CN103638800B - Utilize the device and method of hydrate continuous batch divided gas flow - Google Patents
Utilize the device and method of hydrate continuous batch divided gas flow Download PDFInfo
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Abstract
The invention discloses a kind of device and method utilizing hydrate continuous batch divided gas flow, described device comprises stable air supply unit, stablizes liquid-supply unit, gas hydrate forms resolving cell, high-frequency jet gas-liquid mixed unit, gas-liquid separator, control temperature unit and data acquisition and processing unit; Separation method of the present invention and device are simple, temperature, pressure condition and gas-liquid flow are all controlled voluntarily by control system, convenience and high-efficiency, when guaranteeing that system gas environmental pressure is consistent, gas hydrate is formed to separate in reactor Sum decomposition still respectively with decomposition reaction and occurs, the continuous formation simultaneously achieving gas hydrate and decomposition, admixture of gas be separated the purification with gas component.Also provide theoretical and data basis for realizing hydrate industrial separation gaseous mixture further simultaneously, the commercial Application realizing hydrate gas separaion is had important practical significance.
Description
Technical field:
The present invention relates to mist continuous separation technology, be specifically related to a kind of device and method utilizing hydrate continuous batch divided gas flow.
Background technology:
Gas separation traditional at present comprises chemical absorbing, physical absorption, cryogenic separation, UF membrane etc.But in actual applications, these methods all exist respective problem, the subject matter that such as chemical absorption method exists at present is that energy ezpenditure and investment are all very large, and solution can have corrosiveness to equipment, affects equipment life; Physisorphtion is only applicable to the separation of the higher gas component of partial pressure conditions, and separative efficiency is lower; Low temperature processing equipment investment and energy consumption are all higher; The film of UF membrane is easily subject to the destruction of the chemical substance in gaseous mixture, needs before use to repair and process, even need frequent replacing, and film throughput is limited.Therefore, in order to save energy consumption, improve separative efficiency, need to continually develop new environmentally friendly gas separation.Gas hydrate isolation technics is one of technology newly developed in recent years, because the formation process of hydrate is simple, directly utilize water as carrier, and water can recycle, gas hydrate isolation technics is considered to a kind of new technique of the simple and environmental protection of technique, and obtains concern widely.
Gas hydrate (GasHydrate) is a kind of class ice-like mixed crystal formed by hydrone and object gas molecules, usually formed under cryogenic high pressure condition, hydrone is connected by hydrogen bond, formed a series ofly to vary in size, polyhedron hole that structure is different, the guest molecule of different size enters into these holes, stable existence under the effect of Van der Waals force.The phase balance condition that different guest molecules forms gas hydrate is different, thus, under the same conditions, hydrate has selective to different guest molecules, and the guest molecule of phase balance condition milder can preferentially enter formation gas hydrate, cause the change of the gas component in hydrate phase and gas phase, hydrate mutually in, more easily form the component enrichment of gas hydrate, in the gas phase, then weaken, therefore can realize utilizing hydrate divided gas flow purifying gas from gaseous mixture.
Current, the research of gas hydrate isolation technics is mainly gas hydrate and forms thermodynamics, dynamics and gas hydrate decomposition technique.Thermodynamic study content comprises gas hydrate and forms the research of phase balance condition and form the discussion of decomposition heat, dynamic (dynamical) research then mainly concentrates on gas hydrate and forms induction time, driving force, formation Sum decomposition reaction rate etc., and the research of gas hydrate separating technology then comprises the determination of process conditions, gas hydrate synthesis mode, gas hydrate synthesis promoter (additive), technique and parameter designing, device fabrication etc.The scientist all over the world comprising China forms decomposition heat mechanics to gas hydrate, dynamics has very deep research, also obtain a large amount of experimental datas; In gas hydrate synthesis mode, gas hydrate synthesis promoter (additive) and technological design, scientists also achieves great successes.With separation of C O from flue gas
2for example, flue gas mainly become CO
2/ N
2(17.0/83.0%) gaseous mixture, in pure aquatic system, CO
2/ N
2(17.0/83.0%) phase balance condition of mixed Daqu gas hydrate is very harsh, under 275.35K condition, its vapor pressure is 10.48MPa, this pressure is obviously not suitable for commercial Application, because people have attempted different gas hydrates and formed additive, comprise TBAB, THF etc., (JOURNALOFCHEMICALANDENGINEERINGDATA rolls up Li little Sen etc.: 55 phases: 6 pages: 2180-2184) find, in the TBAB solution of 0.29mol%, CO
2/ N
2(17.0/83.0%) vapor pressure that gaseous mixture forms gas hydrate under 275.35K condition can be reduced to below 1.0MPa, thus, can reduce the cost that gas compression needs significantly; In addition, gas hydrate generation type comprises the methods such as mechanical agitation, spray, bubbling, and object is to promote gas-liquid contact, shortens gas hydrate and forms induction time.But still there is the problems such as comprise that separative efficiency is not high, gas treatment amount is low and technique is immature in gas hydrate isolation technics.Especially, in the continuous processing of hydrate divided gas flow, form owing to being limited by gas hydrate the environmental change occurred in speed, gas separaion efficiency and continuous processing procedure, also there is no continuous processing and the relevant device device of comparative maturity so far.
Summary of the invention:
The object of this invention is to provide that a kind of technique is simple, the device and method utilizing hydrate continuous batch divided gas flow of economical and efficient.
The present invention is achieved by the following technical programs:
Utilize a device for hydrate continuous batch divided gas flow, this device comprises stable air supply unit, stablizes liquid-supply unit, gas hydrate forms resolving cell, high-frequency jet gas-liquid mixed unit, gas-liquid separator, control temperature unit and data acquisition and processing unit; Described stable air supply unit comprises the gas cylinder and three-way pressure control valve that provide stable source of the gas; Described stable liquid-supply unit comprises NaOH solution tank NaOH, provides the stabilizing solution source of liquid for NaOH solution tank NaOH; Described gas hydrate forms resolving cell and comprises for the formation of the reactor of gas hydrate, be used alternatingly No. one and No. two decomposing pots of the parallel connection for decomposition gas hydrate that are communicated with described reactor; Described high-frequency jet gas-liquid mixed unit comprises for generation of the radio-frequency generator of high-frequency signal, ejector and jet pump; Described ejector is arranged on the top of reactor, fully mixed by the gas-liquid mixture in reactor, and jet enters described reactor under the effect of the high-frequency signal that described ejector produces at radio-frequency generator at ejector; Described jet pump is for driving the circulation of gas-liquid mixture between reactor and ejector; Described ejector is also communicated with the three-way pressure control valve stablizing air supply unit; Described NaOH solution tank NaOH is communicated with reactor, and for being provided for the liquid of gas hydrate synthesis reaction in reactor continuously, described NaOH solution tank NaOH is also communicated with decomposing pot, and described decomposing pot is communicated with gas-liquid separator; Described control temperature unit comprise constant water bath box, for program refrigeration refrigeration machine and circulating pump; Described data acquisition and processing unit comprising data collection processor, forming the temperature sensor of resolving cell temperature for monitoring described gas hydrate, form the pressure sensor of the pressure of resolving cell and high-frequency jet gas-liquid mixed unit for monitoring described stable air supply unit and gas hydrate, and described data collection processor connects described temperature sensor and pressure sensor.
Described stable air supply unit also comprises the booster pump connected with gas cylinder, the gas pressure reducer, the gas flowmeter that is provided with between gas pressure reducer and three-way pressure control valve connection line that connect with booster pump.
Described stable liquid-supply unit also comprises the regulating switch valve connected with stabilizing solution source, the negative pressure of vacuum pump connected with regulating switch valve, is located at fluid flowmeter between negative pressure of vacuum pump and NaOH solution tank NaOH connection line.
Described gas hydrate form that resolving cell also comprises that the connecting line of reactor and described decomposing pot is provided with for monitor solution and hydrate slurry position transparent visual window, for regulating the control valve of the flow of the gas hydrate synthesis slurries flowed from reactor to decomposing pot.
Described reactor, decomposing pot, NaOH solution tank NaOH, constant water bath box skin are respectively equipped with water-bath chuck, and described circulating pump drives the circulation of water in described water-bath chuck.
Described data acquisition and processing unit also comprise the gas chromatograph of the component for monitoring residue gas phase Sum decomposition gas.
Described data collection processor, for gathering, treatment and analysis is stablized air supply unit, is stablized liquid-supply unit, gas hydrate forms resolving cell, the data-signal of the temperature of high-frequency jet gas-liquid mixed unit, gas-liquid separator, control temperature unit, pressure, gas flow rate, flow rate of liquid, accumulation gas flow, accumulation fluid flow setting operation condition.
Described stable source of the gas is bi-component or three components, even multicomponent gaseous mixture; Booster pump is used for carrying out boost pressure regulation to the pressure of stable source of the gas; Pressure-reducing valve is used for according to exporting the output pressure after needing modification stability air source pressurizing; Three-way pressure control valve is used for steady orientation system provides stable air pressure; Gas flowmeter is for monitoring induction air flow ratio and calculating integrated flux.
Described stabilizing solution source provides required liquid for system, such as pure water or the aqueous solution containing gas hydrate synthesis promoter or additive; Described NaOH solution tank NaOH is used for the liquid being provided for gas hydrate synthesis reaction in reactor continuously; In system, form certain negative pressure after described negative pressure of vacuum pump startup, utilize negative pressure that liquid is input to NaOH solution tank NaOH from stabilizing solution source, and enter reactor through NaOH solution tank NaOH; Described regulating switch valve is used for the flow velocity that regulates liquid flows to reactor; Described fluid flowmeter is for monitoring feed liquor flow velocity and calculating integrated flux.
Described gas-liquid separator is used for the gas-liquid separation that gas hydrate decomposes rear decomposition gas, because decomposition gas exists entrained liquid phenomenon, realizes isolating cleaner decomposition gas from the decomposition gas of entrained liquid by gas-liquid separator.
The number of described decomposing pot is two or more, the number of decomposing pot can increase as required, according to time and the time sum reached needed for design temperature of again freezing of the gas hydrate decomposed completely in decomposing pot, the time required for hydrate slurry is filled with divided by single decomposing pot, the maximum integer obtained, according to the number of this integer setting decomposing pot, the device obtained thus achieves does not need the middle continuous batch production stopping this process of gas hydrate synthesis.
Described water bath, reactor, decomposing pot, NaOH solution tank NaOH skin is also provided with water-bath chuck for preventing the extraneoas loss of bath temperature, and water enters water-bath chuck through water-bath pipeline, to maintain the temperature constant of described reactor, decomposing pot, NaOH solution tank NaOH.
Can be replaced with spray as required for the high-frequency jet device of gas-liquid mixed in this device or spray or mechanical stirring device, object is for forming gas hydrate fast.
Present invention also offers a kind of method utilizing hydrate continuous batch divided gas flow, utilize the above-mentioned device utilizing hydrate continuous batch divided gas flow, specifically comprise the following steps:
A, at the temperature and pressure of setting, under gas-liquid flow, the solution that the mixed material gas that stable air supply unit provides and stable liquid-supply unit provide fully is mixed by high-frequency jet mode and forms gas hydrate continuously fast in reactor, the gas hydrate slurries obtained flow into a decomposing pot by the road by overflow manner, after a decomposing pot fills with hydrate slurry, stop air feed feed flow and refrigeration; The gas hydrate slurries obtained flow into a decomposing pot by the road by overflow manner; After a decomposing pot fills with hydrate slurry, stop air feed feed flow and refrigeration;
B, a heating decomposing pot all decompose to gas hydrate, and the decomposition gas obtained is trapped by gas-liquid separator separates, and the decomposed solution blowback NaOH solution tank NaOH obtained provides solution for forming gas hydrate again;
C, restart refrigeration, setting pressure system is to operating condition, the solution that NaOH solution tank NaOH provides and unstripped gas form gas hydrate by high-frequency jet mode continuously in reactor, the hydrate slurry formed flows into No. two decomposing pots of uniform pressure system by pipeline, after No. two decomposing pots fill with hydrate slurry, stop air feed feed flow and refrigeration;
D, heating No. two decomposing pots all decompose to gas hydrate, and the decomposition gas obtained is trapped by gas-liquid separator separates, and the decomposed solution blowback NaOH solution tank NaOH obtained provides solution for forming gas hydrate again;
E, repetition step a, so circulate, and realizes serialization batch hydrate gas separaion;
Described temperature, pressure condition and gas-liquid flow are all controlled voluntarily by control data sampling and processing unit and control temperature unit, residue gas phase in hydrate reaction still and the composition of decomposition of gaseous by gas-chromatography tracking measurement at any time, and regulate gas-liquid flow velocity by measurement data.
The temperature range of described setting is 263.15 ~ 293.15K, and pressure limit is 1 ~ 15MPa.
Described mixed material gas is two components or multi-component gaseous mixture.
Described solution is pure water or the aqueous solution containing gas with various gas hydrate synthesis promoter (additive).
The present invention has following beneficial effect:
1) working pressure range of the equipment of this device is 1 ~ 15MPa, and temperature range is 263.15 ~ 293.15K; Day process gas flow can reach 2000 cubic metres, and can corresponding amplification as required;
2) simple, the temperature, pressure condition of separation method of the present invention and device and gas-liquid flow are all controlled voluntarily by control system, convenience and high-efficiency, and the decomposed solution obtained recycles through negative pressure of vacuum pump blowback NaOH solution tank NaOH, economic environmental protection;
3) mixed material gas and solution are fully mixed by high-frequency jet mode and form gas hydrate continuously fast in reactor, and divided gas flow efficiency is high.
4) one-level decomposition of hydrate gas can be made into the unstripped gas of second order reaction through air distribution system, and carries out the separation of secondary hydrate, CO in the secondary decomposition of hydrate gas obtained
2concentration of component more than 90%, thus realizes being continuously separated of continuous flue gas.
In a word, the present invention is when guaranteeing that system gas environmental pressure is consistent, gas hydrate is formed to separate in reactor Sum decomposition still respectively with decomposition reaction and occurs, the continuous formation simultaneously achieving gas hydrate and decomposition, admixture of gas be separated the purification with gas component.Also provide theoretical and data basis for realizing hydrate industrial separation gaseous mixture further simultaneously, the commercial Application realizing hydrate gas separaion is had important practical significance.
accompanying drawing illustrates:
Fig. 1 is the structural representation of device of the present invention;
Wherein, 1, gas cylinder; 2, jet pump; 3,8,11,26,33,45 water-bath chucks; 4, reactor; 5,10, temperature sensor; 6,19,30, gas flowmeter; 7, negative pressure of vacuum pump; 9,12, decomposing pot; 13, circulating pump; 14, constant water bath box; 15, refrigeration machine; 16, booster pump; 17, gas pressure reducer; 18,23,28, pressure sensor; 20, three-way pressure control valve; 21, ejector; 22, radio-frequency generator; 24,27, fluid flowmeter; 25, NaOH solution tank NaOH; 29, gas chromatograph; 31, gas-liquid separator; 32, stabilizing solution source; 34,35,36,37,38,39,40,41, regulating switch valve; 42, data collection processor; 43, gas reclaims and distribution tank; 44, visual window.
detailed description of the invention:
Below further illustrate of the present invention, instead of limitation of the present invention.
Consult shown in Fig. 1, utilize a device for hydrate continuous batch divided gas flow, comprise stable air supply unit, stablize liquid-supply unit, gas hydrate forms resolving cell, high-frequency jet gas-liquid mixed unit, gas-liquid separator, control temperature unit and data acquisition and processing unit, described stable air supply unit comprise connect successively the gas cylinder 1 of stable source of the gas, booster pump 16, gas pressure reducer 17, gas flowmeter 19 and three-way pressure control valve 20 are provided, described stable liquid-supply unit comprise connect successively stabilizing solution source 32, regulating switch valve 40, negative pressure of vacuum pump 7, fluid flowmeter 27 and NaOH solution tank NaOH 25, described stabilizing solution source 32 is communicated with the top of NaOH solution tank NaOH 25 through regulating switch valve 40, negative pressure of vacuum pump 7, fluid flowmeter 27 successively, described stabilizing solution source 32 provides liquid for NaOH solution tank NaOH 25, such as pure water or the aqueous solution containing gas hydrate synthesis promoter or additive, described gas hydrate formation resolving cell comprises the reactor 4 for the formation of gas hydrate, with be used alternatingly No. one and No. two decomposing pots 9,12 of the parallel connection for decomposition gas hydrate that described reactor 4 is communicated with, connect the transparent visual window 44 for monitoring solution and hydrate slurry position that the pipeline of described reactor 4 and described No. one and No. two decomposing pot 9,12 is arranged, for regulating the regulating switch valve 37,38 of the flow of the gas hydrate synthesis slurries flowed from reactor 4 to decomposing pot 9,12, described high-frequency jet gas-liquid mixed unit comprises can reach the radio-frequency generator 22 of the high-frequency signal of 5Khz, ejector 21 and jet pump 2 for generation of frequency, described ejector 21 is arranged on the top of reactor 4, fully mixed by the gas-liquid mixture in reactor 4, and jet enters described reactor 4 under the effect of the high-frequency signal that described ejector 21 produces at radio-frequency generator 22 at ejector 21, jet pump 2 is for driving the circulation of gas-liquid mixture between reactor 4 and ejector 21, the three-way pressure control valve 20 of described stable air supply unit follows the ejector 21 of high-frequency jet gas-liquid mixed unit to be communicated with, described NaOH solution tank NaOH 25 is communicated with reactor 4, and for being provided for the liquid of gas hydrate synthesis reaction in reactor 4 continuously, described NaOH solution tank NaOH 25 is also communicated with decomposing pot 9,12, and described decomposing pot is communicated with gas-liquid separator 31, described control temperature unit comprise constant water bath box 14, for program refrigeration refrigeration machine 15 and circulating pump 13, described reactor 4, decomposing pot 9,12, NaOH solution tank NaOH 25, constant water bath box 14 skin be respectively equipped with water-bath chuck 3,8,11,26,45, described circulating pump 13 drives the circulation of water in described water-bath chuck 3,8,11,26,45, described data acquisition and processing unit comprise data collection processor 42, the temperature sensor 5 of resolving cell temperature is formed for monitoring described gas hydrate, 10, for monitoring described stable air supply unit, gas hydrate forms resolving cell, the pressure sensor 18 of the pressure of high-frequency jet gas-liquid mixed unit, 28, 23 and gas chromatograph 29 for the component of monitoring residue gas phase Sum decomposition gas, described data collection processor 42, connect described temperature sensor 5, 10 and pressure sensor 18, 28, 23, for gathering, air supply unit is stablized described in treatment and analysis, stablize liquid-supply unit, gas hydrate forms resolving cell, high-frequency jet gas-liquid mixed unit, gas-liquid separator, the temperature of control temperature unit, pressure, gas flow rate, flow rate of liquid, accumulation gas flow, the data-signal of accumulation fluid flow setting operation condition.
Embodiment 1:
Be 275.65K at bath temperature, under gaseous environment pressure 3.0MPa condition, utilize 0.29mol%TBAB solution hydrate separating flue Simulated gas CO
2/ N
2(17.0/83.0%) gaseous mixture, setting feed liquor flow velocity is 1.5mL/s, and induction air flow ratio is 16.7mL/s, and rf frequency is 1000Hz, and gas hydrate decomposition temperature is 293.15K.After gas-liquid reaches and imposes a condition in reactor 4 and NaOH solution tank NaOH 25, startup radio-frequency generator 22 and ejector 21 carry out gas-liquid mixed, continuous feed liquor, intake channel is opened after half an hour, gas hydrate is formed continuously in reactor 4, the gas hydrate formed enters the pipeline be communicated with between described reactor 4 Sum decomposition still 9,12 by overflow manner, open the regulating switch valve 37 between described pipeline and a decomposing pot 9, gas hydrate slurries enter a decomposing pot 9; Again after one hour, a decomposing pot 9 fills with gas hydrate, stops gas hydrate synthesis reaction, cuts off gas-liquid pipeline, heat decomposing pot 9 a to gas hydrate and decompose completely, discharged by decomposition gas by gas-liquid separator 31.Between the continuous Formation period of hydrate, in 5 minutes collection reactors 4, gas phase carries out component analysis, and decomposition gas also needs to carry out component analysis after gas-liquid separator 31 is discharged.By analysis, CO in residue gas phase
2concentration of component drop to average out to 10.3% by 17.0% in unstripped gas, and the CO in decomposition gas
2concentration of component is then increased to 61.0%, achieves CO
2the purification of component, for further separation and collection is laid a good foundation; Meanwhile, by data analysis, the gas flow of accumulated process is 60120mL, and obtaining decomposition gas is 7365mL, CO
2pure deduction rate be 42.0%; Again freeze to initial setting conditions afterwards, decomposed solution in a decomposing pot 9 loops back NaOH solution tank NaOH 25 through negative pressure of vacuum pump 7 and re-uses, hydrate formation before repetition, the gas hydrate slurries generated flow into No. two decomposing pots 12 from reactor 4, to No. two decomposing pots 12 fill with gas hydrate slurries, stop gas hydrate forming reactions, and carry out decomposition and component measurement.Obtain CO in gas phase
2average composition concentration be 10.2%, CO in decomposition gas
2concentration of component be 61.2%, accumulation gas treatment amount is 120240mL, and to collect decomposition gas be 14798mL, CO in accumulation
2pure deduction rate be 44.3%.
Embodiment 2:
Be 293.15K at bath temperature, under gaseous environment pressure 3.5MPa condition, utilize 0.29mol%TBAB solution hydrate to be separated IGCC synthesis gas gas CO
2/ H
2(40.0/60.0%) gaseous mixture, setting feed liquor flow velocity is 1.5mL/s, and induction air flow ratio is 10.0mL/s, and rf frequency is 1000Hz, and gas hydrate decomposition temperature is 293.15K.After gas-liquid reaches and imposes a condition in reactor 4 and NaOH solution tank NaOH 25, anti-startup radio-frequency generator 22 and ejector 21 carry out gas-liquid mixed, continuous feed liquor, intake channel is opened after half an hour, gas hydrate is formed continuously in reactor 4, the gas hydrate formed enters the pipeline be communicated with between described reactor 4 Sum decomposition still 9,12 by overflow manner, open the regulating switch valve 37 between described pipeline and a decomposing pot 9, gas hydrate slurries enter a decomposing pot 9.Again after one hour, a decomposing pot 9 fills with gas hydrate, stops gas hydrate synthesis reaction, cuts off gas-liquid pipeline, heat decomposing pot 9 a to gas hydrate and decompose completely, discharged by decomposition gas by gas-liquid separator 31.Between the continuous Formation period of hydrate, in 5 minutes collection reactors 4, gas phase carries out component analysis, and decomposition gas also needs to carry out component analysis after gas-liquid separator 31 is discharged.By analysis, CO in residue gas phase
2concentration of component drop to average out to 18.9% by 40.0% in unstripped gas, and the CO in decomposition gas
2concentration of component is then increased to 92.0%, achieves CO
2the purification of component, for further separation and collection is laid a good foundation; Meanwhile, by data analysis, the gas flow of accumulated process is 36000mL, and obtaining decomposition gas is 7767mL, CO
2pure deduction rate be 58.6%; Again freeze to initial setting conditions afterwards, decomposed solution in a decomposing pot 9 loops back NaOH solution tank NaOH 25 through negative pressure of vacuum pump 7 and re-uses, hydrate formation before repetition, the gas hydrate slurries generated flow into No. two decomposing pots 12 from reactor 4, to No. two decomposing pots 12 fill with gas hydrate slurries, stop gas hydrate forming reactions, and carry out decomposition and component measurement.Obtain CO in gas phase
2average composition concentration be 18.7%, CO in decomposition gas
2concentration of component be 91.4%, accumulation gas treatment amount is 72000mL, and to collect decomposition gas be 15534mL, CO in accumulation
2pure deduction rate be 49.3%.
Embodiment 3:
The implementation case is, is 275.65K at bath temperature, under gaseous environment pressure 3.0MPa condition, utilizes 0.29mol%TBAB solution hydrate separating flue Simulated gas CO
2/ N
2(17.0/83.0%) gaseous mixture, setting feed liquor flow velocity is 1.5mL/s, and induction air flow ratio is 16.7mL/s, and rf frequency is 1000Hz, and gas hydrate decomposition temperature is 293.15K.After gas-liquid reaches and imposes a condition in reactor 4 and NaOH solution tank NaOH 25, startup radio-frequency generator 22 and ejector 21 carry out gas-liquid mixed, continuous feed liquor, intake channel is opened after half an hour, gas hydrate is formed continuously in reactor 4, the gas hydrate formed is by entering the pipeline be communicated with between described reactor 4 Sum decomposition still 9,12 by overflow manner, open the regulating switch valve 37 between described pipeline and a decomposing pot 9, gas hydrate slurries enter a decomposing pot 9.Again after one hour, a decomposing pot 9 fills with gas hydrate, stops gas hydrate synthesis reaction, cuts off gas-liquid pipeline, heat decomposing pot 9 a to gas hydrate and decompose completely, discharged by decomposition gas by gas-liquid separator 31.Between the continuous Formation period of hydrate, in 5 minutes collection reactors 4, gas phase carries out component analysis, and decomposition gas also needs to carry out component analysis after gas-liquid separator 31 is discharged.By analysis, CO in residue gas phase
2concentration of component drop to average out to 10.3% by 17.0% in unstripped gas, and the CO in decomposition gas
2concentration of component is then increased to 61.0%, achieves CO
2the purification of component, for further separation and collection is laid a good foundation; Meanwhile, by data analysis, the gas flow of accumulated process is 60120mL, and obtaining decomposition gas is 7498mL, CO
2pure deduction rate be 42.0%; Again freeze to initial setting conditions afterwards, decomposed solution in a decomposing pot 9 loops back NaOH solution tank NaOH 25 through negative pressure of vacuum pump 7 and re-uses, gas-liquid separator 31 discharge gas in distribution tank through the unstripped gas of distribution as the second-order separation, hydrate formation before repetition, the gas hydrate slurries generated flow into No. two decomposing pots 12 from reactor 4, to No. two decomposing pots 12 fill with gas hydrate slurries, stop gas hydrate forming reactions, and carry out decomposition and component measurement.Obtain CO in gas phase
2average composition concentration be 56.2%, CO in decomposition gas
2concentration of component be 90.6%.Total process accumulated process gas flow is 123084mL, collects CO
2the decomposition gas of concentration of component 90.6% is 9386mL, CO
2pure deduction rate be 40.6%, the continuous used time is 9.4 hours.
Embodiment 4:
Be 263.15K at bath temperature, under gaseous environment pressure 1.0MPa condition, utilize 0.29mol%TBAB solution hydrate separating flue Simulated gas CO
2/ N
2(17.0/83.0%) gaseous mixture, setting feed liquor flow velocity is 1.5mL/s, and induction air flow ratio is 10.0mL/s, and rf frequency is 1000Hz, and gas hydrate decomposition temperature is 293.15K.After gas-liquid reaches and imposes a condition in reactor 4 and NaOH solution tank NaOH 25, startup radio-frequency generator 22 and ejector 21 carry out gas-liquid mixed, continuous feed liquor, intake channel is opened after half an hour, gas hydrate is formed continuously in reactor 4, the gas hydrate formed enters the pipeline be communicated with between described reactor 4 Sum decomposition still 9,12 by overflow manner, open the regulating switch valve 37 between described pipeline and a decomposing pot 9, gas hydrate slurries enter a decomposing pot 9.Again after one hour, a decomposing pot 9 fills with gas hydrate, stops gas hydrate synthesis reaction, cuts off gas-liquid pipeline, heat decomposing pot 9 a to gas hydrate and decompose completely, discharged by decomposition gas by gas-liquid separator 31.Between the continuous Formation period of hydrate, in 5 minutes collection reactors 4, gas phase carries out component analysis, and decomposition gas also needs to carry out component analysis after gas-liquid separator 31 is discharged.By analysis, CO in residue gas phase
2concentration of component drop to average out to 10.0% by 17.0% in unstripped gas, and the CO in decomposition gas
2concentration of component is then increased to 61.4%, achieves CO
2the purification of component, for further separation and collection is laid a good foundation; Meanwhile, by data analysis, the gas flow of accumulated process is 36000mL, and obtaining decomposition gas is 4276mL, CO
2pure deduction rate be 42.9%; Again freeze to initial setting conditions afterwards, decomposed solution in a decomposing pot 9 loops back NaOH solution tank NaOH 25 through negative pressure of vacuum pump 7 and re-uses, hydrate formation before repetition, the gas hydrate slurries generated flow into No. two decomposing pots 12 from reactor 4, to No. two decomposing pots 12 fill with gas hydrate slurries, stop gas hydrate forming reactions, and carry out decomposition and component measurement.Obtain CO in gas phase
2average composition concentration be 9.9%, CO in decomposition gas
2concentration of component be 61.5%, accumulation gas treatment amount is 72000mL, and to collect decomposition gas be 8582mL, CO in accumulation
2pure deduction rate be 43.1%.
Embodiment 5:
Be 275.65K at bath temperature, under gaseous environment pressure 15.0MPa condition, utilize 0.29mol%TBAB solution hydrate separating flue Simulated gas CO
2/ N
2(17.0/83.0%) gaseous mixture, setting feed liquor flow velocity is 1.5mL/s, and induction air flow ratio is 10.0mL/s, and rf frequency is 1000Hz, and gas hydrate decomposition temperature is 293.15K.After gas-liquid reaches and imposes a condition in reactor 4 and NaOH solution tank NaOH 25, startup radio-frequency generator 22 and ejector 21 carry out gas-liquid mixed, continuous feed liquor, intake channel is opened after half an hour, gas hydrate is formed continuously in reactor 4, the gas hydrate formed enters the pipeline be communicated with between described reactor 4 Sum decomposition still 9,12 by overflow manner, open the regulating switch valve 37 between described pipeline and a decomposing pot 9, gas hydrate slurries enter a decomposing pot 9.Again after one hour, a decomposing pot 9 fills with gas hydrate, stops gas hydrate synthesis reaction, cuts off gas-liquid pipeline, heat decomposing pot 9 a to gas hydrate and decompose completely, discharged by decomposition gas by gas-liquid separator 31.Between the continuous Formation period of hydrate, in 5 minutes collection reactors 4, gas phase carries out component analysis, and decomposition gas also needs to carry out component analysis after gas-liquid separator 31 is discharged.By analysis, CO in residue gas phase
2concentration of component drop to average out to 9.7% by 17.0% in unstripped gas, and the CO in decomposition gas
2concentration of component is then increased to 62.3%, achieves CO
2the purification of component, for further separation and collection is laid a good foundation; Meanwhile, by data analysis, the gas flow of accumulated process is 36000mL, and obtaining decomposition gas is 4391mL, CO
2pure deduction rate be 44.7%; Again freeze to initial setting conditions afterwards, decomposed solution in a decomposing pot 9 loops back NaOH solution tank NaOH 25 through negative pressure of vacuum pump 7 and re-uses, hydrate formation before repetition, the gas hydrate slurries generated flow into No. two decomposing pots 12 from reactor 4, to No. two decomposing pots 12 fill with gas hydrate slurries, stop gas hydrate forming reactions, and carry out decomposition and component measurement.Obtain CO in gas phase
2average composition concentration be 9.6%, CO in decomposition gas
2concentration of component be 62.5%, accumulation gas treatment amount is 72000mL, and to collect decomposition gas be 8799mL, CO in accumulation
2pure deduction rate be 44.9%.
Claims (8)
1. one kind utilizes the device of hydrate continuous batch divided gas flow, it is characterized in that, this device comprises stable air supply unit, stablizes liquid-supply unit, gas hydrate forms resolving cell, high-frequency jet gas-liquid mixed unit, gas-liquid separator, control temperature unit and data acquisition and processing unit; Described stable air supply unit comprises the gas cylinder (1) and three-way pressure control valve (20) that provide stable source of the gas; Described stable liquid-supply unit comprises NaOH solution tank NaOH (25), provides the stabilizing solution source (32) of liquid for NaOH solution tank NaOH (25); Described gas hydrate forms resolving cell and comprises for the formation of the reactor (4) of gas hydrate, be used alternatingly No. one and No. two decomposing pots (9,12) of the parallel connection for decomposition gas hydrate that are communicated with described reactor (4); Described high-frequency jet gas-liquid mixed unit comprises for generation of the radio-frequency generator (22) of high-frequency signal, ejector (21) and jet pump (2); Described ejector (21) is arranged on the top of reactor (4), under the effect of the high-frequency signal that described ejector (21) produces at radio-frequency generator (22), the gas-liquid mixture in reactor (4) is fully mixed at ejector (21), and jet enters described reactor (4); Described jet pump (2) is for driving the circulation of gas-liquid mixture between reactor (4) and ejector (21); Described ejector (21) is also communicated with the three-way pressure control valve (20) stablizing air supply unit; Described NaOH solution tank NaOH (25) is communicated with reactor (4), for being provided for the liquid of gas hydrate synthesis reaction in reactor (4) continuously, described NaOH solution tank NaOH (25) is also communicated with decomposing pot (9,12), and described decomposing pot is communicated with gas-liquid separator (31); Described control temperature unit comprise constant water bath box (14), for program refrigeration refrigeration machine (15) and circulating pump (13); Described data acquisition and processing unit comprising data collection processor (42), forming the temperature sensor (5,10) of resolving cell temperature for monitoring described gas hydrate, for the pressure sensor (18,28,23) of monitoring described stable air supply unit, gas hydrate forms the pressure of resolving cell and high-frequency jet gas-liquid mixed unit, described data collection processor (42) connects described temperature sensor (5,10) and pressure sensor (18,28,23).
2. the device utilizing hydrate continuous batch divided gas flow according to claim 1, it is characterized in that, described stable air supply unit also comprises the booster pump (16) connected with gas cylinder (1), the gas pressure reducer (17) connected with booster pump (16), the gas flowmeter (19) that is provided with between gas pressure reducer (17) and three-way pressure control valve (20) connection line.
3. the device utilizing hydrate continuous batch divided gas flow according to claim 1, it is characterized in that, described stable liquid-supply unit also comprises the regulating switch valve (40) connected with stabilizing solution source (32), the negative pressure of vacuum pump (7) connected with regulating switch valve (40), is located at fluid flowmeter (27) between negative pressure of vacuum pump (7) and NaOH solution tank NaOH (25) connection line.
4. the device utilizing hydrate continuous batch divided gas flow according to claim 1, it is characterized in that, described gas hydrate form that resolving cell also comprises that reactor (4) and the connecting line of described decomposing pot (9,12) be provided with for monitor solution and hydrate slurry position transparent visual window (44), for regulating the control valve (37,38) of the flow of the gas hydrate synthesis slurries flowed to decomposing pot (9,12) from reactor (4).
5. the device utilizing hydrate continuous batch divided gas flow according to claim 1, it is characterized in that, described reactor (4), decomposing pot (9,12), NaOH solution tank NaOH (25), constant water bath box (14) skin are respectively equipped with water-bath chuck (3,8,11,26,45), and described circulating pump (13) drives the circulation of water in described water-bath chuck (3,8,11,26,45).
6. the device utilizing hydrate continuous batch divided gas flow according to claim 1, is characterized in that, described data acquisition and processing unit also comprise the gas chromatograph (29) of the component for monitoring residue gas phase Sum decomposition gas.
7. utilize a method for hydrate continuous batch divided gas flow, it is characterized in that utilizing the device utilizing hydrate continuous batch divided gas flow in claim 1 ~ 6 described in any one claim, specifically comprise the following steps:
A, at the temperature and pressure of setting, under gas-liquid flow, the solution that the mixed material gas that stable air supply unit provides and stable liquid-supply unit provide fully is mixed by high-frequency jet mode and forms gas hydrate continuously fast in reactor, the gas hydrate slurries obtained flow into a decomposing pot by the road by overflow manner, after a decomposing pot fills with hydrate slurry, stop air feed feed flow and refrigeration;
B, a heating decomposing pot all decompose to gas hydrate, and the decomposition gas obtained is trapped by gas-liquid separator separates, and the decomposed solution blowback NaOH solution tank NaOH obtained provides solution for forming gas hydrate again;
C, restart refrigeration, setting pressure system is to operating condition, the solution that NaOH solution tank NaOH provides and unstripped gas form gas hydrate by high-frequency jet mode continuously in reactor, the hydrate slurry formed flows into No. two decomposing pots of uniform pressure system by pipeline, after No. two decomposing pots fill with hydrate slurry, stop air feed feed flow and refrigeration;
D, heating No. two decomposing pots all decompose to gas hydrate, and the decomposition gas obtained is trapped by gas-liquid separator separates, and the decomposed solution blowback NaOH solution tank NaOH obtained provides solution for forming gas hydrate again;
E, repetition step a, so circulate, and realizes serialization batch hydrate gas separaion;
Described temperature and pressure condition and gas-liquid flow are all controlled voluntarily by control data sampling and processing unit and control temperature unit.
8. the method utilizing hydrate continuous batch divided gas flow according to claim 7, is characterized in that, the temperature range of described setting is 263.15 ~ 293.15K, and pressure limit is 1 ~ 15MPa.
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| CN105080323A (en) * | 2015-08-12 | 2015-11-25 | 辽宁石油化工大学 | Hydrating method based carbon dioxide capture method and device |
| CN106474904B (en) * | 2016-11-25 | 2019-03-08 | 中国科学院广州能源研究所 | A kind of CO of hydrate joint chemical absorption method2Gas fractionation unit and method |
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| CN107344063A (en) * | 2017-07-31 | 2017-11-14 | 中国科学院广州能源研究所 | A kind of hydrate continuously separates the apparatus and method of gas |
| CN108795526A (en) * | 2018-07-02 | 2018-11-13 | 江阴澄云机械有限公司 | A kind of carbon dioxide gas separator |
| CN110016374B (en) * | 2019-04-25 | 2021-05-11 | 西南石油大学 | Method and equipment for directly separating H2S in natural gas by hydrate method at well head |
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