CN105987579B - The method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas - Google Patents

The method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas Download PDF

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CN105987579B
CN105987579B CN201510052405.4A CN201510052405A CN105987579B CN 105987579 B CN105987579 B CN 105987579B CN 201510052405 A CN201510052405 A CN 201510052405A CN 105987579 B CN105987579 B CN 105987579B
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natural gas
gas
methane
mixed gas
methane mixed
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CN105987579A (en
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冯刚
徐锋
陈琪
李雪勇
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SHANGHAI BAOSTEEL GAS CO Ltd
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SHANGHAI BAOSTEEL GAS CO Ltd
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Abstract

The method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas, includes the following steps:1) methane mixed gas is pre-processed, removes water removal, carbon dioxide;2) heat is provided for tower reactor into two-stage rectification tower after methane mixed gas is cooled to 120~160 DEG C, 150~165 DEG C is further cooled to later and enters the progress rectifying separation of level-one rectifying column, the dichloromethane of concentrate is obtained in tower reactor;3) dichloromethane enters two-stage rectification tower after being decompressed to 5~10barg, carries out rectifying separation again, liquefied natural gas crude product is obtained in tower reactor, through laggard step expenditure and pressure is subcooled to normal pressure, becomes liquefied natural gas product;Meanwhile two-stage rectification tower lateral line discharging or tower reactor discharge to obtain compressed natural gas crude product, are re-compressed into after re-heat to room temperature as compressed natural gas product.The method of the present invention can obtain two kinds of products of compressed natural gas and liquefied natural gas simultaneously, and relatively high using the conventional quality for preparing compressed natural gas product such as absorption, UF membrane.

Description

The method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas
Technical field
The present invention relates to natural gas preparing technical field, especially one kind, and it is natural to produce compression simultaneously from methane mixed gas The method of gas and liquefied natural gas.
Background technology
Coal, oil and natural gas are three big pillars of world today's primary energy, and natural gas disappears in certain energy such as Japan Expense big country has become the second largest energy.Early period in 19th century, the mankind replace firewood as main energy sources, realize industrial leather using coal Life, brings the capitalistic development in the world, is first time energy revolution.20th century mid-term, start with oil be instead of coal Main energy sources bring the prosperity of world economy, are second of energy revolutions.The in the 21st century, whole world will occur with natural It is the energy consumption structure great change again of main energy sources that gas, which replaces oil, and natural gas is in energy consumption structure within 2008 The proportion world average 24.1%, it is contemplated that 2015, natural gas will account for 35~40% in world's energy resource structure, become the first big energy Source will be third time energy revolution.21 century will be a natural gas century, be the epoch of clean energy resource.Since nineteen ninety Increased every year with 23% rate.World energy sources economy is from petroleum-based energy economy to natural gas energy resource transition.
Natural gas has many advantages, such as clean, efficient, resourceful and facilitates storage and transportation, send out energetically as a kind of green energy resource Exhibition natural gas is the effective way alleviated energy shortages, reduced environmental pollution.For this purpose, the Chinese government pays much attention to Gas Industry Development, natural gas will be as the bright spot and one of green energy resource pillar in our country energy development strategy.
Domestic natural gas is in short supply, greatly needs from external import, and natural gas is first generally prepared into liquefaction naturally Gas, then domestic market is sold to by shipping.There is certain dependence to external natural gas.
In recent years, the technology for synthetic natural gas being prepared using coke-stove gas has obtained significant progress.Coke-stove gas passes through Reaction be synthetically generated the synthesis gas rich in methane gas, using the mode of different separating-purifyings prepare compressed natural gas or Liquefied natural gas.The technological means of two kinds of separating-purifyings is entirely different, and used apparatus also has prodigious difference, pressure Contracting natural gas generally use is adsorbed or the conventional separation methods such as UF membrane are produced, the side of liquefied natural gas generally use cryogenic separation Method is produced.Cannot meet the needs of client is to two kinds of products of compressed natural gas and liquefied natural gas simultaneously.
Invention content
The object of the present invention is to provide a kind of from methane mixed gas produces compressed natural gas and liquefied natural gas simultaneously Method can obtain two kinds of products of compressed natural gas and liquefied natural gas simultaneously using this method, and the yield of two kinds of products can To carry out conversion adjusting as desired.The compressed natural gas quality prepared using this method is relatively conventional using absorption, UF membrane etc. The quality for preparing compressed natural gas product is high.
In order to achieve the above objectives, the technical scheme is that:
The method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas comprising following steps:
1) methane mixed gas is pre-processed, removal wherein water, carbon dioxide, water in treated methane mixed gas Content≤1ppm, carbon dioxide content≤50ppm.
2) treated provides heat after methane mixed gas is cooled to -120 DEG C~-160 DEG C into two-stage rectification tower for tower reactor Amount is further cooled to -150 DEG C~-165 DEG C and enters the progress rectifying separation of level-one rectifying column, concentrate is obtained in tower reactor later Dichloromethane, methane content be 80~99% molar percentages, tower top generate the hydrogen containing 80% or more molar percentage The hydrogen rich off gas re-heat of gas is to room temperature;
3) dichloromethane enters two-stage rectification tower after being decompressed to 5~10barg, rectifying separation is carried out again, in tower reactor Liquefied natural gas crude product is obtained, purity meets one class standard of natural gas, methane content >=99%, after supercooling, into one Expenditure and pressure is walked to normal pressure, becomes liquefied natural gas product, purity meets one class standard of natural gas, methane content >=99%; Meanwhile two-stage rectification tower lateral line discharging or tower reactor discharge to obtain compressed natural gas crude product, purity meets natural gas one kind Standard, tower reactor discharging methane content >=99%, lateral line discharging methane content range >=93%, after re-heat to room temperature, recompression is extremely Certain pressure, becomes compressed natural gas product, and purity meets one class standard of natural gas, tower reactor discharging product methane content model >=99% is enclosed, lateral line discharging product methane content range >=93%;The pressure of compressed natural gas product is 2~300barg;Tower top The rich nitrogen tail gas re-heat containing 80% or more nitrogen generated is to room temperature.
Further, step 1) methane mixed gas pretreatment removal water is removed using the method for absorption.
It is taken off also, the pretreatment of step 1) methane mixed gas goes removing carbon dioxide to be removed i.e. wet method using chemical absorption process Carbon and/or use adsorption method are removed i.e. dry method decarburization.
Preferably, step 2) treated methane mixed gas is first cooled to 5~15 DEG C in advance.
In addition, the cold of cooling methane mixed gas is in addition to the compressed natural gas and one rich nitrogen tail gas by re-heat in step 2) Except being provided with one hydrogen rich off gas, provided by azeotrope;Azeotrope be compressed to 20~50barg postcoolings to 30 DEG C~ 40 DEG C, carry out gas-liquid separation, air-liquid two-phase cooled down respectively, liquid phase be cooled to -30 DEG C~-100 DEG C deutomerite flow to 2~ 6barg, gas phase are cooled to -150 DEG C~-165 DEG C deutomerite and flow to 2~6barg, then carry out heat exchange and provide cold, by re-heat to normal Wen Houzai carries out compression cooling, forms azeotrope refrigeration cycle.
Preferably, azeotrope is compressed to 20~50barg postcoolings to 30 DEG C~40 DEG C, then after being cooled to 5 DEG C~15 DEG C in advance Carry out gas-liquid separation.
The overhead condensation low-temperature receiver of two-stage rectification tower is provided by liquid nitrogen;Nitrogen is compressed to 20~50barg postcoolings to 40 DEG C, then cooled down, two strands are divided into after being cooled to -150 DEG C~-165 DEG C, is throttled respectively, is after throttling to 3~5barg Rectifying column provides cold, and re-heat later is to room temperature, then carries out compression cooling, forms nitrogen refrigeration cycle.
Preferably, nitrogen is compressed to 20~50barg postcoolings to 40 DEG C, then is cooled down after being cooled to 5 DEG C~15 DEG C in advance.
The methane mixed gas, azeotrope and nitrogen precooled required cold are provided by chilled water.
In addition, the product proportion of compressed natural gas of the present invention and liquefied natural gas is adjusted as desired, the ratio of adjusting Example is 0:1-1:0.
The operating mode of two-stage rectification tower is adjusted to be realized by adjusting tower bottoms position, overhead reflux amount, overhead condensation amount;Mixing The flow-rate adjustment of cryogen passes through the adjusting of azeotrope suction port of compressor guide vane or inlet adjustment valve, azeotrope compressor The adjusting of return valve, the size in azeotrope driven compressor source are realized;The adjusting of azeotrope component is different by increasing The cryogen amount of component, realizes the variation of refrigerant components;The flow-rate adjustment of nitrogen passes through nitrogen compressor inlet guide vane or entrance The adjusting of regulating valve, the adjusting of the return valve of nitrogen compressor, nitrogen compressor driving source size realize.
The compressed natural gas product prepared using the method for the present invention disclosure satisfy that GB 17820-2012《Natural gas》Middle one kind The standard of natural gas, compared to the existing compression day using technologies separating-purifyings from methane mixed gas such as absorption, UF membranes Right gas product is only capable of for reaching two class natural gas standards, and product quality has obtained great promotion, belongs to good compression day Right gas product.
The present invention the advantage is that for existing liquefied natural gas and compressed natural gas process for separation and purification:
Using the method for the present invention compared to traditional absorption, separation method unitary system for compressed natural gas product and deep cooling point From method unitary system for liquefied natural gas product for, advantage is that compressed natural gas and liquefied natural gas two can be prepared simultaneously Kind product, and pass through the flow of the flow and component of the working condition and azeotrope that adjust two-stage rectification tower, nitrogen, compression The ratio of natural gas and liquefied natural gas can on a large scale be adjusted by control means.
The compressed natural gas product prepared using the method for the present invention is relative to using technologies systems such as traditional absorption, UF membranes For standby compressed natural gas product, product quality has obtained greatly being promoted, and has reached the standard of one class natural gas of national standard.Especially It is even more to have reached the standard of liquefied natural gas that it, which is using the discharge product quality of compressed natural gas that this mode obtains of tower reactor,.
It is natural relative to compression is prepared using liquefied natural gas pressurization vaporization that compressed natural gas is prepared using the method for the present invention It for gas, obtains that compressed natural gas product quality is equally higher, has reached the standard of liquefied natural gas.It the advantage is that, use Energy consumption prepared by the method for the present invention is lower, and economy is more preferable.
Description of the drawings
Fig. 1 is the process schematic representation of the embodiment of the present invention.
Specific implementation mode
Referring to Fig. 1, the method for the invention for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas, Include the following steps:
1) methane mixed gas is pre-processed, removal wherein water, carbon dioxide, water in treated methane mixed gas Content≤1ppm, carbon dioxide content≤50ppm.
2) treated provides heat after methane mixed gas is cooled to -120 DEG C~-160 DEG C into two-stage rectification tower for tower reactor Amount is further cooled to -150 DEG C~-165 DEG C and enters the progress rectifying separation of level-one rectifying column, concentrate is obtained in tower reactor later Dichloromethane, methane content be 80~99% molar percentages, tower top generate the hydrogen containing 80% or more molar percentage The hydrogen rich off gas re-heat of gas is to room temperature;
3) dichloromethane enters two-stage rectification tower after being decompressed to 5~10barg, rectifying separation is carried out again, in tower reactor Liquefied natural gas crude product is obtained, purity meets one class standard of natural gas, methane content >=99%, after supercooling, into one Expenditure and pressure is walked to normal pressure, becomes liquefied natural gas product, purity meets one class standard of natural gas, methane content >=99%; Meanwhile two-stage rectification tower lateral line discharging or tower reactor discharge to obtain compressed natural gas crude product, purity meets natural gas one kind Standard, tower reactor discharging methane content >=99%, lateral line discharging methane content range >=93%, after re-heat to room temperature, recompression is extremely Certain pressure, becomes compressed natural gas product, and purity meets one class standard of natural gas, tower reactor discharging product methane content model >=99% is enclosed, lateral line discharging product methane content range >=93%;The pressure of compressed natural gas product is 2~300barg;Tower top The rich nitrogen tail gas re-heat containing 80% or more nitrogen generated is to room temperature.
Further, step 1) methane mixed gas pretreatment removal water is removed using the method for absorption.
It is taken off also, the pretreatment of step 1) methane mixed gas goes removing carbon dioxide to be removed i.e. wet method using chemical absorption process Carbon and/or use adsorption method are removed i.e. dry method decarburization.
Preferably, step 2) treated methane mixed gas is first cooled to 5~15 DEG C in advance.
In addition, the cold of cooling methane mixed gas is in addition to the compressed natural gas and one rich nitrogen tail gas by re-heat in step 2) Except being provided with one hydrogen rich off gas, provided by azeotrope;Azeotrope be compressed to 20~50barg postcoolings to 30 DEG C~ 40 DEG C, carry out gas-liquid separation, air-liquid two-phase cooled down respectively, liquid phase be cooled to -30 DEG C~-100 DEG C deutomerite flow to 2~ 6barg, gas phase are cooled to -150 DEG C~-165 DEG C deutomerite and flow to 2~6barg, then carry out heat exchange and provide cold, by re-heat to normal Wen Houzai carries out compression cooling, forms azeotrope refrigeration cycle.
Preferably, azeotrope is compressed to 20~50barg postcoolings to 30 DEG C~40 DEG C, then after being cooled to 5 DEG C~15 DEG C in advance Carry out gas-liquid separation.
The overhead condensation low-temperature receiver of two-stage rectification tower is provided by liquid nitrogen;Nitrogen is compressed to 20~50barg postcoolings to 40 DEG C, then cooled down, two strands are divided into after being cooled to -150 DEG C~-165 DEG C, is throttled respectively, is after throttling to 3~5barg Rectifying column provides cold, and re-heat later is to room temperature, then carries out compression cooling, forms nitrogen refrigeration cycle.
Preferably, nitrogen is compressed to 20~50barg postcoolings to 40 DEG C, then is cooled down after being cooled to 5 DEG C~15 DEG C in advance.
The methane mixed gas, azeotrope and nitrogen precooled required cold are provided by chilled water.
In addition, the product proportion of compressed natural gas of the present invention and liquefied natural gas is adjusted as desired, the ratio of adjusting Example is 0:1-1:0.
Embodiment
Methane mixed gas passes through wet method decarburization 1, and dehydration 2 and dry method decarburization 3 pre-process, and remove wherein high boiling component Water, carbon dioxide.Wherein wet method decarburization 1 belongs to option, is determined whether according to the carbon dioxide content in methane mixed gas Increase wet method decarburization.In treated methane mixed gas, the content of water answers≤1ppm, carbon dioxide content to answer≤50ppm.
The methane mixed gas handled well enters pre-cooling unit 4 and is pre-chilled, and heat exchange unit 5 is entered after being cooled to 12 DEG C in advance and is carried out It is cooling, heat is provided for tower reactor into 6 tower reactor reboiler 61 of two-stage rectification tower after being cooled to -127 DEG C, it is single to enter back into heat exchange later It is further cooled down in member 5,7 tower reactor of level-one rectifying column is entered after being cooled to -156 DEG C and carries out rectifying separation, concentrate is obtained in tower reactor Dichloromethane, the content of methane component is 99% in dichloromethane, and hydrogen rich off gas of the tower top containing 80% or more hydrogen is by changing 5 re-heat of hot cell is to room temperature.Dichloromethane enters two-stage rectification tower 6 after throttle valve V6 is decompressed to 7barg, carries out essence again Fraction is from it is 99.2% liquefied natural gas crude product to obtain methane purity in tower reactor, is crossed after being cooled to -162 DEG C, further by throttling Valve V1 is decompressed to normal pressure, becomes liquefied natural gas product;Meanwhile two-stage rectification tower 6 lateral line discharging 1. or tower reactor discharging 2. To compressed natural gas crude product, methane content >=93% in the compressed natural gas crude product obtained using 1. route, using 2. Methane content >=99% in the compressed natural gas crude product that route obtains, by (heat exchanger) re-heat of heat exchange unit 5 to room temperature Afterwards, it is compressed to certain pressure using natural gas compressing unit 8, becomes compressed natural gas product, specific pressure regards compression Depending on the demand of gas product;Tower top contains rich nitrogen tail gas re-heat after heat exchange unit 5 (heat exchanger) of 80% or more nitrogen To room temperature.
5 required cold of heat exchange unit is mainly cold by mixing other than the compressed natural gas of re-heat and two strands of tail gas Agent provides.Azeotrope is compressed to 30barg postcoolings to 40 DEG C by cryogen compression unit 9, is carried out into pre-cooling unit 4 pre- It is cold, liquid separation tank 11 is entered after being cooled to 12 DEG C in advance and carries out gas-liquid separation, liquid phase is sent to heat exchange unit 5 (heat exchanger) and cooled down, cold But to 4barg is decompressed to by throttle valve V4 after -50 DEG C, heat exchange unit 5 is returned again to, meanwhile, gas phase is also sent to heat exchange unit 5 and is carried out 4barg is decompressed to by throttle valve V5 after being cooled to -156 DEG C, heat exchange unit 5 is returned again to and converges with the liquid phase cryogen backflowed, answered Cryogen compression unit 9 is entered back into after heat to room temperature and carries out compression cooling, forms cryogen refrigeration cycle.
Tower top (condenser 62) low-temperature receiver of two-stage rectification tower 6 is provided by liquid nitrogen.Nitrogen is pressed by nitrogen compression unit 10 30barg postcoolings are reduced to 40 DEG C, are pre-chilled into pre-cooling unit 4, are carried out into heat exchange unit 5 after being cooled to 12 DEG C in advance cold But, two strands are divided into after being cooled to -156 DEG C, it is that tower top is (cold that one is decompressed to 5barg to enter two-stage rectification tower 6 by throttle valve V2 Condenser 62) cold is provided, it is tower top (condenser 72) that another stock is decompressed to 5barg to enter level-one rectifying column 7 by throttle valve V3 Cold is provided, the nitrogen after two bursts of heat exchange converge after after the heat exchange of heat exchange unit 5 re-heat enter back into nitrogen compression to room temperature Unit 10 carries out compression cooling, forms nitrogen refrigeration cycle.
The cold of pre-cooling unit 4 is provided by chilled water, and after chilled water enters the heat exchange of pre-cooling unit 4, re-heat to cooling water is returned It returns.Whether determined by freezing water condition using pre-cooling unit 4, if itself has chilled water, or with the item for preparing chilled water Part, you can use pre-cooling unit, otherwise, methane mixed gas, azeotrope and the nitrogen handled well without precooling, directly into Enter heat exchange unit 5 to be cooled down.

Claims (10)

1. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas, characterized in that including walking as follows Suddenly:
1) methane mixed gas is pre-processed, removal wherein water, carbon dioxide, the content of water in treated methane mixed gas ≤ 1ppm, carbon dioxide content≤50ppm;
2) treated provides heat after methane mixed gas is cooled to -120 DEG C~-160 DEG C into two-stage rectification tower for tower reactor, it It is further cooled to -150 DEG C~-165 DEG C afterwards and enters the progress rectifying separation of level-one rectifying column, the methane of concentrate is obtained in tower reactor Solution, methane content are 80~99% molar percentages, the richness for the hydrogen containing 80% or more molar percentage that tower top generates The re-heat of hydrogen tail gas is to room temperature;
3) dichloromethane enters two-stage rectification tower after being decompressed to 5~10barg, carries out rectifying separation again, is obtained in tower reactor Liquefied natural gas crude product, purity meet one class standard of natural gas, and methane content >=99% further saves after supercooling Stream is decompressed to normal pressure, becomes liquefied natural gas product, and purity meets one class standard of natural gas, methane content >=99%;Meanwhile Two-stage rectification tower lateral line discharging or tower reactor discharge to obtain compressed natural gas crude product, and purity meets one class standard of natural gas, Tower reactor discharging methane content >=99%, lateral line discharging methane content range >=93% after re-heat to room temperature, are recompressed to certain Pressure, becomes compressed natural gas product, and purity meets one class standard of natural gas, tower reactor discharge product methane content range >= 99%, lateral line discharging product methane content range >=93%;The pressure of compressed natural gas product is 2~300barg;Tower top generates The rich nitrogen tail gas re-heat containing 80% or more nitrogen to room temperature.
2. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as described in claim 1, It is characterized in, step 1) methane mixed gas pretreatment removal water is removed using the method for absorption.
3. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as described in claim 1, It is characterized in, the pretreatment of step 1) methane mixed gas goes removing carbon dioxide to be removed i.e. wet method decarburization using chemical absorption process And/or i.e. dry method decarburization is removed using adsorption method.
4. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as described in claim 1, It is characterized in, step 2) treated methane mixed gas is first cooled to 5~15 DEG C in advance.
5. purify while preparing compressed natural gas and liquefied natural gas using methane mixed gas as described in claim 1 Method, characterized in that the cold of cooling methane mixed gas is in addition to the compressed natural gas and one rich nitrogen tail by re-heat in step 2) Except gas and one hydrogen rich off gas provide, provided by azeotrope;Azeotrope is compressed to 20~50barg postcoolings to 30 DEG C ~40 DEG C, carry out gas-liquid separation, air-liquid two-phase cooled down respectively, liquid phase be cooled to -30 DEG C~-100 DEG C deutomerite flow to 2~ 6barg, gas phase are cooled to -150 DEG C~-165 DEG C deutomerite and flow to 2~6barg, then carry out heat exchange and provide cold, by re-heat to normal Wen Houzai carries out compression cooling, forms azeotrope refrigeration cycle.
6. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as claimed in claim 5, It is characterized in, azeotrope is compressed to 20~50barg postcoolings to 30 DEG C~40 DEG C, then is cooled to 5 DEG C~15 DEG C laggard promoting the circulation of qi liquid in advance Separation.
7. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as described in claim 1, It is characterized in, the overhead condensation low-temperature receiver of two-stage rectification tower is provided by liquid nitrogen;Nitrogen is compressed to 20~50barg postcoolings to 40 DEG C, It is cooled down again, two strands is divided into after being cooled to -150 DEG C~-165 DEG C, is throttled respectively, be rectifying after throttling to 3~5barg Tower provides cold, and re-heat later is to room temperature, then carries out compression cooling, forms nitrogen refrigeration cycle.
8. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as claimed in claim 7, It is characterized in, nitrogen is compressed to 20~50barg postcoolings to 40 DEG C, then is cooled down after being cooled to 5 DEG C~15 DEG C in advance.
9. the side of compressed natural gas and liquefied natural gas is produced in the slave methane mixed gas as described in claim 2 or 6 or 8 simultaneously Method, characterized in that the methane mixed gas, azeotrope and nitrogen precooled required cold are provided by chilled water.
10. the method for producing compressed natural gas and liquefied natural gas simultaneously from methane mixed gas as described in claim 1, It is characterized in, the product proportion of the compressed natural gas and liquefied natural gas is adjusted as desired, and the ratio of adjusting is 0:1- 1:0。
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