CN101456556A - Carbon dioxide industrial-scale separation and purification system and method in mixture gas by hydrate method - Google Patents
Carbon dioxide industrial-scale separation and purification system and method in mixture gas by hydrate method Download PDFInfo
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- CN101456556A CN101456556A CNA2008102206732A CN200810220673A CN101456556A CN 101456556 A CN101456556 A CN 101456556A CN A2008102206732 A CNA2008102206732 A CN A2008102206732A CN 200810220673 A CN200810220673 A CN 200810220673A CN 101456556 A CN101456556 A CN 101456556A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention discloses a system and a method for industrially separating and purifying CO2 in mixed gas by a hydrate method. The system consists of a feed gas pretreatment system, a hydrate separation tower, a micro-bubble jet-loop reaction system, a column bottom hydrate decomposition system, a CO2 product collection system, a hydrate formation and decomposition heat comprehensive utilization system and a tail gas energy recovery system. The method integrates hydrate bubbling reaction technology, spraying reaction technology and micro-bubble jet reaction technology, adopts CO2 reflux displacement fractionation technology to improve the concentration of the CO2 in a hydrate phase, has simple separation technology and device and high separation rate and efficiency, comprehensively utilizes the formation heat and decomposition heat of the hydrate during refrigeration cycle, simultaneously recovers compression work of tail gas and cold energy for feed gas pretreatment, and has low energy consumption and cost during separation. The system and the method can be applied to industrial and continuous separation and purification of the CO2 in the mixed gas such as flue gas (CO2/N2), IGCC synthetic gas (CO2/H2), biomass synthetic gas (CO2/H2), natural gas (CO2/CH4), coalbed gas and the like.
Description
Technical field
The present invention relates to CO in a kind of mixed gas
2The industrial separation purification techniques, especially a kind of CO that utilizes
2The hydrate process is separated CO in the purification mixed gas
2The industrial separation system and method.
Background technology
Global warming and greenhouse gases CO
2Reduction of discharging is the focus and the difficult point problem of whole world concern at present, and Chinese Government's reduction of greenhouse gas discharge target in 2010 is 1,000,000,000 tons, and it is imperative to reduce discharging, and shoulders heavy responsibilities.CO in the atmosphere
2Concentration raises fast and is mainly derived from extensive energy generation discharging gas in the industry, the CO of generating discharging
2Account for global CO
2More than 37.5% of total emission volumn is CO
2The emphasis place that reduces discharging.It is the country of main energy sources with coal that China is one, and this energy structure will can not change in considerable time from now on.The coal in China major part is used for generating, reduces discharging CO in the power plant
2Extremely urgent.The direct combusting firepower generating of at present traditional coal will be in dominant position, the CO of coal-fired power plant in China's power field in considerable time
2Quantity discharged is the industrial CO of control greatly and concentrated relatively
2The main field of discharging.At present emerging integrated gasification combined cycle plants (IGCC) generation technology is as a kind of " clean coal ", its synthetic gas (CO
2/ H
2) middle CO
2Separation with to seal up for safekeeping be the important component part of IGCC technical study, also be the whether key of real " cleaning " of this technology.
CO
2The reduction of discharging measure can reduce following three classes: (1) improves efficiency of energy utilization and energy-conservation; (2) use non-carbon new and renewable sources of energy; (3) continue to use existing fossil oil, and take measures to capture the CO that seals discharge up for safekeeping
2Because the restriction of development in science and technology level, first and second kind measure respectively can only be as CO
2Reduce discharging the target of mid-term, long-term endeavour, have only the third measure: CO
2Capture and seal technology (CCS) up for safekeeping and just can in short duration, realize global CO
2The extensive reduction of discharging.The CCS technology comprises CO
2Separation and collection, transport and seal up for safekeeping three aspects, wherein CO
2The separation and collection energy consumption is the highest, and economy is the poorest, accounts for whole C O
2Reducing discharging 60～70% of cost, is CO
2The difficult point and the key restraining factors that reduce discharging.Current, the CCS technical study mainly concentrates on high-level efficiency, CO cheaply
2Separating and purifying method and technical study; Developed multiple CO
2Separation method and capture technology (capture of burning back, the preceding decarburization of burning, oxygen-enriched combusting etc.), various CO
2The separation and collection method does not have problems technically, but ubiquity CO
2Separating energy consumption height, defect of high cost.Up to now, at CO
2The separation and collection aspect does not also have any method to become absolute winner to be generally acknowledged by the whole world and accept that various separation methods all have its relative merits and suitable application area.
Separate and contain CO
2The industrial method of gaseous mixture mainly contains chemical absorption, physical adsorption, low temperature separation process, transformation absorption and membrane sepn etc.The chemical absorption range of application is narrow, and it is big that absorption agent reclaims energy consumption.Chinese patent CN1747774A discloses a kind of CO that adopts Separation and Recovery the secondary angry body that chemical absorption method produces from Steel Plant etc.
2Method, this method is utilized Steel Plant's low-grade heat extraction heating recovery chemical absorber, separation costs reduces greatly.The deep cooling process for separating investment is higher, and energy consumption is big, only when unit scale is big, just has preferable economy.The subject matter that pressure swing adsorption process exists is the energy consumption height, facility investment is big, the sorbent material utilization ratio is low and loss is big.Present widely used membrane sepn rule has chemistry and shortcomings such as poor heat stability, selectivity and flux are not high, processing power is limited, product purity is low, poor durability.Develop that novel, efficient gas separates, method of purification has important economic implications.
CO in the hydrate Separation and Recovery mixed gas
2Be based on and contain CO
2Gaseous mixture in the hydrate formation condition difference of each component, each component is separated the back with hydrate and is decomposed in the partition ratio difference of hydrate in mutually in the mixed gas with mixed gas, can reach and separate purification CO
2Purpose.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 absorbing separation method.Compare the CO of hydrate isolation technique in power-plant flue gas with traditional separation method
2And CO in " green coal " integrated gasification combined cycle for power generation
2Separate, put forward dense aspect and have more potentiality.The first, the hydrate isolation technique can carried out more than 0 ℃, can save a large amount of refrigeration energy needed; The second, the gaseous tension 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 technical process is also simple relatively.The hydrate isolation technique has broad application prospects as novel separation means, and might become the isolating mainstream technology of mixed gas.
Though in that some researchs are arranged aspect the hydrate isolation technique, also imperfect abroad, domestic research in this respect then is in the starting stage.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 flow system, this system was confirmed by Los Alamos National Laboratory afterwards, and then confirmed to realize that the industrialization of hydrate isolation technique has very big potentiality (Wong, S.andBioletti, R.Carbon dioxide separation technologies. (2002) .Carbon ﹠amp; EnergyManagement, Alberta Research Council, Edmonton, Alberta, T6N 1E4, Canada.).U.S. Pat 6602326B2 discloses a kind of employing tetrahydrofuran (THF) and forms CO in the promotor 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 equilibrium 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 promotor 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 domestic Chen Guang of China University Of Petroleum Beijing advance etc. to have applied for the multinomial patent of utilizing methane and hydrogen in the Hydrate Technology separating ethene cracking gas (CN1762930, CN1762929, CN1762928).
Carry out the existing certain research of gas delivery though utilize Hydrate Technology, some mechanism, basic problem in science and some gordian techniquies have been solved, and certain patent report is arranged, but do not see the isolating industrial applications report of relevant hydrate mixed gas up to now as yet.Major cause is that the continuous isolation technique of hydrate mixed gas will realize that industrial applications must solve the problem of following five aspects: one, adopt suitable hydrate to form promotor and improve hydrate formation speed, reduce hydrate and form the temperature and pressure condition; Two, adopt suitable gas-liquid mixed 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 sepn process object gas and the purity of gas products, reduce the energy consumption of sepn process.
Domestic scientific research institutions also disclose a kind of hydrate mixed gas continuous separation method and device (CN1973959A), adopt hydrate to form promotor and reduce hydrate formation temperature and pressure condition, adopt microbubble jet perfectly mixed reactor to improve gas liquid contacting efficiency, adopt the external heat exchanger strengthened aqua compound to generate the removal speed of heat, adopt three stage countercurrents series connection hydrate separation system, separate the CO in the power-plant flue gas continuously
2, CO
2The rate of recovery can reach more than 98% products C O
2Concentration can reach more than 99%, segregation rate improves greatly.But also there is certain shortcoming in aforesaid method, mainly shows to adopt three grades of separation, and separating device quantity is many, investment is big, the flow process complexity of gas, liquid, solid three-phase system in system under the condition of high voltage is difficult to control, is unfavorable for energy-conservation and total energy approach etc. in the industrial applications process.
Summary of the invention
The object of the present invention is to provide simple, economic, the CO in the hydrate separating mixed gas efficiently of a kind of separating technology
2Industrial separation purification system and method, simplify hydrate separating device and operating process, reduce cost of investment and separating energy consumption, improve the stability and the reliability of hydrate lock out operation, be applied to stack gas (CO
2/ N
2), IGCC synthetic gas (CO
2/ H
2), biomass synthesis gas (CO
2/ H
2), Sweet natural gas (CO
2/ CH
4), CO in the mixed gas such as coal-seam gas
2Industrialization separate continuously.
For realizing above purpose, the present invention has taked following technical scheme: CO in a kind of hydrate mixed gas
2The industrial separation purification system includes
A, be used for compressing unstripped gas to predetermined pressure and being cooled to the feed gas preprocessing system of preset temperature, it comprises multi-stage compressor, multistage inter-stage interchanger and inter-stage gas-liquid separator, be used for compressing unstripped gas to predetermined pressure and being cooled to preset temperature, adopt prior art to implement;
B, hydrate knockout tower, it is divided into CO from tower still to cat head
2Displacement fractionation zone, blistering reaction district, spray reaction zone are used to receive the unstripped gas that the feed gas preprocessing system carries, and make unstripped gas fully separate in the hydrate knockout tower; CO
2Displacement fractionation zone and blistering reaction district are hollow cylinder, and inner filling water compound slurries are external phase, and the unstripped gas opening for feed is CO
2The dividing point in displacement fractionation zone and blistering reaction district; The gas that hydration reaction does not take place accumulates in the spray reaction zone, is external phase, and liquid-gas interface is the dividing point of blistering reaction district and spray reaction zone; The working pressure in tower Zhong Ge district identical (ignoring the fluid column static pressure), but temperature constantly reduces from tower still to cat head.
C, microbubble jet circulating reaction system are used to aspirate the mixed gas that hydrate reaction does not take place in the described hydrate knockout tower, promote the quick generation of the hydrate in the spray reaction zone; Comprise the microbubble jet reactor that is communicated with the top of described spray reaction zone, also be connected with external primary cooler and recycle pump in turn with this microbubble jet reactor, also be connected with auxiliary cooler between described microbubble jet reactor and external primary cooler, the effect of auxiliary cooler is can not reach cooling at external primary cooler to provide cold energy by the exterior cooling system when requiring; Extract hydrate slurry by recycle pump from the hydrate knockout tower, be cooled to through external primary cooler and auxiliary cooler that supercooled water compound slurries are laggard goes into the microbubble jet reactor, suction function by the microbubble jet reactor sucks the microbubble jet reactor with the mixed gas circulation that hydrate reaction does not take place cat head simultaneously, gas-liquid two-phase returns hydrate and separates cat head behind microbubble jet reactor thorough mixing, the effect of generation spray, promote the quick generation of spray reaction zone hydrate, reach by said process and improve hydrate reaction speed, reduce tail gas concentration and remove the purpose that hydrate generates heat.
D, tower still decomposition of hydrate system comprise decomposition of hydrate device and auxiliary splitter, and the effect of auxiliary splitter is the heat that decomposition of hydrate is provided by the indirect heating system when the decomposition of hydrate device can not satisfy the decomposition of hydrate load; The hydrate slurry that is deposited at the bottom of the tower enters decomposition of hydrate device and auxiliary splitter, and thermal degradation is water and CO
2, water and portion C O
2Because density diminishes, at the bottom of the tower of backflow backwater compound knockout tower, another part CO
2Rise to CO
2The product acquisition system is collected, by control CO
2The collecting amount of product is controlled the quantity of reflux of CO2.
E, CO
2The product acquisition system, it is connected with described tower still decomposition of hydrate system, is used for the isolated CO of acquisition system
2Comprise product collection tube, gas accumulation jar and gather variable valve, this product collection tube one end is communicated with described decomposition of hydrate device respectively and outputs to described CO by porous distribution of reflux device
2In the displacement fractionation zone, its other end is by gas accumulation jar and gas collecting variable valve output gaseous state CO
2, the product collection tube is vertically installed, and extends to the above certain altitude of liquid level of hydrate slurry in the hydrate knockout tower, and gas accumulation jar and collection variable valve are installed in more than the liquid level of hydrate slurry in the hydrate knockout tower equally.
F, hydrate generate and decomposition heat utilization system.By by the refrigeration cycle of liquefied ammonia,, decomposition of hydrate forms heat for providing decomposition heat and remove hydrate as medium.Comprise by with described CO
2Decomposition of hydrate device, auxiliary condenser, ammonia compressor, external primary cooler, auxiliary evaporator, throttle expansion valve that displacement fractionation zone bottom connects constitute refrigeration cycle; In the hydrate sepn process, hydrate generates the removal of heat and the supply of decomposition of hydrate heat, and the energy of consumption is big, because in the sepn process, the generation of hydrate heat is suitable substantially with decomposition heat quantity, but taste is different, directly integrated utilization; The present invention is according to These characteristics, between decomposition of hydrate device and external primary cooler, set up ammonia compressor and throttle expansion valve, adopt liquefied ammonia as refrigerant, set up cooling cycle system, the decomposition of hydrate device is as the condenser of cooling cycle system, and external primary cooler is as the vaporizer of refrigeration system; The compressed machine compression temperature of ammonia steam raises, gasification, and entering the decomposition of hydrate device provides decomposition of hydrate required heat energy, the liquefaction of ammonia vapor condensation, and temperature reduces; Enter through the throttle expansion valve expansion through cooled liquefied ammonia, pressure, temperature all reduce; Low-temperature liquid ammonia enters external primary cooler absorption hydrate and forms heat, the liquefied ammonia vaporization, and temperature raises, and ammonia vaporised steam enters compressor compresses then, finishes refrigeration cycle; For the condensation ability that prevents cooling cycle system decomposition of hydrate device and the steam capability of external primary cooler do not match, in the recycle system, set up auxiliary condenser and auxiliary evaporator compensates.
G, be used to reclaim CO
2The tail gas energy recovery system of separating the back residual exhaust is because CO
2Separate the remaining tail gas in back and have higher pressure and lesser temps, particularly CO in unstripped gas
2When content hanged down, tail gas was large-minded, and wherein pressure potential that is comprised and cold energy quantity are big; The present invention adopts multistage expansion turbine and multistage inter-stage interchanger to reclaim the compression work and the cold energy of tail gas, and the low temperature exhaust gas after expanding is used for the cooling of feed gas preprocessing process, and the tail gas energy removal process adopts prior art to implement.
At the inner column plate of installing of described spray reaction zone; Raw material gas inlet and tower still CO at described hydrate knockout tower
2Porous feed sparger and porous distribution of reflux device are all installed by gas or liquid return mouth place.The column plate that is arranged in the spray reaction zone helps lend some impetus to gas liquid contacting efficiency, and the gas that hydration reaction does not take place accumulates in the spray reaction zone, is external phase; Porous feed sparger and porous distribution of reflux device can improve blistering reaction district and CO
2Displacement fractionation zone gas-liquid or liquid-liquid contact efficiency and hydration reaction speed.
The present invention also provides CO in a kind of hydrate mixed gas
2The industrial separation method of purification comprises the steps:
1) at first inject a certain amount of promotor aqueous solution that contains by recycle pump in whole hydrate separation system, the auxiliary cooler by the microbubble jet reaction recycle system reduces aqueous temperature to hydrate and generates temperature;
2) unstripped gas to be separated separates pre-treatment through stage compression, multistage cooling, multi-stage gas-liquid, makes its pressure be elevated to the working pressure of hydrate knockout tower, and temperature is reduced to hydrate and generates temperature;
3) enter the blistering reaction district of hydrate knockout tower through pretreated unstripped gas through the porous feed sparger, rise, contact formation CO with the low temperature hydrate slurry in the form of blistering reaction district unstripped gas with bubbling
2The mixed gas hydrate that content is high is because CO
2Hydrate density is greater than solution density, and hydrate crystal grain enters CO to deposit
2The displacement fractionation zone, the gas that hydration reaction does not take place rises to the spray reaction zone; Gas rises in the process of cat head and sprays the reverse formation hydrate that contacts of the supercooled water compound slurries that get off from cat head microbubble jet reactor along the spray reaction zone, and hydrate solids is with flowing to the blistering reaction district under the aqueous solution, the CO in the gas phase
2Concentration constantly reduce;
4) be settled down to CO
2The hydrate solids of displacement fractionation zone further to the enrichment of tower bottom sediments, enters tower still decomposition of hydrate system because density is big, is warming up to the decomposition of hydrate temperature, is decomposed into water and liquid state or gaseous state CO
2, water and portion C O
2At the bottom of the porous liquid sparger is back to tower, the CO of backflow
2Because density is less than the density of water, with bubble or drop form along CO
2The displacement fractionation zone rises; Because CO
2Displacement fractionation zone temperature constantly raises from top to bottom, hydrate solids temperature in tower bottom sediments process raises, simultaneously with the CO of the high density that at the bottom of tower, refluxes
2Counter current contact, partially mixed gas hydrate decomposes, and forms CO simultaneously
2Hydrate, the CO in the gas phase
2Displace the difficult gases that form hydrate such as the N2 of hydrate in mutually; Hydrate solids is to the tower bottom sediments, and replacement(metathesis)reaction is carried out continuously, the middle mutually CO of hydrate
2Concentration constantly raise and CO in backflow gas phase or the liquid phase
2Concentration constantly reduces;
5) in the sepn process, extract the part hydrate slurry out from the circulation of hydrate knockout tower middle part, be cooled to through external primary cooler and auxiliary cooler that supercooled water compound slurries are laggard goes into the microbubble jet reactor, suction function by the microbubble jet reactor sucks the microbubble jet reactor with the mixed gas circulation that hydration reaction does not take place cat head simultaneously, gas-liquid two-phase returns hydrate and separates cat head behind microbubble jet reactor thorough mixing, the effect of generation spray, the CO in the cat head mixed gas
2Concentration further reduces, tower top temperature reduces, and reaches separation requirement and removes the purpose that hydrate generates heat;
6) the poor CO of cat head
2Gas stablize extraction as tail gas by the tail gas variable valve, compression work and cold energy by in tail gas energy recovery system recovery low temperature, the highly compressed tail gas are used for the compression and the cooling of feed gas preprocessing system;
7) another part CO of going out of tower still decomposition of hydrate system decomposition
2Rise to CO along product collection tube bubbling
2The product acquisition system is collected, by control CO
2The collecting amount of product is controlled CO
2Quantity of reflux.
The working pressure in hydrate knockout tower Zhong Ge of the present invention district is identical, and temperature raises from top to bottom continuously, gas phase and the middle mutually CO of hydrate
2Concentration raises from top to bottom continuously; Hydrate separates tower top temperature greater than 273.15K, the working pressure of hydrate knockout tower is by cat head service temperature and the decision of tail gas concentration, temperature after the feed gas preprocessing is formed decision by working pressure and unstripped gas, and tower still decomposition of hydrate system temperature is formed decision by working pressure and product; The hydrate phase balance temperature deducted certain condensate depression (generation impellent) under working pressure that described hydrate generation temperature is a knockout tower and mixed gas were formed, and the hydrate phase balance temperature added certain decomposition impellent under working pressure that described decomposition of hydrate temperature is a knockout tower and mixed gas were formed.
The described promotor aqueous solution that contains, the content of its hydrate formation promoter is 0.1%～50%, described hydrate formation promoter is selected from one of following or its mixture: tetrahydrofuran (THF), 1,4-dioxane, acetone, quaternary ammonium salt, sulfonium salt, phosphonium salt, fluorochlorohydrocarbon, high-carbon hydrocarbon, dodecyl sulfate or dodecane sulfonate.
When the working pressure of described hydrate knockout tower less than the decomposition of hydrate device in temperature and CO
2During liquefaction pressure under forming, the decomposition of hydrate product is gaseous state CO
2, CO
2Gas rises along product collection tube bubbling, is focused to the gas accumulation jar, gathers gaseous state CO by the gas collecting variable valve
2Product; When the working pressure of hydrate knockout tower greater than the decomposition of hydrate device in temperature and CO
2During liquefaction pressure under forming, the decomposition of hydrate product is liquid CO
2, liquid CO
2Because of density rises along the product collection tube less than water, and carry out fractionation with the aqueous solution in the product collection tube, accumulate in the top of product collection tube, liquid level is higher than hydrate slurry liquid level in the hydrate knockout tower, can directly gather liquid CO by the liquid acquisition variable valve
2Product.
The present invention compared with prior art has following advantage: the present invention is integrated hydrate blistering reaction technology, spray reaction technology and microbubble jet reaction technology, and adopt CO
2The displacement fractionating technology that refluxes improves the middle mutually CO of hydrate
2Concentration, separation method and system are simple, segregation rate and efficient improve greatly; Utilize hydrate to generate heat by the refrigeration cycle process synthesis, reclaim tail gas compression work and cold energy simultaneously and be used for feed gas preprocessing, significantly reduced the energy consumption and the cost of sepn process with decomposition heat; The present invention can be applicable to stack gas (CO
2/ N
2), IGCC synthetic gas (CO
2/ H
2), biomass synthesis gas (CO
2/ H
2), Sweet natural gas (CO
2/ CH
4), CO in the mixed gas such as coal-seam gas
2Industrialization separate purification continuously.
Description of drawings
Fig. 1 is CO in the hydrate mixed gas of the present invention
2Industrial separation purifying technique flow process and system architecture synoptic diagram;
Description of reference numerals: 1, feed gas compressor, 2, interstage heat exchanger, 3, turbo-expander, 4, the inter-stage gas-liquid separator, 5, the hydrate knockout tower, 501, CO
2The displacement fractionation zone, 502, the blistering reaction district, 503, the spray reaction zone, 5031, column plate, 504, raw material gas inlet, 6, the porous feed sparger, 7, the tail gas variable valve, 8, gas-liquid separator, 9, the microbubble jet reactor, 10, the gas collecting variable valve, 11, the gas accumulation jar, 12, the liquid acquisition variable valve, 13, auxiliary cooler, 14, the product collection tube, 15, recycle pump, 16, external primary cooler, 17, auxiliary evaporator, 18, throttle expansion valve, 19, ammonia compressor, 20, auxiliary condenser, 21, the decomposition of hydrate device, 22, auxiliary splitter, 23, porous distribution of reflux device.
Embodiment
Below in conjunction with the drawings and specific embodiments content of the present invention is described in further details.
Embodiment:
See also shown in Figure 1ly, flow is 100kmol/h, and pressure is 1bar, and temperature is the unstripped gas (power-plant flue gas) of 373.15K, its CO
2Volumetric molar concentration be 17%, flue gas enters hydrate knockout tower 5 from raw material gas inlet 504 by porous feed sparger 6 after 1 compression of three grades of feed gas compressors, 2 coolings of level Four interstage heat exchanger, three grades of inter-stage gas-liquid separator 4 pre-treatment, flue gas pressures reaches 24.46bar, temperature 280.25K; Adopt recycle pump 15 to the hydrate knockout tower inject Tetrabutyl amonium bromide (TBAB) content be 7.5% contain the promotor aqueous solution, make CO
2Displacement fractionation zone 501 and blistering reaction district 502 are full of and contain the promotor aqueous solution; Enter hydrate knockout tower 5 through pretreated flue gas and carry out the hydration separation reaction, the working pressure of hydrate knockout tower is 24.46bar, tower top temperature is 273.65K, gas approach temperature 280.25K, tower still decomposition of hydrate device 21 temperature are 286.45K, and temperature reduces on following continuously in the hydrate knockout tower.
Flue gas enters the blistering reaction district 502 of hydrate knockout tower with the form of bubbling after porous feed sparger 6 disperses, in the blistering reaction district, flue gas contains the promotor aqueous solution with low temperature and contacts, and forms CO
2The mixed gas hydrate crystal grain that content is high, hydrate crystal grain with contain the promotor aqueous solution and form hydrate slurry; The gas that hydration reaction does not take place rises to spray reaction zone 503 along the blistering reaction district, contact the generation mixed gas hydrate closely with the supercooled water compound slurries that spray from cat head microbubble jet reactor 9, hydrate solids is with flowing to blistering reaction district 502 under the aqueous solution, the CO in the gas phase
2Concentration constantly reduces; Generate heat and reduce CO in the cat head tail gas for removing hydrate
2Content, in the sepn process, adopt recycle pump 15 to extract the part hydrate slurry out from the circulation of hydrate knockout tower middle part, be cooled to through external primary cooler 16 and auxiliary cooler 13 that supercooled water compound slurries are laggard goes into the microbubble jet reactor, suction function by the microbubble jet reactor sucks the microbubble jet reactor with the mixed gas circulation that hydration reaction does not take place cat head simultaneously, gas-liquid two-phase returns hydrate and separates cat head behind microbubble jet reactor thorough mixing, the effect of generation spray, the CO in the cat head mixed gas
2Concentration further reduces, tower top temperature reduces; Accumulate in the poor CO of cat head
2Gas is stablized extraction, CO in the tail gas as tail gas by gas-liquid separator 8 and tail gas variable valve 7
2Content is 3.95%, exhaust flow 86.12kmol/h, tail gas pressure 24.46bar, temperature 273.65K; Owing to have higher pressure and lesser temps in the tail gas, adopt two stage turbine decompressor 3 and two-stage inter-stage interchanger 2 to reclaim the compression work and the cold energy of tail gas, be used for the compression and the cooling of feed gas preprocessing system.
The hydrate slurry that blistering reaction district 502 and spray reaction zone 503 generate enters CO because density is bigger to deposit
2Displacement fractionation zone 501 is settled down to CO
2The hydrate solids of displacement fractionation zone 501 is further to the enrichment of tower bottom sediments, enters tower still decomposition of hydrate device 21 and auxiliary splitter 22 and heats up and be decomposed into water and gaseous state CO
2, water and portion C O
2At the bottom of porous distribution of reflux device 23 was back to tower, reflux ratio was 0.5, the CO of backflow
2Because density is little, with bubble form along CO
2Displacement fractionation zone 501 rises; Because CO
2Displacement fractionation zone 501 temperature constantly raise from top to bottom, hydrate solids temperature in tower bottom sediments process raises, simultaneously with the CO of the high density that at the bottom of tower, refluxes
2The back flow of gas contact, partially mixed gas hydrate decomposes, and forms CO simultaneously
2Hydrate, the CO in the gas phase
2Displace the N of hydrate in mutually
2Deng the difficult gas that forms hydrate, hydrate solids is to the tower bottom sediments, and replacement(metathesis)reaction is carried out continuously, the middle mutually CO of hydrate
2Concentration constantly raise and CO in the gas phase
2Concentration constantly reduces; Another part CO that tower still decomposition of hydrate system decomposition goes out
2Gas rises to gas accumulation jar 11 along product collection tube 14 bubblings, stablizes extraction by gas collecting variable valve 10 then, by control CO
2The collecting amount of product is controlled CO
2Quantity of reflux, the CO of collection
2Gas flow is 13.88kmol/h, products C O
2Content 98%.
For the comprehensive utilization hydrate generates heat and decomposition of hydrate heat, reduce separating energy consumption, utilize decomposition of hydrate device 21 and external primary cooler 16 condenser and vaporizer respectively as cooling cycle system, set up ammonia compressor 19 and throttle expansion valve 18, adopt liquefied ammonia as refrigerant, set up cooling cycle system, provide required heat of decomposition of hydrate and hydrate to form required cold by the liquefied ammonia refrigeration cycle, for the condensation ability that prevents decomposition of hydrate device 21 in the cooling cycle system and the steam capability of external primary cooler 16 do not match, in the recycle system, set up auxiliary condenser 20 and auxiliary evaporator 17 compensates.
When the working pressure of hydrate knockout tower greater than the decomposition of hydrate device in temperature and CO
2During liquefaction pressure under forming, the decomposition of hydrate product is liquid CO
2, because liquid CO
2Density is less than the density of water, liquid CO
2Rise along product collection tube 14, and carry out fractionation with the aqueous solution in the product collection tube, accumulate in the top of product collection tube 14, liquid level is higher than hydrate slurry liquid level in the hydrate knockout tower 5, can directly gather liquid CO by liquid acquisition variable valve 12
2Product.
Adopt above-mentioned same technical process, hydrate formation promoter can be used instead and be selected from one of following or its mixture: tetrahydrofuran (THF), 1,4-dioxane, acetone, quaternary ammonium salt, sulfonium salt, phosphonium salt, fluorochlorohydrocarbon, high-carbon hydrocarbon, dodecyl sulfate or dodecyl sodium sulfonate; The content that contains the promotor aqueous solution changes between 0.1%-50%, all can obtain good CO
2Separating effect.
Adopt above-mentioned same technical process, carry out IGCC synthetic gas (CO
2/ H
2), biomass synthesis gas (CO
2/ H
2), Sweet natural gas (CO
2/ CH
4) and coal-seam gas in CO
2Separate, all can obtain good separating effect.
Above-listed detailed description is at the specifying of possible embodiments of the present invention, and this embodiment is not in order to limiting claim of the present invention, and the equivalence that all the present invention of disengaging do is implemented or change, all should be contained in the claim of this case.
Claims (10)
1, CO2 industrial separation purification system in a kind of hydrate mixed gas includes and is used for compressing unstripped gas to predetermined pressure and being cooled to the feed gas preprocessing system of preset temperature, is used to reclaim CO
2Separate the tail gas energy recovery system of back residual exhaust, it is characterized in that, also include:
Hydrate knockout tower (5), microbubble jet circulating reaction system, tower still decomposition of hydrate system, CO
2The product acquisition system, hydrate generates and decomposition heat utilization system;
Hydrate knockout tower (5), it is divided into CO from tower still to cat head
2Displacement fractionation zone (501), blistering reaction district (502), spray reaction zone (503) are used to receive the unstripped gas that the feed gas preprocessing system carries, and make unstripped gas fully separate in the hydrate knockout tower;
Microbubble jet circulating reaction system is used to aspirate the mixed gas that hydrate reaction does not take place in the described hydrate knockout tower (5), promotes the quick generation of the hydrate in the spray reaction zone (503);
Tower still decomposition of hydrate system is used for the hydrate slurry of thermal degradation at the bottom of from described hydrate knockout tower (5) tower, water and portion C O
2Be back at the bottom of hydrate knockout tower (5) tower another part CO
2Output to described CO
2The product acquisition system;
CO
2The product acquisition system, it is connected with described tower still decomposition of hydrate system, is used for the isolated CO of acquisition system
2
Hydrate generates and decomposition heat utilization system, by by the refrigeration cycle of liquefied ammonia as medium, forms heat for decomposition of hydrate provides decomposition heat and removes hydrate.
2, CO in the hydrate mixed gas as claimed in claim 1
2The industrial separation purification system, it is characterized in that: described microbubble jet circulating reaction system comprises the microbubble jet reactor (9) that is communicated with the top of described spray reaction zone (503), also is connected with external primary cooler (16) and recycle pump (15) in turn with this microbubble jet reactor (9).
3, as CO in claim 1, the 2 described hydrate mixed gass
2The industrial separation purification system is characterized in that: also be connected with auxiliary cooler (13) between described microbubble jet reactor (9) and external primary cooler (16).
4, CO in the hydrate mixed gas as claimed in claim 1
2The industrial separation purification system is characterized in that: described hydrate generates and decomposition heat utilization system include by with described CO
2The decomposition of hydrate device (21) that displacement fractionation zone (501) bottom connects, auxiliary condenser (20), ammonia compressor (19), external primary cooler (16), auxiliary evaporator (17), throttle expansion valve (18) constitute refrigeration cycle, provide required heat of decomposition of hydrate and hydrate to form required cold by the liquefied ammonia refrigeration cycle.
5, CO in the hydrate mixed gas as claimed in claim 1
2The industrial separation purification system is characterized in that: the inner column plate (5031) of installing of described spray reaction zone (503); Raw material gas inlet (504) and tower still CO at described hydrate knockout tower (5)
2Porous feed sparger (6) and porous distribution of reflux device (23) are all installed by gas or liquid return mouth place.
6, CO in the hydrate mixed gas as claimed in claim 1
2The industrial separation purification system is characterized in that: described CO
2The product acquisition system includes product collection tube (14), gas accumulation jar (11), gas collecting variable valve (10), these product collection tube (14) one ends are communicated with described decomposition of hydrate device (21) respectively, also output to described CO by porous distribution of reflux device (23)
2In the displacement fractionation zone (501), its other end is by gas accumulation jar (11) and gas collecting variable valve (10) output gaseous state CO
2
7, CO in a kind of hydrate mixed gas
2The industrial separation method of purification is characterized in that, comprises the steps:
(1) injection contains the promotor aqueous solution in the hydrate separation system, reduces aqueous temperature to hydrate by the microbubble jet reaction recycle system and generates temperature;
(2) unstripped gas to be separated separates pre-treatment through stage compression, multistage cooling, multi-stage gas-liquid, makes its pressure be elevated to the working pressure of hydrate knockout tower, and temperature is reduced to hydrate and generates temperature;
(3) the pretreated unstripped gas of process enters the blistering reaction district of hydrate knockout tower, rises in the form of blistering reaction district unstripped gas with bubbling, contacts with the low temperature hydrate slurry and forms CO
2The mixed gas hydrate that content is high, hydrate crystal grain enters CO to deposit
2The displacement fractionation zone, the gas that hydration reaction does not take place rises to the spray reaction zone; Gas rises in the process of cat head and sprays the reverse formation hydrate that contacts of the supercooled water compound slurries that get off from cat head microbubble jet reactor along the spray reaction zone, and hydrate solids is with flowing to the blistering reaction district under the aqueous solution;
(4) be settled down to CO
2The hydrate solids of displacement fractionation zone enters tower still decomposition of hydrate system further to the enrichment of tower bottom sediments, is warming up to the decomposition of hydrate temperature, is decomposed into water and liquid state or gaseous state CO
2, water and portion C O
2At the bottom of porous distribution of reflux device is back to tower, the CO of backflow
2With bubble or drop form along CO
2The displacement fractionation zone rises; Because CO
2Displacement fractionation zone temperature constantly raises from top to bottom, hydrate solids temperature in tower bottom sediments process raises, simultaneously with the CO of the high density that at the bottom of tower, refluxes
2Counter current contact, partially mixed gas hydrate decomposes, and forms CO simultaneously
2Hydrate, the CO in the gas phase
2Displace the N of hydrate in mutually
2Deng the difficult gas that forms hydrate; Hydrate solids is to the tower bottom sediments, and replacement(metathesis)reaction is carried out continuously, the middle mutually CO of hydrate
2Concentration constantly raise and CO in backflow gas phase or the liquid phase
2Concentration constantly reduces;
(5) in the sepn process, extract the part hydrate slurry out from the circulation of hydrate knockout tower middle part, supercooled water compound slurries are laggard goes into the microbubble jet reactor through being cooled to, suction function by the microbubble jet reactor sucks the microbubble jet reactor with the mixed gas circulation that hydration reaction does not take place cat head simultaneously, gas-liquid two-phase returns hydrate and separates cat head behind microbubble jet reactor thorough mixing, the effect of generation spray, the CO in the cat head mixed gas
2Concentration further reduces, tower top temperature reduces, and reaches separation requirement and removes the purpose that hydrate generates heat;
(6) the poor CO of cat head
2Gas stablize extraction as tail gas by the tail gas variable valve, compression work and cold energy by in tail gas energy recovery system recovery low temperature, the highly compressed tail gas are used for the compression and the cooling of feed gas preprocessing system;
(7) another part CO of going out of tower still decomposition of hydrate system decomposition
2Rise to CO along product collection tube bubbling
2The product acquisition system is collected, by control CO
2The collecting amount of product is controlled CO
2Quantity of reflux.
8, CO in the hydrate mixed gas as claimed in claim 7
2The industrial separation method of purification, it is characterized in that: the described promotor aqueous solution that contains, the content of its hydrate formation promoter is 0.1%～50%, described hydrate formation promoter is selected from one of following or its mixture: tetrahydrofuran (THF), 1,4-dioxane, acetone, quaternary ammonium salt, sulfonium salt, phosphonium salt, fluorochlorohydrocarbon, high-carbon hydrocarbon, dodecyl sulfate or dodecane sulfonate.
9, CO in the hydrate mixed gas as claimed in claim 7
2The industrial separation method of purification is characterized in that: when the working pressure of described hydrate knockout tower (5) less than decomposition of hydrate device (21) in temperature and CO
2During liquefaction pressure under forming, the decomposition of hydrate product is gaseous state CO
2, CO
2Gas rises along product collection tube (14) bubbling, is focused to gas accumulation jar (11), gathers gaseous state CO by gas collecting variable valve (10)
2Product; When the working pressure of hydrate knockout tower (5) greater than the decomposition of hydrate device in temperature and CO
2During liquefaction pressure under forming, the decomposition of hydrate product is liquid CO
2, liquid CO
2Because of density rises along product collection tube (14) less than water, and in product collection tube (14), carry out fractionation with the aqueous solution, accumulate in the top of product collection tube (14), liquid level is higher than the interior hydrate slurry liquid level of hydrate knockout tower (5), can directly gather liquid CO by liquid acquisition variable valve (10)
2Product.
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