CN100493672C - Hydrate process and apparatus for separating gas mixture continuously - Google Patents
Hydrate process and apparatus for separating gas mixture continuously Download PDFInfo
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- CN100493672C CN100493672C CNB2006101234897A CN200610123489A CN100493672C CN 100493672 C CN100493672 C CN 100493672C CN B2006101234897 A CNB2006101234897 A CN B2006101234897A CN 200610123489 A CN200610123489 A CN 200610123489A CN 100493672 C CN100493672 C CN 100493672C
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Abstract
The present invention proposes hydrate process and apparatus for separating gas mixture continuously. The countercurrent continuous separation process in three serially connected stages is adopted to raise the CO2 recovering rate from fume, the CO2 concentration in the product and the separation rate and efficiency. Each of the separating systems consists of a hydrate synthesizer, a hydrate decomposer, a circulating pump, a heat exchanger, and a micro bubble mixing and jetting reactor. The present invention is suitable for continuous separation and enrichment of CO2 in the fume of coal burning power plant, and may be also used in the continuous separation and enrichment of gas mixture containing CO2 in chemical industry, metallurgy, petroleum and other fields.
Description
Technical field
The present invention relates to the continuous isolation technics of a kind of mist, the continuous isolation technics of especially a kind of hydrate mist.
Technical background
The reality of global warming is constantly sounded the alarm to the people of countries in the world, and greenhouse gases, particularly CO
2One of hot issue that gas discharging the having become whole world is paid close attention to the most.By the end of the year 2004, the whole world has 141 countries and regions and has ratified to reduce discharging CO
2Be the Kyoto Protocol of aim, and formally effective on February 16th, 2005, require the discharging of each state control greenhouse gases.CO in the atmosphere
2Concentration continue to raise is mainly derived from the industry discharging waste gas in the extensive energy production.It is the country of main energy sources with coal that China is one, and this energy resource structure will can not change in considerable time from now on.The coal in China major part is used for generating, and the direct combusting firepower generating of at present traditional coal will be in leading position, the CO of coal-fired power plant in China's power field in considerable time
2Discharge capacity is the industrial CO of control greatly and concentrated relatively
2The main field of discharging reduces discharging CO in the power plant
2Extremely urgent.CO
2Control mainly comprises separating reclaims, transports and handle (comprise and store and transform) three aspects, and the highest as the separation and recovery technology energy consumption of core technology, economy is the poorest, so becomes CO
2The key that control makes a breakthrough also is to realize CO
2The first step of permanent storage.
Separate and contain CO
2The method of admixture of gas mainly contains chemical absorbing, physical absorption, cryogenic separation, transformation absorption and separates with film etc.The chemical absorbing range of application is narrow, and it is big that absorbent reclaims energy consumption.Chinese patent CN1747774A discloses a kind of CO that separates recovery the secondary angry body that chemical absorption method produces from steel plant etc. that adopts
2Method, this method is utilized steel plant's low-grade heat extraction heating recovery chemical absorbent, separation costs reduces greatly.But the deep cooling process for separating investment is higher, only when unit scale is big, just has preferable economy.The subject matter that pressure swing adsorption method exists is the energy consumption height, equipment investment is big, the adsorbent utilization rate is low and loss is big.Present widely used membrane separation process then has chemistry and shortcomings such as poor heat stability, selectivity and flux are not high, disposal ability is limited, product purity is low, poor durability.Develop that novel, efficient gas separates, method of purification has important economic implications.
Hydrate separates CO in the recovery flue gas
2Be based on and be rich in CO
2Admixture of gas in the difference of each component hydrate formation condition, the obvious advantage of this technology is that it does not need to resemble and uses the regenerating unit of expensive highly energy-consuming to reclaim solvent the solvent method for absorbing and separating.Compare the CO of hydrate isolation technics in power-plant flue gas with traditional separation method
2And CO in " green coal " technology integrated gasification combined cycle for power generation
2Separate, put forward dense aspect and have more potentiality.The first, the hydrate isolation technics can carried out more than 0 ℃, can save a large amount of refrigeration energy needed; The second, the gas pressure height that hydrate obtains after separating, pressure reduction is little before and after separating, and can save the required energy of gas boosting; The 3rd, the water reusable edible after the decomposition of hydrate does not have significant loss on the whole procedural theory, and technological process is also simple relatively.The hydrate isolation technics has broad application prospects as novel separation means, and might become the mainstream technology that mist separates.
Though in that some researchs are arranged aspect the hydrate isolation technics, also imperfect abroad, domestic research in this respect then is in the starting stage, and (mainly be N for flue gas
2And CO
2) middle CO
2The hydrate Research of Separation Technique then still less.CO in the flue gas
2Hydrate separates initial experimental study California Institute of Technology during 1993-1995 to carry out, and states CO in their patent
2Hydrate can generate in a running system.This system was confirmed by Los Alamos National Laboratory afterwards, and then confirmed to realize that the industrialization of hydrate isolation technics has very big potentiality (Wong, S.and Bioletti, R.Carbon dioxide separation technologies. (2002) .Carbon ﹠amp; Energy Management, Alberta ResearchCouncil, Edmonton, Alberta, T6N 1E4, Canada.).U.S. Pat 6602326B2 discloses a kind of employing oxolane and forms CO in the promoter separating mixed gas as hydrate
2With N
2Method and technology, hydrate forms pressure and reduces products C O after three grades of separation greatly
2Concentration can reach 99.8%, but the direct emptying of tail gas after every grade of hydration reaction of this technology causes CO in the flue gas
2The rate of recovery low, be to improve CO
2The rate of recovery must prolong the hydration reaction time, makes hydration reaction reach poised state, causes system's separating power to reduce.U.S. Pat 20050120878A1 discloses a kind of CO that utilizes in the Hydrate Technology separation of methane gas
2Technology.US6352576B1 discloses a kind of employing salt as CO
2Hydrate forms promoter and separates CO in the multicomponent gas
2Method, adopt simultaneously to contain CO
2The water of hydrate nucleus improves hydrate and forms speed, reduces hydrate and forms induction time.
The continuous isolation technics of hydrate mist will realize that industrial applications must solve the problem of following five aspects: one, adopt suitable hydrate to form promoter and improve hydrate formation speed; Two, adopt suitable alr mode, improve the gas liquid contacting efficiency of hydration reaction, improve hydrate and form speed; Three, the strengthened aqua compound of adopting an effective measure generates the removal of heat; Four, adopt suitable separating technology, realize that hydrate formation gas, liquid, solid three-phase separates automatically under the condition of high voltage; Five, adopt the technology of economical rationality, improve the rate of recovery of separation process object gas and the purity of gas products, reduce the energy consumption of separation process.
The present invention for addressing the above problem a kind of hydrate mist continuous separation method and the device of inventing, is particularly suitable for being applied to CO in the flue gas just
2Hydrate continuous separation method and device.
Summary of the invention
The purpose of this invention is to provide a kind of economy, efficiently, hydrate mist continuous separation method and device fast.
For achieving the above object, the present invention has taked following technical scheme:
Hydrate mist continuous separation method of the present invention is formed (seeing also Fig. 1) by following five submodules:
A, feed pretreatment module.Mist earlier through water washing, drying, compress, be precooled to hydrate and form pressure and temperature, enter the hydrate separation module through charging control valve and flowmeter then.
B, hydrate separation module.Adopt three stage countercurrents series connection separating technology to improve CO
2The rate of recovery of gas and CO
2Gas products purity improves the speed and the separative efficiency of separation process simultaneously.
C, data acquisition and control module.Comprise measurement, signal transmission, data acquisition and processing, computer centralized displaying and the control of gas feed rate, pressure, temperature; The pressure of first, second and third grade hydrate quick-speed generation system, the measurement of temperature, signal transmission, data acquisition and processing, computer centralized displaying and control; First, second and third grade hydrate separates the pressure of resolver, measurement, signal transmission, data acquisition and processing, computer centralized displaying and the control of temperature; Contain the measurement and the control of hydrate formation promoter aqueous solution make-up flow, temperature; Feed gas forecooler, first, second and third grade hydrate generate the flow-control of heat exchanger freezing liquid; First, second and third grade hydrate separates the control of resolver heating medium flow.
D, analysis module.Comprise the sampling of gas automatic on-line, sample pretreatment and gas chromatograph auto injection analytical equipment.
E, refrigeration module.Feed system cooling institute chilling requirement.
Described submodule A, C, D, E all adopt prior art, submodule B hydrate separation module) be innovative point of the present invention.
Described submodule B (hydrate separation module) adopts concentration and the rate of recovery of three stage countercurrents series connection continuous separation technology to improve separated gas products, specifically implements as follows (seeing also Fig. 2):
1) contains the hydrate formation promoter aqueous solution to hydrate quick-speed generation system (comprising the first order, the second level, third level hydrate quick-speed generation system) adding;
2) flue gas of compressing, being precooled to behind uniform temperature, the pressure enters second level hydrate quick-speed generation system through the feed rate control system;
3) flue gas fully contacts the generation gas hydrate with the aqueous solution from second level circulating pump in the microbubble jet perfectly mixed reactor of second level hydrate quick-speed generation system, hydrate generates heat and removes by external second level heat exchanger, control second level hydrate quick-speed generation system temperature simultaneously and be lower than hydrate-formation temperature, the hydrate slurry of generation enters second level hydrate by the automatic overflow device and separates resolution system;
4) heating in second level hydrate separation resolution system of hydrate slurry is decomposed into and is rich in CO
2The gas and the aqueous solution, it is recycling that the aqueous solution returns second level hydrate quick-speed generation system by circulating pump;
What 5) parse is rich in CO
2Gas enter third level hydrate quick-speed generation system, further improve CO
2Concentration, from the CO that is rich in of second level hydrate quick-speed generation system
2Gas in the microbubble jet perfectly mixed reactor of third level hydrate quick-speed generation system, fully contact the generation gas hydrate with the aqueous solution from third level circulating pump, hydrate generates heat and removes by external third level heat exchanger, control third level hydrate quick-speed generation system temperature simultaneously and be lower than hydrate-formation temperature, the hydrate slurry of generation enters third level hydrate by the automatic overflow device and separates resolution system;
6) heating in third level hydrate separation resolution system of hydrate slurry is decomposed into high-purity CO
2The gas and the aqueous solution, it is recycling that the aqueous solution returns third level hydrate quick-speed generation system by circulating pump;
7) the high-purity CO that parses
2Gas enters drying system, makes high-purity CO
2The gas dewatering drying, dried high-purity CO
2Gas products enters gas storage system and stores;
8) the poor CO of hydration reaction does not take place in the third level hydrate quick-speed generation system
2Gas returns second level hydrate quick-speed generation system as unstripped gas and continues reaction;
9) the poor CO of hydration reaction does not take place in second level hydrate quick-speed generation system
2Gas enters first order hydrate quick-speed generation system, further improves CO
2The rate of recovery, from the poor CO of second level hydrate quick-speed generation system
2Gas fully contacts with the aqueous solution from first order circulating pump in the microbubble jet perfectly mixed reactor of first order hydrate quick-speed generation system and generates the gas hydrate slurry, hydrate generates heat and removes by external first order heat exchanger, control first order hydrate quick-speed generation system temperature simultaneously and be lower than hydrate-formation temperature, the hydrate slurry of generation enters first order hydrate by the automatic overflow device and separates resolution system;
10) heating in first order hydrate separation resolution system of hydrate slurry is decomposed into and is rich in CO
2The gas and the aqueous solution, it is recycling that the aqueous solution that parses returns first order hydrate quick-speed generation system by circulating pump, what parse is rich in CO
2Gas enter second level hydrate quick-speed generation system as unstripped gas and continue reaction;
11) N of hydration reaction does not take place in the first order hydrate quick-speed generation system
2And trace amounts of CO
2Gas is handled by the tail gas blowdown system.
Described first, second and third grade hydrate quick-speed generation system includes hydrate synthesis reactor, microbubble jet perfectly mixed reactor, circulating pump, heat exchanger.
Described first, second and third grade hydrate separates resolution system and includes two parallel hydrates separation resolvers, during operation, two resolvers switch use, accept hydrate quick-speed generation system overflow water compound slurry for one, be used for gas and separate with the hydrate slurry, realization gas separates with the liquid-solid two-phase mixture; Another heating decomposition water compound slurry parses hydration reaction gas, is used for hydrate and resolves, and realizes that decomposition of hydrate is gentle, liquid two is separated.
Described first, two, between three grades of hydrate quick-speed generation systems, first, two, three grades of hydrate quick-speed generation systems and first, two, the gas flow that three grades of hydrates separate between the resolution system all realizes by pressure differential, the gas flow pressure difference is 0.05～0.5MPa, during operation, second level hydrate separates the pressure of resolution system greater than third level hydrate synthesis reactor pressure, first order hydrate is resolved the pressure of separation resolution system and third level hydrate synthesis reactor greater than second level hydrate synthesis reactor pressure, and second level hydrate synthesis reactor pressure is greater than first order hydrate synthesis reactor pressure.
Described first, second and third grade hydrate quick-speed generation system temperature is respectively 274 ℃, 277 ℃, 280 ℃; The temperature of described hydrate quick-speed generation system is by regulating the flow-control of heat exchanger freezing liquid.
The described aqueous solution is the aqueous solution that contains 0.1%～15% hydrate formation promoter; Described hydrate formation promoter is selected from one of following or its mixture: oxolane, 1,4-dioxane or acetone or quaternary ammonium salt, sulfonium salt, phosphonium salt, lauryl sulfate, dodecane sulfonate.
The described aqueous solution is by containing the intermittently supply of promoter aqueous solution make-up system.
Hydrate mist continuous separation device of the present invention comprises feed preparation unit, hydrate three stage countercurrents series connection continuous separation device, data acquisition and control device, analytical equipment, refrigerating plant, and connecting pipe.
Described data acquisition and control device comprise temperature, pressure, flow measurement device, signal transmitting apparatus, pressure, volume control device and computer centralized displaying and control device; Described analytical equipment comprises gas chromatograph and on-line automatic sampling of gas and pretreatment unit; Described feed preparation unit comprises feed gas preprocessing, gas compressor and forecooler.
Described hydrate three stage countercurrents series connection separator comprises that the quick generating apparatus of first, second and third grade hydrate, first, second and third grade hydrate separate resolver, contain promoter aqueous solution device for supplying, CO
2Drying device, CO
2Caisson, tail gas emptying device.The described hydrate formation promoter aqueous solution device for supplying that contains is connected to the quick generating apparatus of first, second and third grade hydrate respectively by aqueous solution supply pipeline 4.Described CO
2Gas drier is connected to CO through appendix 7
2Caisson.
The described second level quick generating apparatus of hydrate is connected to feed preparation unit by flue gas feed pipe 1, hydrate quick generating apparatus in the described second level is connected to the quick generating apparatus of first order hydrate through second level hydrate synthesis reactor tail gas outlet 3, and hydrate quick generating apparatus in the described second level is connected to second level hydrate through second level hydrate slurry overflow pipe 12 and separates resolver.Described second level hydrate separation resolver is separated gassing escape pipe 10 through second level hydrate and is connected to the quick generating apparatus of third level hydrate.
The quick generating apparatus of described third level hydrate is connected to flue gas feed pipe 1 through third level hydrate synthesis reactor tail gas outlet 11, and the quick generating apparatus of described third level hydrate is connected to third level hydrate through third level hydrate slurry overflow pipe 9 and separates resolver.Described third level hydrate separation resolver is separated gassing escape pipe 8 through third level hydrate and is connected to CO
2Gas drier.
The quick generating apparatus of described first order hydrate links to each other with the tail gas emptying device through first order hydrate synthesis reactor tail gas blow-down pipe 5, and the quick generating apparatus of described first order hydrate is connected to first order hydrate through first order hydrate slurry overflow pipe 6 and separates resolver.Described first order hydrate separation resolver is separated gassing escape pipe 2 through first order hydrate and is connected to flue gas feed pipe 1.
The quick generating apparatus of described first, second and third grade hydrate includes hydrate synthesis reactor, microbubble jet perfectly mixed reactor, circulating pump, heat exchanger; Described first, second and third grade hydrate separates resolver and includes two parallel hydrates and separate resolvers, and two separation resolvers switch and use, and one is used for separating of gas and hydrate slurry, and another is used for the parsing of hydrate.For example described second level hydrate quick-speed generation system and second level hydrate separate resolution system and comprise that second level hydrate synthesis reactor 27, microbubble jet perfectly mixed reactor 21, heat exchanger 14, circulating pump 13, second level hydrate separate resolver 23a, 23b.
Described second level hydrate synthesis reactor 27 and microbubble jet perfectly mixed reactor 21 are connected by flange, described second level hydrate synthesis reactor 27 charging apertures and flue gas feed pipe 1 and separate gassing escape pipe 2 by flue gas feed pipe 1 with third level hydrate synthesis reactor tail gas outlet 11 and first order hydrate and link to each other, described second level hydrate synthesis reactor 27 is connected to the quick generating apparatus of first order hydrate through second level hydrate synthesis reactor tail gas outlet 3.
Described microbubble jet perfectly mixed reactor 21 links to each other with hydrate synthesis reactor 27 tops, the second level by microbubble jet perfectly mixed reactor gas inlet tube 19, links to each other with circulating pump 13 outlets by microbubble jet perfectly mixed reactor liquid inlet tube 20 simultaneously;
Described microbubble jet perfectly mixed reactor 21 can be installed in hydrate synthesis reactor top, contains the thing synthesis reactor by gas, liquid pipeline and water and links to each other, and also can be installed in hydrate synthesis reactor inside.
Described circulating pump 13 links to each other with heat exchanger 14 outlets by pipeline.
Described heat exchanger 14 imports separate resolver respectively by second level hydrate synthesis reactor liquid phase circulation pipe 28 and second level hydrate desorbed solution outlet 26 and link to each other with second level hydrate synthesis reactor 27 and second level hydrate;
Described hydrate synthesis reactor and microbubble jet perfectly mixed reactor are formed hydrate slurry by microbubble jet perfectly mixed reactor liquid inlet tube, circulating pump, heat exchanger and hydrate synthesis reactor liquid phase circulation pipe and are followed bad loop.
Described heat exchanger 14 is tubular heat exchanger or coil exchanger, and described heat exchanger 14 shell sides link to each other with freezing liquid upper hose 29 and freezing liquid return pipe 15 respectively.
Described second level hydrate separates resolver 23 and is connected to second level hydrate synthesis reactor 27 gas-liquid interfaces by hydrate slurry overflow pipe, is connected to the gas phase zone of second level hydrate synthesis reactor 27 simultaneously by gas-liquid equilibrium pipe 22;
It can be jacketed reactor that described second level hydrate separates resolver 23, also built-in coil pipe type reactor, and chuck or built-in coil pipe link to each other with hot water upper hose 25 and hot water return pipe 24;
Described second level hydrate separation resolver 23 is separated gassing escape pipe 10 by second level hydrate and is connected to the quick generating apparatus of third level hydrate.
The present invention has improved the concentration and the rate of recovery of separated gas products greatly, has improved separation process speed and efficient.Be particularly useful for CO in the flue gas
2And CO in " green coal " technology integrated gasification combined cycle for power generation
2Hydrate continuous separation method and device, can realize CO in flue gas and other the industrial mist
2Hydrate separate continuously, the present invention simultaneously also can be applicable to the separation of other field multicomponent mists such as oil, chemical industry, metallurgy.
Description of drawings
Fig. 1 is technical module figure of the present invention;
Fig. 2 is submodule B of the present invention (hydrate separation module) process flow diagram;
Fig. 3 is for the second level of the present invention hydrate quick-speed generation system and separate the resolution system installation drawing.
Description of reference numerals: 1, the flue gas feed pipe, 2, first order hydrate is separated the gassing escape pipe, 3, second level hydrate synthesis reactor tail gas outlet, 4, aqueous solution supply pipeline, 5, first order hydrate synthesis reactor tail gas blow-down pipe, 6, first order hydrate slurry overflow pipe, 7, appendix, 8, third level hydrate is separated the gassing escape pipe, 9, third level hydrate slurry overflow pipe, 10, second level hydrate is separated the gassing escape pipe, 11, third level hydrate synthesis reactor tail gas outlet, 12, second level hydrate slurry overflow pipe, 13, circulating pump, 14, heat exchanger, 15, the freezing liquid return pipe, 16, flowmeter, 17a, 17b, control valve, 18a, 18b, stop valve, 19, microbubble jet reactor gas inlet tube, 20, microbubble jet perfectly mixed reactor liquid inlet tube, 21, microbubble jet perfectly mixed reactor, 22, the gas-liquid equilibrium pipe, 23a, 23b, second level hydrate separates resolver, 24, hot water return pipe, 25, the hot water upper hose, 26, second level hydrate desorbed solution outlet, 27, second level hydrate synthesis reactor, 28, second level hydrate synthesis reactor liquid phase circulation pipe, 29, the freezing liquid upper hose.
The specific embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with accompanying drawing:
As shown in Figure 1, 2, 3, flue gas after preliminary treatment such as water washing, drying, compression, precooling, the CO in the flue gas
2Molar concentration be about 18%, pressure is about 2.0MPa, temperature is 4 ℃, pretreated flue gas enters second level hydrate synthesis reactor 27 through flue gas feed pipe 1, charging control valve 18a, flowmeter 16; Containing 1.0% promoter lauryl sodium sulfate aqueous solution joins in first, second and third grade hydrate synthesis reactor by aqueous solution make-up system and aqueous solution supply pipeline 4; The hydrate formation promoter aqueous solution that contains in the second level hydrate synthesis reactor 27 is cooled to 2 ℃ through second level hydrate synthesis reactor liquid phase circulation pipe 28 to heat exchanger 14, enters microbubble jet perfectly mixed reactor 21 through circulating pump 13 and microbubble jet perfectly mixed reactor liquid inlet tube 20 then; The flue gas of second level hydrate synthesis reactor 27 top gas phase zone enters microbubble jet perfectly mixed reactor 21 through microbubble jet reactor gas inlet tube 19, gas-liquid fully contacts the generation hydration reaction in microbubble jet perfectly mixed reactor 21, the hydrate slurry that generates reaches the gas that hydration reaction does not take place, return second level hydrate synthesis reactor 27 from hydrate synthesis reactor 27 tops, the second level, hydrate generates heat and removes by heat exchanger 14, thereby keeps the temperature constant in the hydrate synthesis reactor; Analyze in the hydrate synthesis reactor 27 of the second level gas phase by on-line automatic analytical system and form, control pressure, the time of staying and the tail gas continuous discharge rate of flue gas in the hydrate quick-speed generation system of the second level in the second level hydrate synthesis reactor 27 automatically by being installed in control valve on the second level hydrate synthesis reactor tail gas outlet 2 simultaneously; The tail gas that hydration reaction does not take place that second level hydrate quick-speed generation system is discharged enters first order hydrate quick-speed generation system through second level hydrate synthesis reactor tail gas outlet 3 and continues to take place hydration reaction, improves CO in the flue gas
2The rate of recovery; Hydrate slurry in the second level hydrate synthesis reactor 27 separates resolver 23a, 23b by overflow pipe 12 automatic overflows to second level hydrate, the gas that second level hydrate separates in the resolver returns second level hydrate synthesis reactor 27 by gas-liquid equilibrium pipe 22, thereby realization gas separates with liquid, solid, after second level hydrate separation resolver is full of the hydrate slurry, realize that by calculating automatic control system two second level hydrates separate the switchings between the resolver; The chuck that separates resolver to the second level hydrate that is full of the hydrate slurry feeds hot water, is warming up to 15 ℃, and decomposition of hydrate produces is rich in CO
2Gas separate gassing escape pipe 10 through second level hydrate and enter the third level hydrate quick-speed generation system hydration reaction continue to take place, improve CO in the product
2The concentration of gas, it is recycling that the aqueous solution that parses returns second level hydrate synthesis reactor 27 through second level hydrate desorbed solution outlet 26, heat exchanger 14 and circulating pump.
The gas that hydration reaction does not take place at first order hydrate quick-speed generation system is by first order hydrate synthesis reactor tail gas blow-down pipe and the continuous emptying of tail gas blowdown system voltage stabilizing; First order hydrate separates the CO that is rich in that resolver resolves goes out
2Gas separate gassing escape pipe 2 as unstripped gas through first order hydrate and enter second level hydrate synthesis reactor 27 and continue reaction.
The gas that hydration reaction does not take place at first order hydrate quick-speed generation system returns second level hydrate synthesis reactor 27 through third level hydrate synthesis reactor tail gas outlet 11 and continues reaction; Third level hydrate separates the high concentration CO that resolver resolves goes out
2Gas is separated gassing escape pipe 8 through third level hydrate and is entered CO
2Gas-drying system, dried CO
2Gas is delivered to CO through appendix
2The gas gas storage system.
By above-mentioned three stage countercurrents series connection hydrate piece-rate system, CO in the flue gas
2The rate of recovery can reach more than 98% products C O
2Concentration can reach more than 99%, the rate of departure improves greatly.
Adopt above-mentioned same technological process, hydrate formation promoter can be used instead and be selected from one of following or its mixture: oxolane, 1,4-dioxane or acetone or quaternary ammonium salt, sulfonium salt, phosphonium salt, lauryl sulfate, dodecane sulfonate, the content that contains the promoter aqueous solution changes between 0.1%-15%, all can obtain good CO
2The rate of recovery.
Claims (7)
1, a kind of hydrate mist continuous separation method, form by feed pretreatment module, hydrate separation module, data acquisition and control module, analysis module and refrigeration module, described hydrate separation module adopts three stage countercurrents series connection continuous separation technology, is separated resolution system, is contained hydrate formation promoter aqueous solution make-up system, CO by first, second and third grade hydrate quick-speed generation system, first, second and third grade hydrate
2Gas-drying system, CO
2Gas storage system and tail gas blowdown system are formed: first, second and third grade hydrate quick-speed generation system includes hydrate synthesis reactor, microbubble jet perfectly mixed reactor, circulating pump and heat exchanger, first, second and third grade hydrate separates resolution system and includes two parallel hydrates separation resolvers, two separation resolvers switch use, one is used for separating of gas and hydrate slurry, and another is used for the parsing of hydrate; Described hydrate separation module comprises following processing step:
1) contains the hydrate formation promoter aqueous solution to the adding of first, second and third grade hydrate quick-speed generation system;
2) flue gas of compressing, be precooled to predetermined pressure, temperature enters second level hydrate quick-speed generation system;
3) flue gas generates the gas hydrate slurry in the microbubble jet perfectly mixed reactor of second level hydrate quick-speed generation system, hydrate generates heat and removes by external second level heat exchanger, and keeping second level hydrate quick-speed generation system temperature to be lower than hydrate-formation temperature, the hydrate slurry automatic overflow of generation to second level hydrate separates resolution system;
4) heating in second level hydrate separation resolution system of hydrate slurry resolves to and is rich in CO
2The gas and the aqueous solution, it is recycling that the aqueous solution that parses returns second level hydrate quick-speed generation system by circulating pump;
What 5) parse is rich in CO
2Gas enter third level hydrate quick-speed generation system and further improve CO
2Concentration, in the microbubble jet perfectly mixed reactor of third level hydrate quick-speed generation system, generate the gas hydrate slurry, hydrate generates heat and removes by external third level heat exchanger, and keeping third level hydrate quick-speed generation system temperature to be lower than hydrate-formation temperature, the hydrate slurry automatic overflow of generation to third level hydrate separates resolution system;
6) heating in third level hydrate separation resolution system of hydrate slurry is decomposed into high-purity CO
2The gas and the aqueous solution, it is recycling that the aqueous solution returns third level hydrate quick-speed generation system by circulating pump;
7) the high-purity CO that parses
2Gas enters and enters the gas storage system storage after drier dehydrates;
8) the poor CO of hydration reaction does not take place in the third level hydrate quick-speed generation system
2Gas returns second level hydrate quick-speed generation system as unstripped gas and continues reaction;
9) the poor CO of hydration reaction does not take place in second level hydrate quick-speed generation system
2Gas enters first order hydrate quick-speed generation system, further improves CO
2The rate of recovery, poor CO
2Gas generates the gas hydrate slurry in the microbubble jet perfectly mixed reactor of first order hydrate quick-speed generation system, hydrate generates heat and removes by external first order heat exchanger, and keeping first order hydrate quick-speed generation system temperature to be lower than hydrate-formation temperature, the hydrate slurry automatic overflow of generation to first order hydrate separates resolution system;
10) the hydrate slurry separates in the resolution system at first order hydrate and adds thermal decomposition, parsing the aqueous solution, to return first order hydrate quick-speed generation system by circulating pump recycling, and the gas that parses returns second level hydrate quick-speed generation system as raw material and continues reaction;
11) N of hydration reaction does not take place in the first order hydrate quick-speed generation system
2And trace amounts of CO
2Gas is by the emptying of tail gas blowdown system.
2, hydrate mist continuous separation method as claimed in claim 1, it is characterized in that gas flows between each equipment in system all realizes by pressure differential, the gas flow pressure difference is 0.05～0.5MPa, during operation, second level hydrate separates the pressure of resolver greater than third level hydrate synthesis reactor pressure, first order hydrate separates the pressure of resolver and third level hydrate synthesis reactor greater than second level hydrate synthesis reactor pressure, and second level hydrate synthesis reactor pressure is greater than first order hydrate synthesis reactor pressure.
3, hydrate mist continuous separation method as claimed in claim 1, it is characterized in that the described content that contains the hydrate formation promoter aqueous solution is 0.1%-15%, described hydrate formation promoter is selected from one of following or its mixture: oxolane, 1,4-dioxane or acetone or quaternary ammonium salt, sulfonium salt, phosphonium salt, lauryl sulfate, dodecane sulfonate.
4, hydrate mist continuous separation method as claimed in claim 1, it is characterized in that first, second and third grade hydrate quick-speed generation system temperature is respectively 274 ℃, 277 ℃, 280 ℃, the temperature of first, second and third grade hydrate quick-speed generation system is by regulating the flow-control of heat exchanger freezing liquid.
5, a kind of hydrate mist continuous separation device comprises feed preparation unit, the series connection of hydrate three stage countercurrents continuous separation device, data acquisition and control device, analytical equipment, refrigerating plant and connecting pipe; Described hydrate three stage countercurrents series connection continuous separation device comprises that the quick generating apparatus of first, second and third grade hydrate, first, second and third grade hydrate separate resolver, contain hydrate formation promoter aqueous solution device for supplying, CO
2Gas drier, CO
2Caisson and tail gas emptying device; The quick generating apparatus of described first, second and third grade hydrate includes hydrate synthesis reactor, microbubble jet perfectly mixed reactor, circulating pump and heat exchanger; Described first, second and third grade hydrate separates resolver and includes two parallel hydrates and separate resolvers, and two separation resolvers switch and use, and one is used for separating of gas and hydrate slurry, and another is used for the parsing of hydrate; The described hydrate formation promoter aqueous solution device for supplying that contains is connected to the quick generating apparatus of first, second and third grade hydrate respectively by aqueous solution supply pipeline; Described CO
2Gas drier is connected to CO through appendix
2Caisson.
6, hydrate mist continuous separation device as claimed in claim 5, hydrate quick generating apparatus in the described second level is connected to feed preparation unit by flue gas feed pipe (1), second level hydrate synthesis reactor (27) is connected to the quick generating apparatus of first order hydrate through second level hydrate synthesis reactor tail gas outlet (3), hydrate quick generating apparatus in the described second level is connected to second level hydrate through second level hydrate slurry overflow pipe (12) and separates resolver, and described second level hydrate separation resolver is separated gassing escape pipe (10) by second level hydrate and linked to each other with the quick generating apparatus of third level hydrate; The quick generating apparatus of described third level hydrate is connected to flue gas feed pipe (1) through third level hydrate synthesis reactor tail gas outlet (11), the quick generating apparatus of described third level hydrate is connected to third level hydrate through third level hydrate slurry overflow pipe (9) and separates resolver, and described third level hydrate separates resolver and separates gassing escape pipe (8) and CO by third level hydrate
2Drying device links to each other; The quick generating apparatus of described first order hydrate links to each other with the tail gas emptying device through first order hydrate synthesis reactor tail gas blow-down pipe (5), the quick generating apparatus of described first order hydrate is connected to first order hydrate through first order hydrate slurry overflow pipe (6) and separates resolver, and described first order hydrate separation resolver is separated gassing escape pipe (2) through first order hydrate and is connected to flue gas feed pipe (1).
7, hydrate mist continuous separation device as claimed in claim 5, it is characterized in that described hydrate synthesis reactor is connected by flange with microbubble jet perfectly mixed reactor, described microbubble jet perfectly mixed reactor links to each other with hydrate synthesis reactor top by microbubble jet reactor gas inlet tube, forms the hydrate slurry closed circuit by microbubble jet perfectly mixed reactor liquid inlet tube, circulating pump, heat exchanger and hydrate synthesis reactor liquid phase circulation pipe simultaneously; Described hydrate synthesis reactor separates between the resolver with hydrate and is connected by hydrate slurry overflow pipe.
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