CN103881775A - Preparation and energy recycling system of coal-bed gas hydrate - Google Patents
Preparation and energy recycling system of coal-bed gas hydrate Download PDFInfo
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Abstract
The invention provides a preparation and energy recycling system of coal-bed gas hydrate. The preparation and energy recycling system comprises a coal-bed gas booster pump, a refrigerant heat exchanger, a tail gas cooling capacity recycler, an un-reacted coal-bed gas cooling capacity recycler, a hydrate reactor, a hydrate decomposer, a saturated absorption liquid cooling capacity recycler, an absorption liquid circulating pump, and the like. A coal-bed gas is pressurized, cooled by saline water and liquid nitrogen through multiple steps; the coal-bed gas is ventilated from the bottom of the reactor to carry out countercurrent contact reaction with the adsorption liquid sprayed from the top of the reactor; saturated methane adsorption slurry is pumped into the decomposer by a discharging pump from the lower part of the reactor; the saturated absorption slurry carries out countercurrent indirect heat exchange with the absorption liquid entering the decomposer, and is re-pumped into the hydrate reactor after being cooled by the saline water; and methane discharged by the hydrate decomposer through a vent valve enters an LNG (liquefied natural gas) production system. Production cost of extracting methane from the coal-bed gas hydrate is greatly lowered by recycling the cooling capacity in the tail gas exhaustion gas, the cooling capacity in the un-reacted coal-bed gas, and cooling capacity in the statured absorption liquid.
Description
Technical field
The present invention relates to a kind of coalbed methane hydrate dissociation separation of methane and energy-recuperation system device, belong to coalbed methane hydrate dissociation preparation and energy recovery and utilize technical field.
Background technology
China has abundant coal bed gas resource, it is estimated that the coal bed gas resource amount of buried depth in 2000m is about 30～35 × 10
12m
3.Along with the reduction of technical development and cost of winning, cbm development, just fast to mass-producing, industrialized development, forms and produces 200～300 × 10 per year gradually
8m
3throughput.Along with the continuous expansion of cbm development scale, traditional industry technology directly affects the formation of coal gas industry chain, become the bottleneck place of coal-seam gas industrial development, use of the new technology and extraction coal-seam gas is carried out to Handling and transportation as Hydrate Technology etc., undoubtedly can be for coal-seam gas industrial expansion injects new life under the normal conditions, 1m
3methane hydrate portability 150～170m
3methane gas.Research shows, methane hydrate can, at 2～6MPa, be prepared under the condition of 0～20 ℃, more than normal pressure-15 ℃ stably stored, and heating or step-down can realize its decomposition.The gas storage and transportation technology occurring with solid-state form is the novel storaging and transport technology that is different from pipeline (gaseous form) conveying, liquefaction (liquid form) technology completely, the gas storage condition that it is gentle and relatively high gas storage capability make the Storage And Transportation In Solid State mode of coal-seam gas become possibility, and the decomposition of hydrate need to absorb amount of heat.It is reported, Norway has successfully developed the technology with hydrate state transport gas under-15 ℃ and normal pressure, and cost lower temperature (160 ℃) liquefaction is carried and approximately reduced 26%.Methane is a kind of strong greenhouse gases, and its Greenhouse effect are about 21 times of CO2, and in atmospheric environment, methane up to 18%, is only second to CO2 to the contribution rate of Global Greenhouse Effect.The methane of the movable annual discharge of world's coal mining reaches 360～58,000,000,000 m
3, account for 5%～8% of global methane emission.China's coal-seam gas annual emissions is about 80～10,000,000,000 m
3, account for global CBM Drainage high-volume 1/4.1999, in the high gas in more than 1000, the whole nation and Gas Outburst mine, only there are 158 collieries to set up drainage system and ground gas transmission system under coal bed gas well, year extraction coal-seam gas 7.4 hundred million m
3, the average down-hole coal bed gas extraction rate in the whole nation is only 23%.And because shortage is utilized facility and effectively utilized approach, coal-seam gas year, utilization was less than 500,000,000 m
3.In addition, due to extraction pipeline and method unreasonable, considerable part methane concentration lower than 30% coal-seam gas because of without industrial application value, conventional cost for purification is high is directly discharged in atmosphere, has both caused environmental pollution, wastes again resource.Therefore, utilize hydrate method, it is a kind of feasible approach that extraction coal-seam gas is purified, the coal-seam gas that drainage system flows out is pressurization after dehydration, in reactor, after low temperature hydration, dehydrofreezing becomes solid hydrate, and non-hydrated gas is by discharging in reactor.The generative process of coal-seam gas formation hydrate is namely removed the purification process of non-hydrated gas.With solid-state form accumulating coal-seam gas, there is the features such as safe, cost is low, likely become a kind of important gas storage and transportation mode.
Coalbed methane hydrate dissociation be the methane in a kind of coal-seam gas react with water generate cage compound, gases methane and liquid water need to be cooled in advance-5～15 ℃, more than 3MPa, water molecules, host molecule, by hydrogen bond action, form the lattice main body with certain size hole, less gas molecule, guest molecule are mainly methane CH
4, be included in hole, thereby form the solid compounds of outer appearnce like snowflake or ice, its density is 0.905～0.910g/cm
3.Under the normal conditions, the methane that the typical hydrate of 1 volume comprises 164 volumes, reduced 164 times of namely for methane volume.
According to estimates, Coalbed Methane In China reserves are about 31.54 trillion m
3, be considered to one of the most promising new forms of energy.Lot of documents has been reported synthetic, the formation mechanism of coalbed methane hydrate dissociation, in the generative process of the Water Under compounds such as not siliceous, aluminium, ferriferous oxide, affect the factor of generating rate, as pressure, temperature, condensate depression, stir speed (S.S.), gas-to-liquid contact interfacial area, kinds of surfactants, addition etc.; The relation of hydrate induction time and condensate depression, as synthetic in constant volume under methane hydrate Static and dynamic condition/decomposition course, induction time and growth velocity etc. in hydrate building-up process; Pressure-temperature change curve in synthesize/decomposition course of hydrate constant volume, the impact of condensate depression on hydrate crystal surface energy; Under identical pressure (3MPa) condition, hydrate compound experiment result while having contrasted 1 ℃ of temperature and 5 ℃, condensate depression generates the impact of the transformation efficiency of hydrate on different components in coal-seam gas; The impact of condensate depression component on hydrate as synthetic motivating force; The impact of condensate depression on methane hydrate induction time; The kinetic equation that hydrate generates after nucleation of having derived, has introduced effective surface integration rate, pressure index, condensate depression correction parameter, has obtained the improved kinetic equation that air water system hydrate generates.But the energy for coalbed methane hydrate dissociation in preparation process, as balance and the recovery of cold (heat) amount, rarely has reported in literature.Therefore patent of the present invention is intended to fully reclaim the energy in coalbed methane hydrate dissociation production process, reduces the production cost of hydrate, and this industrialization for coalbed methane hydrate dissociation is significant
Summary of the invention
One object of the present invention is to extract cost recovery when methane and cross the problems such as high in order to solve coalbed methane hydrate dissociation, and provide a kind of coalbed methane hydrate dissociation to reclaim methane system, this retrieving arrangement has energy recovery utilizing system, the tail gas that it discharges coalbed methane hydrate dissociation reactor head carries out adverse current indirect heat exchange by circulation and the coal-seam gas initially entering, thereby reclaim its cold, reach the object that reduces coal-seam gas initial temperature; The coal-seam gas of the not complete reaction that hydrate reactor top is discharged is mixed direct heat exchange by circulation with the coal-seam gas initially entering, thereby reclaims its cold, and reduces coal-seam gas initial temperature; The methane saturated absorption liquid that hydrate reactor lower end is discharged by with absorption liquid adverse current indirect contact from splitter, thereby reclaim the cold in saturated absorption liquid, and reach the object that reduces circulating absorption solution temperature.Coal-seam gas is cooling by three grades, i.e., after precooling (circulation gas cold recovery), brine refrigeration and cooled with liquid nitrogen, enter reactor from hydrate reactor bottom gas distributor; In reactor, reaction heat is taken away by the chilled brine in spiral coil cooling tube, and controls temperature.In reactor, spiral coil cooling tube is prepared by copper metallic substance, and the low temperature of metallic surface and thermal conductivity, can accelerate the growth of hydrate nucleus.
Technical scheme of the present invention
Coalbed methane hydrate dissociation methane separation and energy recycle device, comprise and do not absorb coal-seam gas circulation line, air pump, interchanger, refrigerant (chilled brine) water cooler, gas increases pump, refrigerant (liquid nitrogen) water cooler, hydrate reactor, decomposition of hydrate device, absorption liquid circulation line, absorption liquid storage tank, absorption liquid recycle pump, interchanger, refrigerant (chilled brine) water cooler, absorption liquid recycle pump, tail gas cold recovery circulation line, methane (high density) gas outlet valve, tail gas is (containing nitrogen, oxygen etc.) outlet valve, saturated absorption liquid reclaims cold pipeline, in hydrate reactor, absorption liquid is the tetrahydrofuran aqueous solution containing mass percent 15-30%.
Described air pump is by 0.1MPa, be pressurized to 0.3～0.4MPa containing the coal-seam gas of methane 30%, described interchanger by the fresh coal-seam gas of room temperature to 35 ℃ with absorb tail gas carry out indirect contact, by heat exchange reclaims 0 ℃ of left and right in absorption tail gas low temperature cold, fresh coal-seam gas is carried out to precooling; With the unreacted coal-seam gas (0 ℃ of left and right) of circulation, directly contact and mix, by fresh coal-seam gas precooling and reduce temperature; Described interchanger refrigerant is calcium chloride chilled brine, and coal-seam gas is cooled to 0 ℃ of left and right; Described gas increases pump the coal-seam gas of 0.3～0.4MPa is pressurized to 0.7～0.8MPa; Described cooled with liquid nitrogen device is reduced to-25 ℃, increase condensate depression by coal-seam gas from 0 ℃; Gas-to-liquid contact area in the coal-seam gas that described hydrate reactor object is to provide enough between methane gas and absorption liquid, to accelerate hydrate formation speed; Reaction heat in hydrate reactor removes by the chilled brine in spiral coil cooling tube in tower, absorption liquid is mainly the tetrahydrofuran aqueous solution of 10-15%, absorption liquid is sprayed and is entered reactor by tower top, with contact by the upstream methane of gas distributor at the bottom of tower, gas liquid film generation quality and heat transmission, reaction heat removes by the chilled brine in spiral coil cooling tube; Methane in gas phase by liquid-gas interface enter liquid phase, through inductive phase, nucleation period, crystal vegetative period, generate methane hydrate, be discharged from from reactor lower end, enter splitter by pipeline, after reclaiming cold by interchanger, the unreacted oxygen of tower top and nitrogen and a small amount of methane discharges, while containing higher methane gas in hydrate reactor top discharge, return to feed end by circulation line, directly mix with fresh coal-seam gas, reclaim the cold in circulation gas; Described pipeline is that methane saturated absorption liquid reclaims cold by interchanger, enters splitter, and hydrate decomposes by 25～30 ℃ of hot water, and top methane enters LNG by outlet valve; The absorption liquid of resolving from splitter by storage tank, is pumped to interchanger through recycle pump, carries out heat exchange with methane saturated absorption liquid, then enter water cooler cooling by chilled brine after, be recycled pump and squeeze into hydrate reactor, enter reactor from tower top spraying; Fresh absorption liquid is added to hydrate reactor by water cooler and liquid circulating pump.
Coalbed methane hydrate dissociation disclosed in this invention preparation and energy recovery: the coal-seam gas of 30% left and right is prepared into hydrate, and main energy expenditure has: 1, by coal-seam gas pressure from normal pressure pressurizing to about 0.7～0.8MPa, gas boosting pump horsepower consumes required energy.2, by coal-seam gas from refrigerant for room temperature and 35 ℃ (recycled offgas, unreacted coal-seam gas circulates) first cooling, use freezing salt, liquid nitrogen cooling to-25 ℃ of required thermal loads again; The thermal load that shifts out, needs supply of 3, coalbed methane hydrate dissociation liquid spray power consumption, gas liquid reaction Heat of Formation; 4, methane adsorption liquid is cooled to 0～3 ℃ of required thermal load from room temperature to 35 ℃.
Accompanying drawing explanation
Fig. 1 is that coalbed methane hydrate dissociation separates and ability recovery system schematic flow sheet (embodiment), wherein 110 for not absorbing coal-seam gas circulation line, 1 is air pump, 2 is interchanger, 3 is refrigerant (chilled brine) water cooler, 4 is air pump, 5 is refrigerant (liquid nitrogen) water cooler, 6 is hydrate reactor, 7 is decomposition of hydrate device, 111 is absorption liquid circulation line, 8 is absorption liquid storage tank, 9 is absorption liquid recycle pump, 10 is interchanger, 11 is refrigerant (chilled brine) water cooler, 12 is absorption liquid recycle pump, 112 is tail gas cold recovery circulation line, 13 is methane (high density) gas outlet valve, 14 is that tail gas is (containing nitrogen, oxygen etc.) outlet valve, 113 is saturated absorption liquid recovery cold pipeline, 15, 16 is water cooler, 17 is air pump, 18 is heating agent, 19 is refrigerant, 20 is saturated absorption liquid discharging pump, 21 is absorption liquid nozzle.
Embodiment
In embodiments of the invention, chilled brine used is the calcium chloride brine of ammonia refrigerating compressor system, and refrigeration agent is liquefied ammonia; The liquid nitrogen that the present invention uses is for coal-seam gas gas cooling, and object is to add atmospheric condensate depression, promotes liquid phase hydration reaction speed;
Embodiment 1
Fig. 1 is that coalbed methane hydrate dissociation separates and ability recovery system schematic flow sheet (embodiment), wherein 110 for do not absorb coal-seam gas circulation line, 1 for air pump, 2 for interchanger, 3 for refrigerant (chilled brine) water cooler, 4 for air pump, 5 for refrigerant (liquid nitrogen) water cooler, 6 for hydrate reactor, 7 for decomposition of hydrate device, 111 for absorption liquid circulation line, 8 be absorption liquid storage tank (absorption liquid is the tetrahydrofuran aqueous solution containing mass percent 15-30%).9 is that absorption liquid recycle pump, 10 is that interchanger, 11 is that refrigerant (chilled brine) water cooler, 12 is that absorption liquid recycle pump, 112 is that tail gas cold recovery circulation line, 13 is that methane (high density) gas outlet valve, 14 is that tail gas (containing nitrogen, oxygen etc.) outlet valve, 113 is saturated absorption liquid recovery cold pipeline, 15,16 is water cooler, 17 is air pump, 18 is heating agent, 19 is refrigerant, 20 is saturated absorption liquid discharging pump, and 21 is absorption liquid nozzle.
Described air pump 1 is by 0.1MPa, be pressurized to 0.3～0.4MPa containing the coal-seam gas of methane 30%, described interchanger 2 be by the fresh coal-seam gas of room temperature to 40 ℃ with absorb tail gas 112 carry out indirect contact, by heat exchange reclaims 0 ℃ of left and right in absorption tail gas low temperature cold, fresh coal-seam gas is carried out to precooling, heat exchange; Or be 0 ℃ of left and right with the coal-seam gas 110 of circulation, directly contact, mix, by fresh coal-seam gas precooling, reduce temperature; Described interchanger 3 is calcium chloride chilled brine water cooler, and coal-seam gas is cooled to 0 ℃ of left and right; The coal-seam gas of 0.3～0.4MPa is pressurized to 0.7～0.8MPa by described air pump 4; Described cooled with liquid nitrogen device is reduced to-25 ℃, increase condensate depression by coal-seam gas from 0 ℃; Contact area in the coal-seam gas that described hydration reactor 6 objects are to provide enough between methane gas and absorption liquid, to accelerate hydrate formation speed; Reaction heat in hydration reactor 6 removes by the chilled brine in spiral coil cooling tube in tower, absorption liquid is sprayed and is entered reactor by tower top, with contact by the upstream methane of gas distributor at the bottom of tower, gas liquid film generation quality and heat transmission, remove heat of reaction by the chilled brine in spiral coil cooling tube; Methane in gas phase enters liquid phase, through inductive phase, nucleation period, crystal vegetative period, generate solid hydrate, enter splitter 7 by pipeline 113, after reclaiming cold by interchanger 2, the unreacted oxygen of tower top and nitrogen and a small amount of methane discharges, while containing higher methane gas in hydration reactor 6 tower top dischargings, return to feed end by circulation line 110, carry out directly mixing with fresh coal-seam gas the cold reclaiming in circulation gas; Described pipeline 113 reclaims cold for methane saturated absorption liquid by interchanger 10, enters splitter 7 by 25～30 ℃ of hot water water of decomposition compounds, and methane enters LNG by outlet valve 13; The absorption liquid of resolving from splitter 7 is by storage tank 8, through recycle pump 9 by pump as interchanger 10, carry out heat exchange with methane saturated absorption liquid, then enter water cooler 11 cooling by chilled brine after, be recycled pump and squeeze into hydration reactor 6 tower tops; Fresh absorption liquid is added to hydration reactor 6 by water cooler 11 and recycle pump 12.
Claims (8)
1. methane and an energy-recuperation system in coalbed methane hydrate dissociation, is characterized in that comprising metal cools coil pipe cooling system in hydrate generates and methane extraction element, hydrate reactor top are discharged through vent valve unreacted coal seam gas circulation and cold recovery, the tail gas cold recovery that discharges at hydrate reactor top, the saturated absorption liquid cold recovery that discharges through bleeder valve hydrate reactor lower end, hydrate reactor.
2. hydrate generation and methane extraction element thereof comprise air pump, multistage refrigerant heat exchanger, gas boosting pump, hydrate reactor, decomposition of hydrate device, absorption liquid recycle pump, absorption liquid water cooler according to claim 1.
3. air pump according to claim 2, is characterized by coal-seam gas is forced into 0.3～0.4MPa and with circulating water from normal pressure.Described multistage refrigerant heat exchanger, it is characterized by 1) to adopt cold cycle coal-seam gas be refrigerant, 2) to adopt low temperature exhaust gas discharge gas be refrigerant, 3) employing chilled brine is refrigerant, 4) employing liquid nitrogen is refrigerant, carry out multistage coolingly to entering the coal-seam gas of hydrate reactor respectively, be cooled to 0 ℃ to-25 ℃ from 25 ℃～35 ℃～100 ℃.Described gas boosting pump, is characterized by coal-seam gas is pressurized to 0.8～1.0MPa and with circulating water, the temperature causing because of gas pressurization is raise and lowered the temperature from 0.3～0.4MPa.
4. hydrate reactor according to claim 3, it is characterized by reactor head side has tail gas relief outlet and coal-seam gas circulation gas to discharge return port through vent valve, there is absorption liquid relief outlet reactor bottom side, reactor bottom has coal-seam gas inlet gas sparger, and reactor head has absorption liquid entry nozzle.In described hydrate reactor absorption liquid be containing mass percent 15 ?30% tetrahydrofuran aqueous solution.
5. unreacted coal seam, hydrate reactor according to claim 4 top gas is discharged and is carried out cold recovery through vent valve, it is characterized in that directly mixing with charging coal-seam gas, cold being passed to charging coal-seam gas.The saturated methane adsorption liquid generating from hydrate reactor from bottom through bleeder valve after absorption liquid recycle pump and absorption liquid interchanger, pump into decomposition of hydrate device.
6. the tail gas cold energy reclamation device that discharge through vent valve at hydrate reactor according to claim 5 top, is characterized in that this tail gas indirect contacts, cold is conducted to initial import coal-seam gas through interchanger wall with initial coal-seam gas.The methane decomposing in described decomposition of hydrate device enters LNG production system from splitter top after vent valve is discharged.
7. the saturated absorption liquid that discharge through bleeder valve hydrate reactor according to claim 6 lower end enters cold energy reclamation device, it is characterized in that the absorption liquid of this derivation and the absorption liquid from splitter is resolved methane carry out indirect contact, cold is conducted to circulation (being resolved) absorption liquid by interchanger wall.
8. metal cools coil pipe refrigerating unit in hydrate reactor according to claim 7, it is characterized in that flowing to chilled brine from spiral coil cooling tube below, flowing out chilled brine from top, in reactor, the temperature of reaction solution is controlled in 0～3 ℃, to remove reaction heat, in reactor, spiral coil cooling tube is prepared by copper metallic substance, the low temperature of metallic surface and thermal conductivity, can accelerate the growth of hydrate nucleus.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779049A (en) * | 2015-11-24 | 2016-07-20 | 北京化工大学 | Method for preparing coalbed methane hydrate |
| CN107903969A (en) * | 2017-11-29 | 2018-04-13 | 常州大学 | A kind of device that methane in mixed empty coal bed gas is continuously separated using hydrate |
| CN110862851A (en) * | 2019-12-16 | 2020-03-06 | 北京化工大学 | Method for preparing gas hydrate |
| CN113117504A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy recovery type hydrate method |
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| CN1873285A (en) * | 2005-06-02 | 2006-12-06 | 中国科学院过程工程研究所 | Method and equipment for enriching and storing and transporting coalbed gas by using hydrate |
| CN101530719A (en) * | 2008-03-13 | 2009-09-16 | 中国石油大学(北京) | Method and device for low-pressure processing of coal bed gas |
| CN101554560A (en) * | 2008-04-09 | 2009-10-14 | 中国石油大学(北京) | Method for treating coal bed gas at low pressure |
| CN203319966U (en) * | 2013-07-10 | 2013-12-04 | 安徽理工大学 | Separation and purification system for coal bed gas hydrate |
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| CN1873285A (en) * | 2005-06-02 | 2006-12-06 | 中国科学院过程工程研究所 | Method and equipment for enriching and storing and transporting coalbed gas by using hydrate |
| CN101530719A (en) * | 2008-03-13 | 2009-09-16 | 中国石油大学(北京) | Method and device for low-pressure processing of coal bed gas |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779049A (en) * | 2015-11-24 | 2016-07-20 | 北京化工大学 | Method for preparing coalbed methane hydrate |
| CN105779049B (en) * | 2015-11-24 | 2019-03-01 | 北京化工大学 | A method of manufacture coalbed methane hydrate dissociation |
| CN107903969A (en) * | 2017-11-29 | 2018-04-13 | 常州大学 | A kind of device that methane in mixed empty coal bed gas is continuously separated using hydrate |
| CN110862851A (en) * | 2019-12-16 | 2020-03-06 | 北京化工大学 | Method for preparing gas hydrate |
| CN113117504A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy recovery type hydrate method |
| CN113117504B (en) * | 2019-12-31 | 2023-03-28 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy recovery type hydrate method |
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