with the gas output end of described gas-liquid separation unit,
The coolant outfan of these three grades of heat exchanger E3 is connected with the first coolant input of described first-class heat exchanger E1,
First coolant outfan of this first-class heat exchanger E1 is connected with described compression unit;
The coolant input of described secondary heat exchanger E2 is connected with the finished product outfan of described gas-liquid separation unit,
Or it is connected with the outfan of described first-class heat exchanger E1, the coolant outfan of this secondary heat exchanger E2 and institute
State compression unit to connect.
For preferably realizing this utility model, may further be:
Described expansion liquefaction unit is made up of nozzles with injector M1 and nozzles with injector M2, described gas-liquid separation unit
It is made up of knockout drum S1, knockout drum S2, knockout drum S3 and knockout drum S4, wherein said three grades of heat exchangers
The outfan of E3 is connected with described nozzles with injector M1 and nozzles with injector M2 input respectively, this nozzles with injector
M1 and nozzles with injector M2 outfan input with described knockout drum S1 and knockout drum S2 respectively is connected, institute
The coolant input of the gas output end and described three grades of heat exchanger E3 of stating knockout drum S1 is connected, described separation
First branch road of tank S1 finished product outfan is adjusted valve and is connected with the coolant input of described secondary heat exchanger E2,
Second branch road is connected through the input of choke valve with described knockout drum S2, the gas output end of this knockout drum S2
Being connected with the input of described nozzles with injector M1, the finished product outfan of described knockout drum S2 is through choke valve and institute
State knockout drum S3 input connect, the input of this knockout drum S3 also with storage system gas output end
Connecting, gas output end is connected with the input of described nozzles with injector M2, and finished product outfan is adjusted valve and institute
The input stating storage system connects.
The fixed gas outfan of described knockout drum S4 is adjusted the second coolant of valve and described first-class heat exchanger E1
Input connects, and the second coolant outfan of this first-class heat exchanger E1 is connected with fixed gas reutilization system.
The gas phase outlet of described knockout drum S1 is yet adjusted the input of valve and described knockout drum S3 inner coil pipe
Connecting, the outfan of this coil pipe is connected with the input of described knockout drum S4, the product of described knockout drum S4
Outfan is connected with the input of described knockout drum S2.
Described compression unit is provided with feed gas compressor system C1 and recycle gas compressor system C2, wherein
The input of feed gas compressor system C1 is connected with unstripped gas, outfan and described first-class heat exchanger E1
Input connects, the first branch road of this first-class heat exchanger E1 outfan and the input of described secondary heat exchanger E2
End connects, and the second branch road coolant input with described secondary heat exchanger E2 after choke valve is connected, these two grades
The input of the outfan of heat exchanger E2 and three grades of heat exchanger E3 connects, coolant outfan and described circulating air
The input of compressor assembly C2 connects, the input of this recycle gas compressor system C2 also with described one-level
The first coolant outfan of heat exchanger E1 connects, and the outfan of described recycle gas compressor system C2 is with described
The input of first-class heat exchanger E1 connects.
The beneficial effects of the utility model are: this utility model utilizes process stream to substitute refrigeration machine as coolant
Middle tradition coolant, simplifies technique, saves refrigerator system part in traditional handicraft, and whole technique is simpler
Single practical, it is easy to operation, and assemble simple, it is easier to sledge massing, greatly reduce cost of investment, do not have
Refrigeration machine power consumption and the pollution of conventional coolant, running more energy-saving and environmental protection.
Accompanying drawing explanation
Fig. 1 is the structural representation of this utility model embodiment one;
Fig. 2 is the structural representation of this utility model embodiment two;
Fig. 3 is the structural representation of this utility model embodiment three.
Detailed description of the invention
Below in conjunction with the accompanying drawings preferred embodiment of the present utility model is described in detail, so that of the present utility model
Advantage and feature can be easier to be readily appreciated by one skilled in the art, thus do protection domain of the present utility model
Go out apparent clear and definite defining.
Embodiment one: as it is shown in figure 1, a kind of gas cryogenic liquefying system, be provided with compression unit, heat exchange
Unit, expansion liquefaction unit and gas-liquid separation unit, wherein compression unit is provided with feed gas compressor system
C1 and recycle gas compressor system C2, heat exchange unit be provided be sequentially connected in series first-class heat exchanger E1, two grades
Heat exchanger E2 and three grades of heat exchanger E3, expands liquefaction unit and is provided with nozzles with injector M1 and nozzles with injector M2,
Gas-liquid separation unit is made up of knockout drum S1, knockout drum S2, knockout drum S3 and knockout drum S4;
Concrete annexation is that the input of feed gas compressor system C1 is connected with unstripped gas, outfan and
The input of described first-class heat exchanger E1 connects, and the first branch road of this first-class heat exchanger E1 outfan is with described
The input of secondary heat exchanger E2 connects, the second branch road cold with described secondary heat exchanger E2 after choke valve
Matchmaker's input connects, and the outfan of this secondary heat exchanger E2 and the input of three grades of heat exchanger E3 connect, cold
Matchmaker's outfan is connected with the input of described recycle gas compressor system C2, this recycle gas compressor system C2
Input be also connected with the first coolant outfan of described first-class heat exchanger E1, described recycle gas compressor system
The outfan of system C2 is connected with the input of described first-class heat exchanger E1;
The outfan of described three grades of heat exchanger E3 inputs with described nozzles with injector M1 and nozzles with injector M2 respectively
End connects, and coolant outfan is connected with the first coolant input of described first-class heat exchanger E1, this nozzles with injector
M1 and nozzles with injector M2 outfan input with described knockout drum S1 and knockout drum S2 respectively is connected, institute
The coolant input of the gas output end and described three grades of heat exchanger E3 of stating knockout drum S1 is connected, described separation
Tank S1 finished product outfan is connected through the input of choke valve with described knockout drum S2, the gas of this knockout drum S2
Outfan is connected with the input of described nozzles with injector M1, and the finished product outfan of described knockout drum S2 is through throttling
Valve is connected with the input of described knockout drum S3, the input of this knockout drum S3 also with storage system gas
Outfan connects, and gas output end is connected with the input of described nozzles with injector M2, and finished product outfan is adjusted
Valve is connected with the input of described storage system;
The gas phase outlet of described knockout drum S1 is yet adjusted the input of valve and described knockout drum S3 inner coil pipe
Connecting, the outfan of this coil pipe is connected with the input of described knockout drum S4, the product of described knockout drum S4
Outfan is connected through the input of choke valve with described knockout drum S2, the fixed gas output of described knockout drum S4
End is adjusted valve coolant input defeated with the second of described first-class heat exchanger E1 and is connected, this first-class heat exchanger E1
The second coolant outfan, be connected with fixed gas reutilization system;
The present embodiment is achieved in that as a example by natural gas liquefaction, and purification purified, dried is natural
Gas first passes through feed gas compressor system C1 and is compressed to 18~22MPa, 35 DEG C, then with from circulating air
The 18~22MPa of compressor assembly C2,35 DEG C of natural gas mixing, enter the cooling of ice chest first-class heat exchanger E1
Then being divided into two-way to 10 DEG C, it is two grades that a road enters secondary heat exchanger E2 as coolant after choke valve
Heat exchanger E2 lowers the temperature, and enters compressor assembly C2 afterwards and is compressed circulation;Another road is as process stream
Enter secondary heat exchanger E2 and be cooled to about-35 DEG C, enter back into three grades of heat exchangers and be cooled to about-68 DEG C, it
Rear high-pressure natural gas is divided into two parts, respectively enters two nozzles with injectors and expands at a high speed cooling liquefaction;
A part of high pressure mixing natural gas enter nozzles with injector M1 and with the low pressure natural gas from knockout drum S2
(-134 DEG C, 0.6MPa) mix, and after expanding cooling, (-122 DEG C, 1.2MPa) entrance knockout drum S1 enters
Row gas-liquid separation, another part high pressure mixing natural gas enter nozzles with injector M2 and with from knockout drum S3's
Low pressure natural gas (-149 DEG C, 0.15MPa) mixes, and after expanding cooling, (-133 DEG C, 0.6MPa) enter
Knockout drum S2 carries out gas-liquid separation;
Gas phase natural gas in knockout drum S1 is divided into two parts: mostly as circulating air, enters three grades
Heat exchanger E3 cold recycles, and with high pressure mixing heat exchange gas, temperature rises to-45 DEG C, 1.2MPa, it
Rear entrance first-class heat exchanger E1 rises to 20 DEG C and secondary heat exchanger with high pressure mixing heat exchange gas temperature again
The coolant natural gas (20 DEG C, 1.2MPa) that E2 comes enters recycle gas compressor system C2 together and is compressed,
It is mixed into E1 heat exchanger with feed gas compressor system C1 outlet raw natural gas afterwards again to expand
Circulation;Fraction is adjusted valve from knockout drum S1 and enters the condenser within knockout drum S3, in condenser
Cooling enters knockout drum S4 for gas-liquid mixture (-144 DEG C, 1.2MPa), in knockout drum S4 further
Liquid enters knockout drum S2 through choke valve, and the gas phase in knockout drum S4 first passes through heat exchange as low temperature fixed gas
After device E1 reclaims cold further, discharger recycles;
Liquid in knockout drum S1 enters together with liquid point in choke valve is throttled to 0.6Mpa with S4
From tank S2;Liquid in knockout drum S2 is decompressed to 0.15MPa through choke valve, enters knockout drum S3,
In S3, liquid is delivered to stocking system through overregulating valve and cryopump, and from the BOG gas of stocking system
Enter nozzles with injector M2 together with gas phase natural gas in knockout drum S3 in entering knockout drum S3 and again carry out swollen
Swollen liquefaction.
Embodiment two: as in figure 2 it is shown, a kind of gas cryogenic liquefying system, be provided with compression unit, heat exchange
Unit, expansion liquefaction unit and gas-liquid separation unit, wherein compression unit is provided with feed gas compressor system
C1 and recycle gas compressor system C2, heat exchange unit be provided be sequentially connected in series first-class heat exchanger E1, two grades
Heat exchanger E2 and three grades of heat exchanger E3, expands liquefaction unit and is provided with nozzles with injector M1 and nozzles with injector M2,
Gas-liquid separation unit is made up of knockout drum S1, knockout drum S2, knockout drum S3 and knockout drum S4;
Concrete annexation is that the input of feed gas compressor system C1 is connected with unstripped gas, outfan and
The input of described first-class heat exchanger E1 connects, and first-class heat exchanger E1 outfan inputs with secondary heat exchanger E2
End connects, and secondary heat exchanger E2 outfan and three grades of heat exchanger E3 inputs connect, three grades of heat exchanger E3
Outfan be connected with described nozzles with injector M1 and nozzles with injector M2 input respectively, this nozzles with injector M1
Input with described knockout drum S1 and knockout drum S2 is connected respectively with nozzles with injector M2 outfan, described
The gas output end of knockout drum S1 is connected with the coolant input of described three grades of heat exchanger E3, these three grades of heat exchange
The coolant outfan of device E3 is connected with the first coolant input of described first-class heat exchanger E1, described knockout drum
First branch road of S1 finished product outfan is adjusted valve and is connected with the coolant input of described secondary heat exchanger E2, should
The coolant outfan of secondary heat exchanger E2 and the first coolant outfan of described first-class heat exchanger E1 all with circulation
The input of air compressor system C2 connects, the outfan of this recycle gas compressor system C2 and one-level heat exchange
The input of device E1 connects,
Second branch road of described knockout drum S1 finished product outfan is through the input of choke valve Yu described knockout drum S2
Connecting, the gas output end of this knockout drum S2 is connected with the input of described nozzles with injector M1, described separation
The finished product outfan of tank S2 is connected through the input of choke valve with described knockout drum S3, and this knockout drum S3's is defeated
Enter the end gas output end also with storage system to be connected, gas output end and the input of described nozzles with injector M2
Connecting, finished product outfan is adjusted valve and is connected with the input of described storage system, and described knockout drum S4 is not
Solidifying gas outfan is adjusted valve and is connected with the second coolant input of described first-class heat exchanger E1, first-class heat exchanger
The second coolant outfan of E1 is connected with fixed gas reutilization system, and the finished product outfan of knockout drum S4 is through throttling
Valve is connected with the input of described knockout drum S2;
The gas phase outlet of described knockout drum S1 is yet adjusted the input of valve and described knockout drum S3 inner coil pipe
Connecting, the outfan of this coil pipe is connected with the input of described knockout drum S4.
In the present embodiment, other principle is identical with embodiment one, and distinctive points is, utilizes knockout drum S1
In finished product liquid process gas be that secondary heat exchanger E2 carries out heat exchange as coolant, the liquid process that heat exchange completes
Gas becomes gaseous state and is again introduced into blood circulation after recycle gas compressor system C2 is compressed.
Embodiment three: as it is shown on figure 3, a kind of gas cryogenic liquefying system, be provided with compression unit, heat exchange list
Unit, expansion liquefaction unit and gas-liquid separation unit, wherein compression unit is provided with feed gas compressor system C1
With recycle gas compressor system C2, heat exchange unit is provided with first-class heat exchanger E1, the secondary heat exchange being sequentially connected in series
Device E2 and three grades of heat exchanger E3, expands liquefaction unit and is provided with nozzles with injector M1 and nozzles with injector M2, gas
Liquid separative element is made up of knockout drum S1, knockout drum S2, knockout drum S3 and knockout drum S4;
Concrete annexation is that the input of feed gas compressor system C1 is connected with unstripped gas, outfan and
The input of described first-class heat exchanger E1 connects, the first branch road of the outfan of this first-class heat exchanger E1 and two
The input of level heat exchanger E2 connects, defeated with the coolant of secondary heat exchanger E2 after the second branch road concatenation choke valve
Entering end to connect, the coolant outfan of this secondary heat exchanger E2 is connected with recycle gas compressor system C2 input,
The outfan of this recycle gas compressor system C2 is attempted by the input of first-class heat exchanger E1;
The input of the outfan of secondary heat exchanger E2 and three grades of heat exchanger E3 connects, three grades of heat exchanger E3
Outfan be connected with described nozzles with injector M1 and nozzles with injector M2 input respectively, this nozzles with injector M1
Input with described knockout drum S1 and knockout drum S2 is connected respectively with the outfan of nozzles with injector M2, institute
The coolant input of the gas output end and described three grades of heat exchanger E3 of stating knockout drum S1 is connected, and these three grades are changed
The coolant outfan of hot device E3 is connected with the first coolant input of described first-class heat exchanger E1, described separation
With the coolant input of described secondary heat exchanger E2 after first branch road concatenation regulation valve of tank S1 finished product outfan
Connect, the first coolant outfan of described first-class heat exchanger E1 and the input of recycle gas compressor system C2
Connect;
With the input of described knockout drum S2 after second branch road concatenation choke valve of knockout drum S1 finished product outfan
Connecting, the gas output end of this knockout drum S2 is connected with the input of described nozzles with injector M1, described separation
It is connected with the input of described knockout drum S3 after the finished product outfan concatenation choke valve of tank S2, this knockout drum S3
Input also with storage system gas output end be connected, gas output end is defeated with described nozzles with injector M2's
Entering end to connect, finished product outfan is connected with the input of described storage system after being adjusted valve, described knockout drum
The fixed gas outfan of S4 is connected with the second coolant input of described first-class heat exchanger E1 after being adjusted valve, and one
The second coolant outfan of level heat exchanger E1 is connected with fixed gas reutilization system, and the finished product of knockout drum S4 is defeated
Go out end and be connected through the input of choke valve with described knockout drum S2;
The gas phase outlet of described knockout drum S1 is yet adjusted the input of valve and described knockout drum S3 inner coil pipe
Connecting, the outfan of this coil pipe is connected with the input of described knockout drum S4.
The present embodiment is identical with other operation logic of embodiment one and two, and distinctive points is, secondary heat exchanger
The coolant of E2 uses first-class heat exchanger E1 output process gas and the finished product liquid work of knockout drum S1 outfan simultaneously
Skill gas, can be selected by regulation valve, in whole system running status first, because the knockout drum of rear class
S1 also cannot provide finished product liquid process gas as coolant, and first-class heat exchanger E1 now can be used to export process gas
As coolant after choke valve is lowered the temperature, whole system can be made to rapidly enter duty.
Claims (5)
1. a gas cryogenic liquefying system, it is characterised in that: it is provided with compression unit, heat exchange unit, swollen
Swollen liquefaction unit and gas-liquid separation unit, first-class heat exchanger E1 that wherein said heat exchange unit includes being sequentially connected in series,
Secondary heat exchanger E2 and three grades of heat exchanger E3, the input of wherein said first-class heat exchanger E1 and described compression
The outfan of unit connects, the outfan of described three grades of heat exchanger E3 and the input of described expansion liquefaction unit
Connecting, the outfan of described expansion liquefaction unit is connected with described gas-liquid separation unit;
The coolant input of described three grades of heat exchanger E3 is connected with the gas output end of described gas-liquid separation unit,
The coolant outfan of these three grades of heat exchanger E3 is connected with the first coolant input of described first-class heat exchanger E1,
First coolant outfan of this first-class heat exchanger E1 is connected with described compression unit;
The coolant input of described secondary heat exchanger E2 is connected with the finished product outfan of described gas-liquid separation unit,
Or it is connected with the outfan of described first-class heat exchanger E1, the coolant outfan of this secondary heat exchanger E2 and institute
State compression unit to connect.
Gas cryogenic liquefying system the most according to claim 1, it is characterised in that: described expansion liquefaction is single
Unit is made up of nozzles with injector M1 and nozzles with injector M2, and described gas-liquid separation unit is by knockout drum S1, separation
Tank S2, knockout drum S3 and knockout drum S4 composition, the outfan of wherein said three grades of heat exchanger E3 respectively with
Described nozzles with injector M1 and nozzles with injector M2 input connect, this nozzles with injector M1 and nozzles with injector M2
Outfan input with described knockout drum S1 and knockout drum S2 respectively is connected, the gas of described knockout drum S1
Outfan is connected with the coolant input of described three grades of heat exchanger E3, described knockout drum S1 finished product outfan
First branch road is adjusted valve and is connected with the coolant input of described secondary heat exchanger E2, and the second branch road is through choke valve
It is connected with the input of described knockout drum S2, the gas output end of this knockout drum S2 and described nozzles with injector M1
Input connect, the finished product outfan of described knockout drum S2 is through the input of choke valve Yu described knockout drum S3
End connect, the input of this knockout drum S3 also with storage system gas output end is connected, gas output end and
The input of described nozzles with injector M2 connects, and finished product outfan is adjusted the input of valve and described storage system
Connect.
Gas cryogenic liquefying system the most according to claim 2, it is characterised in that: described knockout drum S4
Fixed gas outfan be adjusted valve and be connected with the second coolant input of described first-class heat exchanger E1, this one-level
The second coolant outfan of heat exchanger E1 is connected with fixed gas reutilization system.
Gas cryogenic liquefying system the most according to claim 2, it is characterised in that: described knockout drum S1
Gas phase outlet be yet adjusted valve and be connected with the input of described knockout drum S3 inner coil pipe, the output of this coil pipe
End is connected with the input of described knockout drum S4, and the output of products end of described knockout drum S4 is through choke valve and institute
The input stating knockout drum S2 connects.
Gas cryogenic liquefying system the most according to claim 1, it is characterised in that: described compression unit sets
It is equipped with feed gas compressor system C1 and recycle gas compressor system C2, wherein feed gas compressor system C1
Input be connected with unstripped gas, outfan is connected with the input of described first-class heat exchanger E1, and this one-level is changed
Hot device E1 outfan the first branch road is connected with the input of described secondary heat exchanger E2, and the second branch road is through throttling
After valve, the coolant input with described secondary heat exchanger E2 is connected, the outfan and three of this secondary heat exchanger E2
The input of level heat exchanger E3 connects, coolant outfan and the input of described recycle gas compressor system C2
Connecting, the input of this recycle gas compressor system C2 is also defeated with the first coolant of described first-class heat exchanger E1
Go out end to connect, the outfan of described recycle gas compressor system C2 and the input of described first-class heat exchanger E1
Connect.
Priority Applications (1)
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CN201620283647.4U CN205561413U (en) | 2016-04-07 | 2016-04-07 | Gaseous cryogenic liquefying system |
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CN201620283647.4U CN205561413U (en) | 2016-04-07 | 2016-04-07 | Gaseous cryogenic liquefying system |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105698486A (en) * | 2016-04-07 | 2016-06-22 | 重庆鲍斯可燃气工程有限公司 | Gas cryogenic liquefying system |
CN108014740A (en) * | 2017-12-21 | 2018-05-11 | 常州大学 | A kind of new gas hydrate pipeline generating means |
-
2016
- 2016-04-07 CN CN201620283647.4U patent/CN205561413U/en not_active Withdrawn - After Issue
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105698486A (en) * | 2016-04-07 | 2016-06-22 | 重庆鲍斯可燃气工程有限公司 | Gas cryogenic liquefying system |
CN105698486B (en) * | 2016-04-07 | 2017-11-10 | 重庆鲍斯可燃气工程有限公司 | A kind of gas cryogenic liquefying system |
CN108014740A (en) * | 2017-12-21 | 2018-05-11 | 常州大学 | A kind of new gas hydrate pipeline generating means |
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GR01 | Patent grant | ||
AV01 | Patent right actively abandoned |
Granted publication date: 20160907 Effective date of abandoning: 20171110 |
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AV01 | Patent right actively abandoned |