CN101104825B - Method for producing liquefied natural gas of mine gas - Google Patents

Method for producing liquefied natural gas of mine gas Download PDF

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Publication number
CN101104825B
CN101104825B CN2007100242759A CN200710024275A CN101104825B CN 101104825 B CN101104825 B CN 101104825B CN 2007100242759 A CN2007100242759 A CN 2007100242759A CN 200710024275 A CN200710024275 A CN 200710024275A CN 101104825 B CN101104825 B CN 101104825B
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gas
pipeline
amine
utilizes
utilize
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CN2007100242759A
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Chinese (zh)
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CN101104825A (en
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吴其蒙
曹荣
韦恩润
冯宏伟
徐家龙
殷强
陈猛
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无锡永大天然气集团有限公司
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0022Hydrocarbons, e.g. natural gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003Processes 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
    • F25J1/0047Processes 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
    • F25J1/0052Processes 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0211Processes 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 multi-component refrigerant [MCR] fluid in a closed vapor compression cycle
    • F25J1/0212Processes 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 multi-component refrigerant [MCR] fluid in a closed vapor compression cycle as a single flow MCR cycle
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02Processes 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
    • F25J1/0243Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2220/00Processes or apparatus involving steps for the removal of impurities
    • F25J2220/60Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
    • F25J2220/62Separating low boiling components, e.g. He, H2, N2, Air

Abstract

The invention relates to a technique of producing liquefied natural gas (LNG) from gas emitted from mines for comprehensive utilization by cryogenic separation and cryogenic liquefaction. According to the technique proposal of the invention, the purification and separation of the gas and the producing of LNG comprise four processes of deoxidation, carbon dioxide (CO2) removal, dehydration, cryogenic separation and liquefaction. The integration of air separation, natural gas treatment, chemical purification, cryogenic refrigeration in the invention forms a unique technique of producing LNG from mine gas, wherein the gas can be compressed safely and the methane content is increased as well as the heat value, and by cryogenic process, the gas is turned from gaseous fuel into liquid fuel which is easy for transportation and wide application.

Description

A kind of natural gas liquids of mine gas gas generates Apparatus and method for

Technical field

The present invention relates to the coal mine gas of a large amount of dischargings of mine is taked low temperature separation process, the cryogenic liquefying mode is prepared into the Technology that natural gas liquids (LNG) is fully utilized.

Technical background

Gas be a kind of association in the coal seam, the multicomponent gas that contains methane of when producing coal, overflowing.Gas has asphyxiating, incendivity under finite concentration.In coal production process, gas is gushed out, is flowed to the scope of operation, flows in the atmosphere of mine from the coal seam, brought threat to safety in production.For preventing the harm of gas to personnel safety, control measures has been taked to gas in the colliery.A kind of mode of gas control is discharging modes.Strengthen ventilation to the mine that has gas to gush out, the gas in the underground air is diluted in the security regulations, with the distinguished and admirable ground that is discharged into of gas companion.The control emission mode of gas is only applicable to the little colliery of gas emission, and is subjected to the ventilation quantitative limitation allowable of mine ventilation ability and down-hole.Another kind side is the extraction mode, by coming gas extraction to working seam or contiguous coal bed drilling, is discharged into ground.The general methane content of gas that the employing discharging modes are discharged into ground is lower, and the methane content that the extraction mode is obtained is generally higher.Most of collieries take sky to be discharged to the atmosphere mode to extraction to the gas on ground, do not add utilization.Contiguous city, minority colliery or worker homestead district are also arranged, use as life fuel; Also have as application such as methane electrical generatioies.Because the big multi-position in colliery is remote, be difficult to collection and fail, generating is subjected to the restriction that networks, be unable to do without the restriction of using on the spot in the colliery, add that the methane content of general coal mine gas is on the low side, calorific value is not high, be difficult to compress reasons such as transmission ﹠ distribution, so these are used and to fail large-scale popularization all the time.The gas of China's coal-mine still major part is discharged in the air.The main ingredient methane that contains in the gas is more than 20 times of carbonic acid gas to the pollution level of atmospheric Greenhouse effect.

Summary of the invention

The objective of the invention is to design a kind of natural gas liquids generation Apparatus and method for of mine gas gas, coal mine gas can be compressed safely, pass through process for separating and purifying, improve the methane content of coal mine gas, improve its calorific value, by the deep cooling mode it is become liquid fuel from gaseous fuel again, can conveniently transport widespread use.

Mine gas purification, separation, LNG generate technology mainly by deoxidation, decarbonation (CO 2), dehydration and 4 sub-process procedures compositions of low temperature separation process and liquefaction.The present invention will belong to that air separation, gas conditioning, chemical industry are purified, the cryogenic refrigeration Technology is blended into one, and form unique " mine gas LNG generates Gong Yi Ji Intraoperative ".

According to technical scheme provided by the invention, the used equipment of natural gas liquids generation method of described mine gas gas, comprise and utilize the interconnective equipment that is used for deoxidation of pipeline successively, the equipment that is used for decarbonation, the equipment that is used to dewater and be used for low temperature separation process and the equipment of liquefaction, it is characterized in that: be used for the equipment of deoxidation, the import of mine gas is set at the input terminus of wet storage holders, output terminal at wet storage holders utilizes the pipe connection feed gas compressor, the output terminal of feed gas compressor utilizes pipeline to be connected with a passage of preheater, the outlet of this passage utilize pipeline with in have the import of the oxidation reactor of catalytic oxidant bed to be connected; The outlet of oxidation reactor utilizes pipeline to be connected with another passage of preheater, and the outlet of this another passage utilizes pipeline to be connected with the import of waste heat boiler; The outlet of waste heat boiler utilizes pipeline to be connected with water cooler, and the outlet of water cooler utilizes pipeline to be connected with water separator, and the outlet of water separator utilizes pipeline to be connected with storage tank; On the pipeline of water separator and storage tank, utilize the import of another root pipe connection recycle compressor, the outlet of recycle compressor utilize pipeline and be positioned at waste heat boiler and water cooler between pipe connection; And pipeline is set on the outlet conduit of recycle compressor again is communicated with the outlet of feed gas compressor.

In the equipment of decarbonation, the bottom on absorption tower is provided with the import of mine gas, utilize pipe connection amine recycle pump on the top on absorption tower, the amine recycle pump utilizes pipeline to be connected with strainer, strainer utilizes pipeline to be connected with the amine topping-up pump, and the amine topping-up pump utilizes pipeline to be connected with watercooler, the outlet of watercooler utilize pipeline with poor/after rich amine interchanger is connected, be connected with poor amine jar, the outlet of poor amine jar utilizes pipeline to be connected with the bottom of regenerator column again; Utilize two pipelines to be connected simultaneously in the bottom of regenerator column, constitute the loop separately with reboiler;

After the top on absorption tower utilizes the pipe connection watercooler, be connected with the middle part that absorbs overhead separator again, the pipeline of the mine gas after discharging decarbonation is set on the top that absorbs overhead separator, utilizes pipeline to be connected with the amine holding tank in the bottom that absorbs overhead separator; On the amine holding tank, utilize pipe connection amine collecting pump;

The amine collecting pump utilizes pipeline to be connected with strainer, and connects the amine make-up pump on this pipeline, and the amine make-up pump utilizes pipeline to be connected with raw material amine flow container;

Utilize pipe connection amine liquid flash tank in the bottom on absorption tower, utilize on the amine liquid flash tank pipeline with poor/be connected with the upper end of regenerator column again after rich amine interchanger is connected, utilize two pipelines to be connected with regenerator reflux pump with the regenerator column condenser respectively simultaneously in the upper end of regenerator column, the regenerator column condenser utilizes pipeline to be connected with the regenerator column return tank again, and the bottom of regenerator column return tank utilizes pipeline to be connected with regenerator reflux pump;

On amine liquid flash tank, be provided for discharging the pipeline of CO 2 waste gas.

The equipment that is being used for dewatering, the import of mine gas is set in the bottom of strainer, utilize pipe connection first adsorber and second adsorber in the upper end of strainer, utilize the pipe connection dust filter unit in the bottom of two adsorbers, dust filter unit utilizes pipeline to be connected with process furnace, after the top of two adsorbers utilizes the pipe connection watercooler, be connected with water separator again, the pipeline that utilizes again of water separator is connected with supercharger, after supercharger utilized pipe connection supercharger water cooler, the import with two adsorbers was connected again.

At the equipment that is used for low temperature separation process and liquefaction, main heat exchanger and rectifying tower are positioned at ice chest, and main heat exchanger is positioned at the top of rectifying tower; The lower end of rectifying tower is provided with the import of mine gas, is provided for discharging the pipeline of dirty nitrogen on the top of rectifying tower, is provided for discharging the pipeline of finished product in the bottom of rectifying tower, utilizes pipe connection coal mine gas throttling valve between the top of rectifying tower and bottom; Utilize pipeline to be connected with separator on main heat exchanger, separator utilizes pipeline to be connected with water cooler again, and water cooler utilizes pipeline to be connected with the refrigerant cycle compressor, and the refrigerant cycle compressor utilizes pipeline cryogen suction tank to connect again.

The natural gas liquids generation method of described mine gas gas comprises:

A, deoxidation, mine gas at first should adopt strong oxidizing reaction method of catalyzer or pressure swing adsorption process to carry out deoxidation treatment, to eliminate the hidden danger of necessary high pressure compressed when generating natural gas liquids; The strong oxidizing reaction deoxidization technique of catalyzer is under normal pressure, and 600~700 ℃ of temperature, coal mine gas be by the catalyst bed in the oxidation reactor, makes the oxygen in the coal mine gas and the oxidizing reaction of the methane generation flames of anger, generates carbonic acid gas and water; Pressure swing absorption process is to select for use void diameter greater than the oxygen molecule diameter, less than the molecular sieve of molecular diameter of methane, and oxygen in the adsorption gas gas; Gas oxygen level after the deoxidation should be controlled at below 0.5%;

B, decarbonation, mine gas also should carry out decarbonation to be handled, to prevent low temperature CO 2Form the dry ice occluding device; When handling, decarbonation select for use methyldiethanolamine to make CO 2Absorption agent, CO in the coal mine gas behind the decarbonation 2Content is controlled at below the 50ppm;

The sorbent material of molecular sieve as water molecules selected in c, dehydration for use, makes coal mine gas pass through molecular sieve, utilizes molecular sieve adsorption to fall water in the coal mine gas; After the dehydration, the moisture controlled in the coal mine gas is below 5ppm;

D, low temperature separation process and liquefaction, liquefaction process is finished in the main heat exchanger of ice chest, and all cold is provided by single loop azeotrope refrigeration cycle; Natural gas liquids separates from rectifier bottoms, and residual gas gas and nitrogen are discharged by the rectifying tower top.

When adopting the strong oxidizing reaction technology of catalyzer to carry out deoxidation, the oxidation reactor of oxidation catalyst bed is arranged in being provided with, the temperature of reaction height is controlled by regulating the gas oxygen level; Waste heat boiler also is set simultaneously, the heat energy of emitting when making full use of deoxidation; When adopting the pressure swing absorption process deoxidation, be provided with two adsorption beds: an adsorption bed is used for adsorption of oxygen work, and another adsorption bed is used for discharging and discharging oxygen, to the molecular sieve activation of regenerating; The molecular sieve void diameter is 3.6A.

When low temperature separation process and liquefaction, used cryogen is the mixed cooling medium of methane, ethene, propane, penta hexane, nitrogen; Select for use spiral-lobe compressor to carry out the refrigerant cycle compression; Have ice chest, the main heat exchanger that transmits cold and deep cooling gas is arranged in the ice chest, be used for rectifying tower that gas-liquid separation generates natural gas liquids, can make cryogen and gas throttling valve by decompression refrigeration.

Mine gas gas generates that institute consumes electric energy in whole technological processs of natural gas liquids, adopts the supply of generating electricity of present low gas engine power generation unit; Generating set use by pump drainage in the mine or generate the remaining low methane gas of natural gas liquids and act as a fuel.

The present invention takes special deoxidization technique to gas in advance, by after certain compression, takes decarbonation, dewatering process to carry out decarburization, dehydration more then.At last to take purify methane and methane liquefaction generated natural gas liquids (LNG) of the mode of low temperature separation process through the coal mine gas of deoxidation, decarburization, dehydration.LNG is a kind of liquid fuel based on methane of present extensive application.Its volume is 1/625th of a Sweet natural gas, and the high compression volume ratio of LNG makes it to adopt easily conventional mode of transport such as car and boat, provides the key city gasification to make civil natural gas and uses or do city emergency deposit source of the gas.LNG is through behind the purifying and liquefying, and its calorific value increases substantially, can be simultaneously as industrial special fuel, automobile with compressed natural gas fuel, LNG automobile fuel.Its Application Areas is not subjected to the restriction of region, is equivalent to the application of the oil product fuel of bavin, gasoline.

Description of drawings

Fig. 1 is the deoxygenation system schema.Fig. 2 is the decarbonation schema.

Fig. 3 is the dewatering system schema.Fig. 4 is a low temperature separation process liquefaction system schema.

Embodiment

As shown in the figure: the used equipment of natural gas liquids generation method of mine gas gas comprises and utilizes the interconnective equipment that is used for deoxidation of pipeline successively, the equipment that is used for decarbonation, the equipment that is used to dewater and be used for low temperature separation process and the equipment of liquefaction, be used for the equipment of deoxidation, the import of mine gas 1 is set at the input terminus of wet storage holders 2, output terminal at wet storage holders 2 utilizes pipe connection feed gas compressor 3, the output terminal of feed gas compressor 3 utilizes pipeline to be connected with a passage of preheater 4, and the outlet of this passage utilizes pipeline to be connected with the import of oxidation reactor 5; The outlet of oxidation reactor 5 utilizes pipeline to be connected with another passage of preheater 4, and the outlet of this another passage utilizes pipeline to be connected with the import of waste heat boiler 9; The outlet of waste heat boiler 9 utilizes pipeline to be connected with water cooler 6, and the outlet of water cooler 6 utilizes pipeline to be connected with water separator 7, and the outlet of water separator 7 utilizes pipeline to be connected with storage tank 50; Utilize the import of another root pipe connection recycle compressor 8 on the pipeline of water separator 7 and storage tank 50, the outlet of recycle compressor 8 utilizes pipeline and is positioned at waste heat boiler 9 and the pipe connection of 6 in water cooler; And pipeline is set on the outlet conduit of recycle compressor 8 again is communicated with the outlet of feed gas compressor 3.

In the equipment of decarbonation, the bottom on absorption tower 13 is provided with the import of mine gas, 13 top utilizes pipe connection amine recycle pump 15 on the absorption tower, amine recycle pump 15 utilizes pipeline to be connected with strainer 18, strainer 18 utilizes pipeline to be connected with amine topping-up pump 20, amine topping-up pump 20 utilizes pipeline to be connected with watercooler 21, the outlet of watercooler 21 utilize pipeline with poor/after rich amine interchanger 22 is connected, be connected with poor amine jar 27, the outlet of poor amine jar 27 utilizes pipeline to be connected with the bottom of regenerator column 23 again; Utilize two pipelines to be connected simultaneously in the bottom of regenerator column 23, constitute the loop separately with reboiler 28;

After the top on absorption tower 13 utilizes pipe connection watercooler 17, be connected with the middle part that absorbs overhead separator 19 again, the pipeline of the mine gas after discharging decarbonation is set on the top that absorbs overhead separator 19, utilizes pipeline to be connected with amine holding tank 11 in the bottom that absorbs overhead separator 19; On amine holding tank 11, utilize pipe connection amine collecting pump 12;

Amine collecting pump 12 utilizes pipeline to be connected with strainer 18, and connects amine make-up pump 14 on this pipeline, and amine make-up pump 14 utilizes pipeline to be connected with raw material amine flow container 16;

13 bottom utilizes pipe connection amine liquid flash tank 10 on the absorption tower, utilize on the amine liquid flash tank 10 pipeline with poor/be connected with the upper end of regenerator column 23 again after rich amine interchanger 22 is connected, utilize two pipelines to be connected with regenerator reflux pump 26 with regenerator column condenser 24 respectively simultaneously in the upper end of regenerator column 23, regenerator column condenser 24 utilizes pipeline to be connected with regenerator column return tank 25 again, and the bottom of regenerator column return tank 25 utilizes pipeline to be connected with regenerator reflux pump 26;

On amine liquid flash tank 10, be provided for discharging the pipeline of CO 2 waste gas.

The equipment that is being used for dewatering, the import of mine gas is set in the bottom of strainer 30, utilize pipe connection first adsorber 31 and second adsorber 32 in the upper end of strainer 30, bottom at first adsorber 31 and second adsorber 32 utilizes pipe connection dust filter unit 33, dust filter unit 33 utilizes pipeline to be connected with process furnace 34, after the top of first adsorber 31 and second adsorber 32 utilizes pipe connection watercooler 38, be connected with water separator 37 again, the pipeline that utilizes again of water separator 37 is connected with supercharger 35, after supercharger 35 utilizes pipe connection supercharger water cooler 36, be connected with the import of second adsorber 32 with first adsorber 31 again.

At the equipment that is used for low temperature separation process and liquefaction, main heat exchanger 40 is positioned at ice chest 44 with rectifying tower 42, and main heat exchanger 40 is positioned at the top of rectifying tower 42; The lower end of rectifying tower 42 is provided with the import of mine gas, be provided for discharging the pipeline of dirty nitrogen on the top of rectifying tower 42, be provided for discharging the pipeline of finished product in the bottom of rectifying tower 42, between the top of rectifying tower 42 and bottom, utilize pipe connection coal mine gas throttling valve 43; Utilize pipeline to be connected with separator 45 on main heat exchanger 40, separator 45 utilizes pipeline to be connected with water cooler 46 again, and water cooler 46 utilizes pipeline to be connected with refrigerant cycle compressor 47, and refrigerant cycle compressor 47 utilizes pipeline cryogen suction tank 48 to connect again.

Technology of the present invention is as follows:

1, the deoxidation treatment technology of mine gas

According to technical scheme provided by the invention, mine gas is earlier through first sub-technical process: deoxidation treatment.Because feedstock mine gas 1 under elevated pressures, carries out low ternperature separation process and liquefaction can obtain the better economic requirement.Therefore decarburization, dehydration, low temperature separation process and the liquefaction process flow process of the technical program all are set under the higher bleed pressure and carry out.Mine gas becomes flammable explosive gas owing to contain oxygen.It is not treated that coal mine gas is carried out high pressure compression is that safety production rules institute is unallowed.

One of method of deoxidation of the technical program is the strong oxidizing reaction deoxidation of catalyzer.As shown in Figure 1, the feedstock mine gas 1 of equality circuit air inlet requirement enters a wet storage holders 2 that has a constant volume to require.This wet storage holders 2 is used for the composition of balanced mine gas 1 to be changed.The operating pressure of wet storage holders 2 is about 2.5KPa (G).

The feedstock mine gas 1 incoming stock air compressor 3 that wet storage holders 2 comes out is pressurized to 0.05MPa (G), after circulation gas that recycle compressor 8 is come mixes, being mixed with meets the requirements contains the coal mine gas of oxygen ratio, through preheater 4 preheatings, then in oxidation reactor 5, generate carbonic acid gas and water and deoxidation by oxygen in the mine gas 1 and methane reaction.The mine gas 1 that removes behind the oxygen enters preheater 4 once more, for preheater 4 provides heat.The mine gas 1 that goes out preheater 4 enters waste heat boiler 9 and water cooler 6 in succession, is cooled to that normal temperature is laggard goes into water separator 7.Mine gas 1 remove moisture in water separator 7 after enters storage tank 50.Deoxidation coal mine gas oxygen level in the storage tank 50 can enter next decarbonization process flow process less than 0.5%.

Gas temperature of oxidizing reaction in reaction tower is to control by the oxygen proportion in the allotment gas.From deoxidation gas, extract part gas after recycle compressor 8 compressions, be sent to the delivery port of feed gas compressor 3,, under the control of flow quantity control instrument, carry out blending according to preset proportion.Except that participating in blending part gas, the unnecessary deoxidation gas of recycle compressor 8 compression outlets is still sent the inlet of water cooler 6 back to, enters storage tank 50 after the processing.

Two of the method for deoxidation of the technical program is to adopt the deoxidation of low pressure pressure swing absorption process.Processing method is described as follows:

The principle of low pressure transformation absorption deoxidation is: difference (the oxygen molecule diameter 3.5A that utilizes oxygen molecule and molecular diameter of methane in the gas, molecular diameter of methane is 3.8A), select for use void diameter can pass through oxygen molecule, can not make absorption filtering material (is 3.6A as void diameter) by the molecular sieve of methane molecule.When gas enters molecular sieve under the low pressure state, oxygen molecule wherein since diameter less than the void diameter of molecular sieve by molecular sieve adsorption, methane molecule is isolated in outside the molecular sieve, and effectively breaks away from oxygen molecule.

The tooling of low pressure transformation absorption deoxidation is by two adsorption bed A, B, switch valve, and PLC controller and pipeline are formed.When mine gas 1 enters the A adsorption bed under low-pressure state, oxygen is adsorbed, A adsorption bed bottom pipeline output anaerobic or low oxygen content gas; After the molecular sieve hole in the A adsorption bed was filled oxygen, PLC controlled switch valve, and mine gas is introduced the B adsorption bed, closes the A adsorption bed simultaneously, entered next deoxidation adsorption cycle.B adsorption bed adsorption of oxygen work this moment, molecular sieve carries out the regeneration activation that low pressure discharges in the A adsorption bed, so that drop into absorption work again at next adsorption cycle.

2, the decarbonization process of mine gas

As shown in Figure 2, the mine gas of deoxidation at first enters the decarburization compressor compresses to more than the 3MPa (G), enters 13 decarburizations of amine absorption tower after cooling.Mine gas is through water cooler 17 cooling after the decarburization, and carry out gas and separate with amine liquid entering top, absorption tower separator behind the wherein residual amine vapor condensation: amine liquid is discharged by tower bottom, enters amine holding tank 11; Gas after the decarburization is input to subsequent processing by top of tower.CO in the gas 2Content should be less than 50ppm.

The amine liquid of mine gas decarburization recycles.Working cycle is as follows:

In amine absorption tower 13, high pressure amine liquid (being called as poor amine) is squeezed into from cat head by amine liquid recycle pump 15, and the amine liquid of spray contacts with the mine gas that enters from the bottom simultaneously and absorbs wherein CO from top to bottom 2Be full of CO 2Amine liquid (being called as rich amine) by discharging at the bottom of the tower on absorption tower 13, enter amine liquid flash tank 10.The rich amine liquid a part of CO that overflows in by flash distillation in amine liquid flash tank 10 2, aerial through flare discharge.Sloughed a part of CO 2Rich amine liquid enter poor/rich amine preheater 22.After the rich amine liquid after the preheating is by the throttling valve step-down, enter amine regenerator column 23 and carry out the regeneration of amine liquid.Amine liquid regenerative process is such description: the amine liquid after regenerator column 23 regeneration becomes poor amine by rich amine.The part of these poor amine imports poor amine jar 27 from regenerator column bottom, another part is drawn in the reboiler 28, becomes the poor amine steam that boils again through steam heating.The poor amine steam that boils again reenters amine regenerator column 23 at the bottom of the tower and flows from bottom to top, the rich amine liquid under regenerator column 23 overhead stream is heated, with the CO in the rich amine liquid 2Be evaporated, make the poor amine of its regeneration.The CO that evaporates 2Discharge by the cat head of regenerator column 23 with residual amine steam, enter in the regenerator column condenser 24 be cooled, condensation.Wherein the rich amine liquid of condensation formation enters return tank 25, returns regenerator column 23 and other rich amine mixing by reflux pump 26 pump drainages, regenerates; The waste gas that is cooled then discharges in the air.

Collect in the poor amine liquid of the high temperature heat exchange in poor/rich amine interchanger 22 earlier in the poor amine jar 27,, in next watercooler 21, get cooling to the end then by rich amine liquid precooling from amine absorption tower 12.Cooled poor amine liquid is after 20 superchargings of amine topping-up pump, filter by two-stage filter 18 (A among Fig. 2, B), become the poor amine liquid that has recovered the absorbing carbon dioxide ability after the regeneration, squeeze into 13 tops, amine absorption tower again, participate in new absorbing carbon dioxide circulation by amine recycle pump 15.

The absorption agent of intending in the design adopting is methyldiethanolamine (MDEA) solution.Among Fig. 2 11 is the amine holding tank, and 12 is the amine collecting pump, and 14 is the amine make-up pump, and 16 is raw material amine flow container.This has partly been formed amine and has recycled the additional liquid Department system that adds of the outer amine of technology chain: although the amine steam that is contained in the gas after the amine decarburization is collected in the amine holding tank 11 after reclaiming by watercooler 17, absorption overhead separator 19; Although after the amine steam in the waste gas of being discharged by regenerator column 23 tops separates by 24 condensations of regenerator column water cooler, regenerator column return tank 25, squeeze into regenerator column regeneration again by regenerator reflux pump 26.But amine liquid is still lossy in recycling.Its loss is partly by amine make-up pump 14, and extraction amine liquid replenishes or extracts amine liquid by amine collecting pump 12 from amine holding tank 11 and replenish from raw material amine flow container 16.

3, the dewatering process of mine gas

As shown in Figure 3, remove and enter dewatering system after mine gas behind the carbonic acid gas leaves the amine treatment system.Filtration/separation device 30 is used for separating the belongings from upstream amine system.The gas that leaves filtration/separation device 30 enters first adsorber 31 or second adsorber 32, wherein moisture removal.Dewatering system is provided with two cover sieve adsorpting beds, and 1 is enclosed within lineman's another set of reproduced state that is in when doing.

Feedstock mine gas enters the molecular sieve bed of the first online adsorber 31, and moisture is adsorbed when gas stream is crossed molecular sieve bed in first adsorber 31.Exsiccant, the unstripped gas mine gas of carbonated and moisture not leave the bottom of online molecular sieve bed, before sending into liquefaction system, enter dust filter unit 33 and filter.Dust filter unit 33 disposes two according to 100% ability.

In any given time, the moisture in the molecular sieve bed on-line adsorption unstripped gas in the adsorber is arranged all.When the molecular sieve bed adsorption moisture of a cover in online first adsorber 31 wherein after saturated, will switch to regenerated offline, the molecular sieve bed in off-line second adsorber 32 after the another set of regeneration then becomes online.Molecular sieve bed in the first saturated adsorber 31 will enter regeneration circulation.The dry coal mine gas of drawing from dust filter unit 33 outlets forms resurgent gases after the process furnace heating, feed the bottom that needs regenerated first adsorber 31.Resurgent gases flows through the molecular sieve bed from the bottom to top, removes the moisture in the molecular sieve bed.The resurgent gases that has adsorption moisture is exported by first adsorber, 31 tops, after watercooler 38 coolings, enter in the water separator 37 and separate water of condensation, again by supercharging blower 35 superchargings, charge cooler 36 coolings, be circulated to dewatering system inlet, and reenter 31 dehydrations of first adsorber after other gas blending of need dewatering.First adsorber 31 after being reproduced is about to the second saturated adsorber 32 with preparing to take over, and works online again.In a typical circulation, online 12 hours of the molecular sieve bed in adsorber, thermal regeneration 6.25 hours cool off 3.75 hours, standby switching respectively 1 hour.

The mine gas that comes out from dewatering system has satisfied the requirement of low temperature separation process and liquefaction, can enter next system and separate and liquefy.

4, low temperature separation process and liquefaction

Low temperature separation process and liquefaction process carry out in ice chest 44.Main heat exchanger 40, rectifying tower 42, coal mine gas throttling valve 43, cryogen throttling valve 41 are installed in the ice chest 44.Liquefaction process is finished in main heat exchanger 40.Main heat exchanger 40 is made up of an intravital brazed aluminum heat exchanger made of shell that is enclosed in ice chest 44.Be full of the pearlife thermal insulation material in the housing of ice chest 44.Main heat exchanger 40 is vertically installed, and the raw material methane gas enters main heat exchanger 40 by the top, flows downward to the cold junction of main heat exchanger 40 bottoms.Cryogenic liquid only appears at main heat exchanger 40 bottoms.An aluminum rectifying tower 42 that is filled with Stainless Steel Helices also is housed in the ice chest.All adopt being connected of welding between main heat exchanger 40, rectifying tower 42 and cryogen throttling valve 41 and the coal mine gas throttling valve 43.Therefore, internal duct and equipment can not leak.Liquid LNG product is directly drawn at the bottom of the tower of rectifying tower 42.All cold is provided by single loop azeotrope refrigeration cycle.

The raw material coal-mine gas enters cold energy cooling and the partial liquefaction that at first mixed cooling agent provides behind the main heat exchanger 40.Gas flows in main heat exchanger 40 from top to bottom, and mixed cooling medium flows from bottom to top.Formed gas top-down cold energy exchange gradient in main heat exchange 40 devices like this: the bottom of main heat exchanger 40 is the coldest, partly cryogenic liquid can occur, forms liquid methane.Entered rectifying tower 42 from the bottom by the gas-liquid mixed methane of deep cooling, once more by cold excessively, its supercooling temperature will be lower than the liquefaction temperature of methane in the bottom of rectifying tower 42.Cross cold after gas liquid through throttling valve 43, enter the cat head of rectifying tower 42 after the expenditure and pressure refrigeration again, carry out rectifying in the tower.Cat head participates in the existing liquid state and a small amount of gaseous methane, the nitrogen that the gas-liquid attitude is arranged again and deposit in the cold fluid crossed of rectifying.Because the boiling point of liquid nitrogen is far below liquid methane, therefore by cat head when tower bottom flow is moving, gases such as the nitrogen in the fluid gather at cat head, also are pooled to cat head after the liquid nitrogen generation flash distillation.These are rich in the mixing steam of nitrogen, and the cold passage that enters main heat exchanger 40 as cold flow has discharged behind the cold energy promptly as useless nitrogen discharged.Methane flow direction after the flash distillation at the bottom of the tower, obtain purified product LNG at the bottom of making tower.Methane content is higher than 99.2% among the product LNG, and oxygen level is lower than 0.5%.

Cryogen is a kind of mixture, is made up of nitrogen and the hydrocarbon polymer from methane to iso-pentane.Screw-type compressor is adopted in the cryogen compression, by electric motor driving.Single loop azeotrope refrigerating is simple in structure, when efficient liquefaction process is provided, pipe arrangement still less, the reference mark still less, number of devices still less.

A simple enclosed refrigeration cycle has been adopted in this device technique design, and cryogen is compressed, partial condensation, cooling, expansion, is heated and provides cold then.Cryogen is the component ratio according to gas, the calculating of the needs of different steps cooling cold energy during to the gas cryogenic liquefying, the mixture that components such as nitrogen, methane, ethene, propane and iso-pentane are prepared by different ratios.Single loop mixed cooling medium refrigeration work process description is as follows: as shown in Figure 4, the low pressure cryogen that has cooled off gas from bottom to top and discharged cold in main heat exchanger 40 has been gas phase, is discharged by the top, enters cryogen suction tank 48.Enter the input terminus of refrigerant cycle compressor 47 then by suction tank 48.What come out from the defeated outlets of cryogen compressor 47 is gas phase high pressure cryogen through high pressure compressed.This cryogen enters separator 45 and carries out gas-liquid separation after water cooler 46 coolings.Because each component dew point difference of azeotrope, form different phases: the component that dew point is high is condensed into liquid state as penta hexane, propane etc.; The component that dew point is low such as nitrogen, methane etc. still are high-pressure gaseous.This gas-liquid mixed cryogen separates in gas-liquid separator 45.High pressure vapor after the separation and liquid phase cryogen from top to bottom flow into main heat exchanger 40 respectively, and converge in main heat exchanger 40 inside.Take gas phase and liquid phase cryogen respectively input mode be that cryogen for the plate beam passage that guarantees to enter main heat exchanger 40 can come the cold of reasonable distribution cryogen in main heat exchanger 40 to supply with gradient by regulating the gas, liquid flow of cryogen.

When the high pressure cryogen flows through main heat exchanger 40 from top to bottom, cooled off from bottom to top by the nitrogen that is in cryogenic of discharging from the rectifying tower top.When cryogen is flowed out by the bottom of main heat exchanger 40, all be condensed into liquid state.Flowing through then is called as the cryogen throttling valve 41 of Tom Si-joule valve, through decompression and part evaporation, the temperature of cryogen is further reduced, and is in the low pressure and the deeply-liquefied state of cooling.This state cryogen will reenter main heat exchanger 40, flow from bottom to top.This moment, the bottom of main heat exchanger 40 was cold junction.When gas enters main heat exchanger 40 from top to bottom, to the temperature that the time is cooled of bottom minimum.Heated, gasify by gas when cryogen is come out by main heat exchanger 40 upper ends.Gaseous state low pressure cryogen enters cryogen suction tank 48 once more, and then by 47 compressions of refrigerant cycle compressor, has constituted a closed circulation.Cryogen suction tank 48 can protect refrigerant cycle compressor 47 not have liquid to enter.The cryogen that enters suction tank 48 all is gas usually.If any small amount of liquid also just in the bottom of suction tank 48.Be provided with a gasification installation herein: introduce hot gas flow from 47 outlets of refrigerant cycle compressor, liquid is gasified by generating tube.

The LNG that mine gas generates after purification, low temperature separation process, liquefaction is a kind of cryogenic liquid fuel that contains high purity methane, high heating value.Can generally be used for domestic gas, vehicle fuel, industrial special fuel, and carry conveniently, can use automobile, steamer to grow distance and carry

Technical scheme of the present invention is applicable to handles methane content at the mine gas more than 25%.Adopt the technical program to handle day and to process 1 ten thousand stere to 15 ten thousand stere and amount to the mine gas of 100% pure methane amount.The following processing facility of 5 ten thousand stere Regulations moulds can be made into skid mounted equipment, can install easily and move, to adapt to the unsettled characteristics of mine gas gas production rate.

Contract machine, amine recycle pumps etc. of all sound equipment that technical scheme of the present invention is selected such as coal mine gas low pressure compressor, coal mine gas high pressure compressor, refrigerant cycle all adopt driven by power.Required electric energy takes the methane electrical generation mode to supply with voluntarily.Major programme be make full use of methane content in the mine be lower than 20% coal mine gas and gas is purified, the remaining low levels coal mine gas of low temperature separation process process, select the generating set of low levels gas engine configuration for use, with the fuel driven generating set generating that is used as power of low levels gas.The electricity that sends is supplied with the processing to the high-content coal mine gas, the need that processing generates LNG.No matter high-content gas or low levels gas all obtain fully like this, comprehensively comprehensive utilization.

Claims (5)

1. the natural gas liquids of a mine gas gas generates equipment, comprise and utilize the interconnective equipment that is used for deoxidation of pipeline successively, the equipment that is used for decarbonation, the equipment that is used to dewater and be used for low temperature separation process and the equipment of liquefaction, it is characterized in that: be used for the equipment of deoxidation, the import of mine gas (1) is set at the input terminus of wet storage holders (2), output terminal at wet storage holders (2) utilizes pipe connection feed gas compressor (3), the output terminal of feed gas compressor (3) utilizes pipeline to be connected with a passage of preheater (4), the outlet of this passage utilize pipeline with in have the import of the oxidation reactor (5) of catalytic oxidant bed to be connected; The outlet of oxidation reactor (5) utilizes pipeline to be connected with another passage of preheater (4), and the outlet of this another passage utilizes pipeline to be connected with the import of waste heat boiler (9); The outlet of waste heat boiler (9) utilizes pipeline to be connected with water cooler (6), and the outlet of water cooler (6) utilizes pipeline to be connected with water separator (7), and the outlet of water separator (7) utilizes pipeline to be connected with storage tank (50); On the pipeline of water separator (7) and storage tank (50), utilize the import of another root pipe connection recycle compressor (8), the outlet of recycle compressor (8) utilize pipeline and be positioned at waste heat boiler (9) and water cooler (6) between pipe connection; And pipeline is set on the outlet conduit of recycle compressor (8) again is communicated with the outlet of feed gas compressor (3);
In the equipment of decarbonation, the bottom on absorption tower (13) is provided with the import of mine gas, the top of (13) utilizes pipe connection amine recycle pump (15) on the absorption tower, amine recycle pump (15) utilizes pipeline to be connected with strainer (18), strainer (18) utilizes pipeline to be connected with amine topping-up pump (20), amine topping-up pump (20) utilizes pipeline to be connected with watercooler (21), the outlet of watercooler (21) utilize pipeline with poor/after rich amine interchanger (22) is connected, be connected with poor amine jar (27), the outlet of poor amine jar (27) utilizes pipeline to be connected with the bottom of regenerator column (23) again; Utilize two pipelines to be connected in the bottom of regenerator column (23) simultaneously, constitute the loop separately with reboiler (28);
After the top of absorption tower (13) utilizes pipe connection watercooler (17), be connected with the middle part that absorbs overhead separator (19) again, the pipeline of the mine gas after discharging decarbonation is set on the top that absorbs overhead separator (19), utilizes pipeline to be connected with amine holding tank (11) in the bottom that absorbs overhead separator (19); On amine holding tank (11), utilize pipe connection amine collecting pump (12);
Amine collecting pump (12) utilizes pipeline to be connected with strainer (18), and connects amine make-up pump (14) on this pipeline, and amine make-up pump (14) utilizes pipeline to be connected with raw material amine flow container (16);
The bottom of (13) utilizes pipe connection amine liquid flash tank (10) on the absorption tower, utilize on the amine liquid flash tank (10) pipeline with poor/be connected with the upper end of regenerator column (23) again after rich amine interchanger (22) is connected, utilize two pipelines to be connected with regenerator reflux pump (26) with regenerator column condenser (24) respectively simultaneously in the upper end of regenerator column (23), regenerator column condenser (24) utilizes pipeline to be connected with regenerator column return tank (25) again, and the bottom of regenerator column return tank (25) utilizes pipeline to be connected with regenerator reflux pump (26);
On amine liquid flash tank (10), be provided for discharging the pipeline of CO 2 waste gas;
The equipment that is being used for dewatering, the import of mine gas is set in the bottom of strainer (30), utilize pipe connection first adsorber (31) and second adsorber (32) in the upper end of strainer (30), bottom at first adsorber (31) and second adsorber (32) utilizes pipe connection dust filter unit (33), dust filter unit (33) utilizes pipeline to be connected with process furnace (34), after the top of first adsorber (31) and second adsorber (32) utilizes pipe connection watercooler (38), be connected with water separator (37) again, water separator (37) utilizes pipeline to be connected with supercharger (35) again, after supercharger (35) utilizes pipe connection supercharger water cooler (36), be connected with the import of first adsorber (31) respectively again with second adsorber (32);
At the equipment that is used for low temperature separation process and liquefaction, main heat exchanger (40) is positioned at ice chest (44) with rectifying tower (42), and main heat exchanger (40) is positioned at the top of rectifying tower (42); The lower end of rectifying tower (42) is provided with the import of mine gas, be provided for discharging the pipeline of dirty nitrogen on the top of rectifying tower (42), be provided for discharging the pipeline of finished product in the bottom of rectifying tower (42), between the top of rectifying tower (42) and bottom, utilize pipe connection coal mine gas throttling valve (43); On main heat exchanger (40), utilize pipeline to be connected with separator (45), separator (45) utilizes pipeline to be connected with water cooler (46) again, water cooler (46) utilizes pipeline to be connected with refrigerant cycle compressor (47), and refrigerant cycle compressor (47) utilizes pipeline to be connected with cryogen suction tank (48) again.
2. use the method for the natural gas liquids generation equipment generation natural gas liquids of the described mine gas gas of claim 1, it is characterized in that:
A, deoxidation, mine gas at first adopt strong oxidizing reaction method of catalyzer or pressure swing adsorption process to carry out deoxidation treatment, to eliminate the hidden danger of necessary high pressure compressed when generating natural gas liquids; The strong oxidizing reaction deoxidization technique of catalyzer is under normal pressure, and 600~700 ℃ of temperature, coal mine gas be by the metal catalyst on the catalyst bed in the oxidation reactor, makes the oxygen in the coal mine gas and the oxidizing reaction of the methane generation flames of anger, generates carbonic acid gas and water; Pressure swing absorption process is to select for use void diameter greater than the oxygen molecule diameter, less than the molecular sieve of molecular diameter of methane, and the oxygen in the adsorption gas gas; Gas oxygen level after the deoxidation should be controlled at below 0.5%;
B, decarbonation, mine gas also carry out decarbonation to be handled, to prevent low temperature CO 2Form the dry ice occluding device; Taking off CO 2Select for use methyldiethanolamine to make CO during processing 2Absorption agent takes off CO 2After coal mine gas in CO 2Content is controlled at below the 50ppm;
The sorbent material of molecular sieve as water molecules selected in c, dehydration for use, makes coal mine gas pass through molecular sieve, utilizes molecular sieve adsorption to fall water in the coal mine gas; After the dehydration, the moisture controlled in the coal mine gas is below 5ppm;
D, low temperature separation process and liquefaction, liquefaction process is finished in the main heat exchanger of ice chest, and all cold is provided by single loop azeotrope refrigeration cycle; Natural gas liquids separates from rectifier bottoms, and residual gas and nitrogen are discharged by the rectifying tower top.
3. as method as described in the claim 2, it is characterized in that: when adopting the strong oxidizing reaction technology of catalyzer to carry out deoxidation, the oxidation reactor of oxidation catalyst bed is arranged in being provided with, the temperature of reaction height is controlled by regulating the gas oxygen level; Waste heat boiler also is set simultaneously, the heat energy of emitting when making full use of deoxidation; When adopting the pressure swing absorption process deoxidation, be provided with two adsorption beds: an adsorption bed is used for adsorption of oxygen, and another adsorption bed is used for discharging and discharging oxygen, to the molecular sieve activation of regenerating; The molecular sieve void diameter is 3.6A.
4. as method as described in the claim 2, it is characterized in that: when low temperature separation process and liquefaction, used cryogen is the mixed cooling medium of methane, ethene, propane, penta hexane, nitrogen; Select for use spiral-lobe compressor to carry out the refrigerant cycle compression; Be provided with ice chest, the main heat exchanger that transmits cold and deep cooling gas arranged in the ice chest, be used for rectifying tower that gas-liquid separation generates natural gas liquids, can make cryogen and gas throttling valve by decompression refrigeration.
5. as method as described in the claim 2, it is characterized in that: mine gas gas generates that institute consumes electric energy in whole technological processs of natural gas liquids, adopts the supply of generating electricity of present low gas engine power generation unit; Generating set use by pump drainage in the mine or generate the remaining low methane gas of natural gas liquids and act as a fuel.
CN2007100242759A 2007-07-27 2007-07-27 Method for producing liquefied natural gas of mine gas CN101104825B (en)

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