CN204714766U - A kind of methanation fluidized bed plant and methanation system - Google Patents
A kind of methanation fluidized bed plant and methanation system Download PDFInfo
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- CN204714766U CN204714766U CN201520275518.6U CN201520275518U CN204714766U CN 204714766 U CN204714766 U CN 204714766U CN 201520275518 U CN201520275518 U CN 201520275518U CN 204714766 U CN204714766 U CN 204714766U
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Abstract
The utility model belongs to chemical field, relate to a kind of methanation fluidized bed plant and methanation system, superheated vapour can be produced in methanation simultaneously, and can after-treatment system be set, when operational load fluctuates between 30 ~ 120%, methanation fluidized-bed reactor is in normal fluidized state, and a methanation fluidized-bed reactor just can make reaction carry out completely; When operational load fluctuates between 0 ~ 30%, methanation fluidized-bed reactor is in improper fluidized state, and the method adding steam in unstripped gas must be adopted to maintain the normal fluidized state of beds.Owing to having added steam in the unstripped gas entering methanation fluidized-bed reactor, methanation reaction can be made like this to move to reverse direction, caused CO and CO
2transformation efficiency declines.From methanation fluidized-bed reactor gas out, after being separated water outlet, then enter isothermal low-temperature methanator, make reaction carry out completely, the Sweet natural gas that output is qualified.
Description
Technical field
The utility model belongs to chemical field, relates to a kind of methanation fluidized bed plant and methanation system.
Background technology
At present, industrial synthetic natural gas mainly contains coke-oven gas preparing natural gas and coal preparing natural gas two kinds.The committed step of synthetic natural gas is methanation reaction, and its reaction formula is:
CO+3H
2＝CH
4+H
2O △H
298＝－206KJ/mol
CO
2+4H
2＝CH
4+2H
2O △H
298＝－165KJ/mol
Methanation reaction is strong heat release reversible reaction, and under typical methanation reaction condition, the thermal insulation warming that in gas, every 1%CO transforms is about 72 DEG C, every 1%CO
2the thermal insulation warming transformed is about 60 DEG C.
In existing methanation process, methanator is adiabatic reaction form, and namely after beds adiabatic reaction, gas goes out reactor, then produces vapor recovery heat through high-duty boiler.
Due to CO and CO in the unstripped gas of synthetic natural gas
2content is very high, in order to control temperature, and the mode that methanator must adopt multiple stage to connect, and adopt the mode of a large amount of gas circulation to reduce CO and CO in Reactor inlet gas
2content (general control CO+CO
2: 3 ~ 5%).If the first methanator gas inlet temperature is 300 DEG C, then temperature out is 600 ~ 700 DEG C.
Existing synthetic natural gas methanation process is high-temperature methane metallization processes, must use the methanation catalyst of ability 700 DEG C of high temperature, to meet the requirement of this technique.
There is following shortcoming in high-temperature methane metallization processes:
1. temperature of reaction is high, and equipment material requires high, poor stability.
Because temperature of reaction is high, especially the first methanation reaction actuator temperature is 600 ~ 700 DEG C, and need to use resistant to elevated temperatures material to make, equipment manufacturing cost is high.If there is CO and CO in methanator inlet gas
2when content increases suddenly, reactor is easy to overtemperature accident occurs, and safe reliability is poor.
2. catalyzer cost is high.
Methanation catalyst main active ingredient is nickel, take aluminum oxide as carrier.In common methanation catalyst, nickel content is about 20 ~ 30%, and its use temperature scope is 200 ~ 400 DEG C.In high-temperature methanation catalyst, nickel content is about 40 ~ 50%, and its use temperature scope is 300 ~ 700 DEG C.High-temperature methanation catalyst manufacturing cost is high, expensive.
3. high temperature carbon deposit.
High-temperature methane metallization processes is adiabatic reaction, and catalyst in reactor bed temperature is 300 ~ 700 DEG C.Easily produce carbon deposit reaction when temperature is more than 400 DEG C, cause catalyst surface carbon deposit, make the activity decrease of catalyzer, affect the work-ing life of catalyzer.
4. power consumption is high.
Due to CO and CO in methanation reaction unstripped gas
2high (the CO+CO of content
2: 20 ~ 25%), in order to control temperature, the mode of a large amount of gas circulation must be adopted to reduce CO and CO in Reactor inlet gas
2content (general control CO+CO
2: 3 ~ 5%), its recycle gas flow is about 5 times of fresh gas flow, and power consumption is higher.
The Chinese patent of the patent No. 201320842753.8 provides the methanator of a kind of energy continuous and effective heat radiation to solve the problem, liberated heat continuous in methanation reaction can be removed with another kind of medium by time, maintains reaction and carries out under cryogenic thermostat.
Another kind of methanator is methanation fluidized-bed reactor, and this kind of catalyst reactor is in fluidized state, and its beds (emulsion zone) mass-and heat-transfer efficiency is high.As long as arrange enough heat transfer tubes in beds (emulsion zone), the phase transformation of heat exchange liquid in pipe just can be utilized to be removed in time by a large amount of reaction heat.The methanation fluidized-bed reactor that the Chinese patent application of application number 201410255842.1 provides, it is provided with the heat-exchanger rig of many groups of heat transfer tube compositions in catalytic bed, often organize heat transfer tube lower end to be communicated with water inlet house steward, water inlet house steward is communicated with drum water out, often organize heat transfer tube upper end to be communicated with vapour outlet house steward, vapour outlet house steward is communicated with the steam inlet of drum; Liberated heat continuous in methanation reaction can be removed with another kind of medium by time, maintains reaction and carries out under cryogenic thermostat.In a device, the steam produced is discharged outside reaction system by vapour outlet house steward.
Concerning existing methanation fluidized-bed reactor, there is the defect that turndown ratio is little, its normal running range of load fluctuation is between 30 ~ 120%.When device is in abnomal condition (such as system start-stop car or other malfunction), when its operational load is 0 ~ 30%, catalyst in reactor fluidisation is bad, and the method adding steam must be adopted to maintain the normal fluidized state of beds.
Utility model content
One of the utility model object is the methanation fluid bed reaction apparatus providing a kind of production performance and economic worth to promote further.
Two of the purpose of this utility model is to provide a kind of methanation reaction system with larger turndown ratio.
Three of the purpose of this utility model is to provide the methanation process based on aforesaid device and system.
Utility model is achieved through the following technical solutions above-mentioned purpose.
Utility model provides a kind of methanation fluidized bed plant, the gas distributor in the housing inner bottom part space that comprises housing, is positioned at the raw material gas inlet of housing bottom, is positioned at, is positioned at gear gas fly-ash separator above gas distributor, is positioned at the reaction gas outlet on housing; Enclosure interior forms the solid particulate freeboard of fluidized bed be in above gear gas fly-ash separator, and is positioned at the solid particulate emulsion zone below gear gas fly-ash separator; It is characterized in that, in described equipment, be also provided with heat-exchange system; Described heat-exchange system comprises at least one the emulsion zone heat-exchanger rig being located at solid particulate emulsion zone, be located at least one freeboard of fluidized bed heat-exchanger rig of solid particulate freeboard of fluidized bed, and be located at the drum that hull outside connects described emulsion zone heat-exchanger rig and freeboard of fluidized bed heat-exchanger rig.
Equipment as claimed in claim 1, is characterized in that described emulsion zone heat-exchanger rig has an emulsion zone entrance and an emulsion zone outlet; Described freeboard of fluidized bed heat-exchanger rig has a freeboard of fluidized bed entrance and a freeboard of fluidized bed outlet; Described emulsion zone entrance is communicated with the drum water outlet be located at bottom drum, and described emulsion zone outlet is communicated with the medial inlet being located at drum, and described freeboard of fluidized bed entrance is communicated with the drum air outlet being located at drum top.
Drum is used for moisturizing, water cycle and produces steam.When device start runs, water bottom drum flows into the emulsion zone heat-exchanger rig in solid particulate emulsion zone by emulsion zone entrance, now, owing to carrying out the reaction of very exothermic in this emulsion zone, water is heated rapidly vaporization becomes steam, and the medial inlet of drum is inputed to from emulsion zone outlet, in drum, steam rises further and inputs to the freeboard of fluidized bed entrance of freeboard of fluidized bed heat-exchanger rig from the drum air outlet at drum top through pipeline, through being further heated as superheated vapour, superheated vapour exports to outside reaction system from freeboard of fluidized bed outlet again.
Be cleverly, in this reaction system, by being arranged in freeboard of fluidized bed by heat-exchanger rig, utilize the temperature difference of reaction gas and saturation steam, the saturation steam that heat-exchanger rig in emulsion zone produces can be transformed into superheated vapour, now the utility value of steam will promote greatly.
In an embodiment of the present utility model, be the saturation steam of about 310 DEG C from the steam of drum air outlet input, after the freeboard of fluidized bed heat-exchanger rig heating of excess temperature at about 400 DEG C, the steam of output is the superheated vapour of 350 ~ 380 DEG C.In other words, in this reaction system, only need to arrange simple heat transfer tube in the solid particulate freeboard of fluidized bed of equipment, namely can become the vapor superheater that can produce superheated vapour.
Except this, by the setting of aforesaid device, the temperature that reaction gas can be made to export reduces, and transformation efficiency promotes.
In a preferred embodiment of the present utility model, from the gas that reaction gas outlet exports, H
2content is below 1.5%.
The described vapor superheater for generation of superheated vapour should not be arranged in solid particulate emulsion zone.
Preferably, be that described emulsion zone heat-exchanger rig and freeboard of fluidized bed heat-exchanger rig all have the heat transfer tube of a group or more; Preferably, described emulsion zone heat-exchanger rig and freeboard of fluidized bed heat-exchanger rig all have many groups heat transfer tube in parallel.
As the preferred embodiment of one, be provided with the emulsion zone heat-exchanger rig of the parallel connection of two groups or more at described solid particulate emulsion zone; Described many groups emulsion zone heat-exchanger rig all has the emulsion zone entrance that the water supply that is communicated to drum water outlet enters, water enters the heat transfer tube of emulsion zone heat-exchanger rig by emulsion zone entrance, is heated and becomes steam and export from the emulsion zone outlet of emulsion zone heat-exchanger rig.
In a preferred embodiment of the present utility model, heat-exchanger rig I and heat-exchanger rig II is arranged in the solid particulate emulsion zone of methanation fluidized-bed reactor bottom, within heat-exchanger rig I is positioned at catalyzer static bed height, heat-exchanger rig II is positioned at above catalyzer static bed height, all arrange heat transfer tube in the emulsion zone of whole beds, be conducive to a large amount of reaction heat to shift out in time.
Through methanation reaction, the gas exported from the reaction gas outlet of fluidized-bed reactor becomes reaction gas, is called first step reaction gas, the second stage reaction gas produced with the after-treatment system being different from latter alternative in the utility model.
As the preferred embodiment of one, gas-solid separation equipment can also be provided with in fluid bed reaction apparatus of the present utility model, for before being exported by reaction gas (first step reaction gas), the most solid catalyst of first Separation and Recovery, makes it fall after rise to reaction system.Optional gas-solid separation equipment can be described in the Chinese patent of such as application number 201410255842.1.
Preferably, the gas distributor in this fluid bed reaction apparatus comprises a gas distributor and secondary air sparger.Optional gas distributor can be described in the Chinese patent of such as application number 201410255842.1.
The utility model provides a kind of methanation system simultaneously, and containing, for example the arbitrary described methanation fluidized bed plant of claim 1-4, the reaction gas outlet of fluidized bed plant connects hot-air filter, the first water cooler, the first gas-liquid separator further successively.
Hot-air filter is for filtering the catalyst fines in reaction gas.Gas-liquid separator is for separating of water.
As the preferred scheme of one, in above-mentioned methanation system, the first preheater for heat exchange is also provided with between connection hot-air filter and the first water cooler, now unstripped gas first inputs in the first preheater, fluid bed reaction apparatus is entered by raw material gas inlet again after preheating, after methanation reaction, hot-air filter is entered again by reaction gas outlet, after the catalyzer of separating residual wherein, enter the first preheater again, after carrying out heat exchange with unstripped gas wherein, then enter further and be connected to the first water cooler with the first preheater.Like this, unstripped gas can utilize the heat of reaction gas, carries out preheating; And reaction gas also can tentatively cool simultaneously, thus make full use of the energy.
Now, the mode of connection of this methanation system is: methanation fluidized bed plant is connected with hot-air filter, the first preheater, the first water cooler and the first gas-liquid separator successively, first preheater has the pipeline being connected to methanation fluidized bed plant raw material gas inlet simultaneously, and for the preheater unstripped gas entrance that unstripped gas enters.
In the first gas-liquid separator, in the first step reaction gas of the first water cooler cooling, contained moisture stays the bottom of the first gas-liquid separator, becomes Separation of Water; The gas be separated after water then becomes gas product (first step gas product).This first step gas product can detect alternatively, if CO, CO in gas
2, H
2content lower than target value, then gaseous constituent reaches qualified gas product standard; If higher than target value, then process further by isothermal low-temperature methanator, now, the first gas-liquid separator will connect a treatment system further, and this treatment system comprises:
Isothermal low-temperature methanator, the second preheater for heat exchange be connected with isothermal low-temperature methanator, the second water cooler for cooling reaction gas be connected with the second preheater, the second gas-liquid separator for separating of water be connected with the second water cooler.
As the preferred scheme of one, first gas-liquid separator can first connect the second preheater, now first step gas product in the second preheater after preheating, input to isothermal low-temperature methanator again, second stage reaction gas is become after reacting in isothermal low-temperature methanator, and re-enter in the second preheater alternatively, heat exchange is carried out with first step gas product in the second preheater, after preliminary reduction temperature, be delivered to the second water cooler, the second gas-liquid separator further successively again, become second stage gas product.Now, the mode of connection of this treatment system is: the first described gas-liquid separator is connected with second preheater with heat exchange function, second preheater is connected with isothermal low-temperature methanator in system one end, is connected successively with the second water cooler, the second gas-liquid separator at the other end.First gas-liquid separator by after being connected with the second preheater, then is connected with isothermal low-temperature methanator inlet mouth by the second preheater; And the second preheater also has the pipeline being communicated with isothermal low-temperature methanator air outlet simultaneously.
Above-mentioned isothermal low-temperature methanator can be existing isothermal low-temperature reactor, such as but not limited to, the isothermal low-temperature reactor disclosed in the Chinese patent of the patent No. 201320842753.8, comprising:
Be located at the opening for feed bottom isothermal low-temperature methanator, for passing into first step gas product, discharge port is positioned at reactor bottom center, for the second stage reaction gas produced in output-response device;
Being positioned at the heat-exchanger rig of isothermal low-temperature methanator basket inside, for removing reaction heat, and producing steam;
Second drum is connected with isothermal low-temperature methanator main body, for moisturizing, water cycle and generation steam.
Now, this system adopts methanation fluidized-bed reactor and isothermal low-temperature methanator tandem process, has both overcome methanation fluidized-bed reactor and there is the little defect of turndown ratio, and overcome again the deficiency that isothermal low-temperature methanator heat transfer coefficient is low.
In existing methanation fluidized-bed reaction system, usually load lower than 50% time, namely fluidized reaction is affected, and is in particular in that fluidisation is uneven, the temperature difference expands, degradation under heat transfer coefficient; Load lower than 30% time, the Biased flow phenomenon of generation aggravates further, and heat transfer coefficient reduces further.In order to tackle this situation, existing technology normally adopts the mode of logical steam, but this can make reaction carry out to reverse direction, affects transformation efficiency.
And adopt tandem process of the present utility model, can guarantee that device all can normal running in the scope of producing load 0 ~ 120%.
In a preferred embodiment of the present utility model, H in the gas product that tandem process produces
2content is below 1%.
Equipment provided by the utility model and system, can adapt to CO+CO in unstripped gas
2high-content (CO+CO
2≤ 25%) synthetic natural gas methanation process.
Alternatively, utilize the utility model for the synthesis of natural gas methane metallization processes, comprise the steps:
1., when operational load fluctuates between 30 ~ 120%, normal operating state is belonged to
---in methanation fluidized-bed reactor, carry out CO and CO
2respectively with H
2the reaction of synthesizing methane, the temperature maintaining described reactor 300 ~ 450 DEG C, pressure is between 0.1 ~ 5.0MPa;
---reaction is generated conductance and enters hot-air filter, a small amount of catalyst fines carried secretly in gas is crossed through hot-air filter and is filtered;
---the air-flow from hot-air filter being imported the first preheater, is cooled to 100 ~ 200 DEG C, enter the first water cooler, through being cooled to about 30 ~ 40 DEG C, entering the first gas-liquid separator, be separated the later gas product of water outlet and go to workshop section of dewatering;
2., when operational load fluctuates between 0 ~ 30%, upset operation state is belonged to
---in methanation fluidized-bed reactor, carry out CO and CO
2respectively with H
2the reaction of synthesizing methane.When operational load lower than 30% time, methanation fluidized-bed reactor inner catalyst fluidisation is bad, the temperature difference increase, mass-and heat-transfer decrease in efficiency.In order to maintain the normal fluidized state of methanation fluidized-bed reactor, the method adding steam in unstripped gas must be adopted, the temperature maintaining described reactor 300 ~ 450 DEG C, pressure is between 0.1 ~ 5.0MPa;
---owing to having added steam in the unstripped gas entering methanation fluidized-bed reactor, methanation reaction can be made like this to move to reverse direction, caused CO and CO
2transformation efficiency declines, CO, CO in namely for methane fluidized-bed reactor exit gas
2and H
2content is higher, and this gaseous constituent can not reach the requirement of gas product;
---reaction is generated conductance and enters hot-air filter, a small amount of catalyst fines carried secretly in gas is crossed through hot-air filter and is filtered;
---the air-flow from hot-air filter is imported the first preheater, be cooled to 100 ~ 200 DEG C, enter the first water cooler, through being cooled to about 30 ~ 40 DEG C, enter the first gas-liquid separator, be separated the later gas of water outlet and enter isothermal low-temperature methanator behind the second preheater preheats to 200 ~ 300 DEG C;
---in isothermal low-temperature methanator, carry out CO and CO
2respectively with H
2the reaction of synthesizing methane, the temperature maintaining described reactor 250 ~ 350 DEG C, pressure is between 0.1 ~ 5.0MPa;
---reaction is generated conductance and enters the second preheater, being cooled to 100 ~ 150 DEG C, then entering the second water cooler, through being cooled to 30 ~ 40 DEG C, entering the second gas-liquid separator, be separated the later gas product of water outlet and go to workshop section of dewatering.
The utility model synthetic natural gas methanation process, carries out series combination by methanation fluidized-bed reactor and isothermal low-temperature methanator, has the following advantages:
1. system capacity is large.
Methanation fluidized-bed reactor has the advantage of larger-scale unit, the fluidized-bed reactor of a DN8000mm, just can process the material gas quantity of annual output 40 billion cubic meter Sweet natural gas.
2. CO+CO in unstripped gas is adapted to
2high-content.
Because methanation fluidized-bed reactor has the high advantage of mass-and heat-transfer efficiency, CO+CO in unstripped gas
2content up to 20 ~ 25% time, all can normal running, therefore, various coal gasifying process can be adapted to.
3. system operation elasticity is large.
Adopt methanation fluidized-bed reactor and isothermal low-temperature methanator to carry out the technique of series combination, its turndown ratio is large.Produce load to fluctuate in 0 ~ 120% scope, all can normal running.
4. gas product quality better.
Methanation fluidized-bed reactor and isothermal low-temperature methanator is adopted to carry out the technique of series combination, because the temperature of reaction of isothermal low-temperature methanator is low, CO and CO
2transformation efficiency is high, CH in gas product
4> 98%, CO
2< 0.5%, H
2< 1.5% (being butt gas composition above).
5. steam quality is good.
Owing to arranging vapor superheater in freeboard of fluidized bed in methanation fluidized-bed reactor, utilize the heat heating saturation steam of reaction gas, saturation steam is become superheated vapour, improves the quality of steam, namely improve purposes and the value of steam.
6. energy consumption is low.
Because methanation fluidized-bed reactor and isothermal low-temperature methanator all arrange heat transfer tube in beds, utilize liquid phase-change to be removed by a large amount of reaction heat, to keep reaction bed temperature invariable, gas does not need circulation, and power consumption is low.
Accompanying drawing illustrates:
Fig. 1 is the schematic diagram of the utility model methanation fluidized bed plant;
Fig. 2 is the connection diagram of each equipment in the preferred methanation system of the utility model.
1-housing; 11-raw material gas inlet; 12-reaction gas exports; 13-gas-solid separation equipment;
2-gas distributor;
3-keeps off gas fly-ash separator;
4-emulsion zone heat-exchanger rig; 41-emulsion zone entrance; 42-emulsion zone exports;
5-freeboard of fluidized bed heat-exchanger rig; 51-freeboard of fluidized bed entrance; 52-freeboard of fluidized bed exports;
6-drum; 61-drum water outlet; 62-medial inlet; 63-drum air outlet;
71-hot-air filter; 72-first preheater; 73-first water cooler; 74-first gas-liquid separator; 721-preheater unstripped gas entrance;
8-isothermal low-temperature methanator;
81-second preheater; 82-second water cooler; 83-second gas-liquid separator;
91-variable valve; 92-rotary back-blowing device; 93-back-flushing valve;
10-second drum; 101-second variable valve.
Embodiment:
Following specific embodiment is the further explaination to technical solutions of the utility model.Embodiment is only used for the example that technical scheme is described, but not the restriction to the utility model protection domain.
Embodiment 1
Methanation fluidized bed plant has a columniform housing 1, and housing bottom has a raw material gas inlet 11, and in order to unstripped gas to be inputted the reaction chamber of enclosure interior, top has a reaction gas outlet 12, in order to derive the rear gas produced of reaction.The place be positioned at above housing 1 inner bottom part space, raw material gas inlet 11 has a gas distributor 2, is provided with gear gas fly-ash separator 3 above gas distributor 2.Housing 1 inside forms the solid particulate freeboard of fluidized bed be in above gear gas fly-ash separator 3, and the solid particulate emulsion zone between gear gas fly-ash separator 3 and gas distributor 2, when device start runs, in solid particulate emulsion zone, have the catalyzer of higher concentration, gas carries out comparatively violent reaction in this region.Heat-exchange system is provided with in equipment, comprise two the emulsion zone heat-exchanger rigs 4 being located at solid particulate emulsion zone, two emulsion zone heat-exchanger rigs are connected in parallel to drum 6, be located at a freeboard of fluidized bed heat-exchanger rig 5 of solid particulate freeboard of fluidized bed, and be located at the drum 6 of the housing 1 outside described emulsion zone heat-exchanger rig 4 of connection and freeboard of fluidized bed heat-exchanger rig 5; Emulsion zone heat-exchanger rig 4 has emulsion zone entrance 41 and emulsion zone outlet 42; Described freeboard of fluidized bed heat-exchanger rig 5 has a freeboard of fluidized bed entrance 51 and a freeboard of fluidized bed outlet 52; Described emulsion zone entrance 41 is communicated with the drum water outlet 61 be located at bottom drum 6, and described emulsion zone outlet 42 is communicated with the medial inlet 62 being located at drum 6, and described freeboard of fluidized bed entrance 51 is communicated with the drum air outlet 63 being located at drum 6 top.Emulsion zone heat-exchanger rig 4 and freeboard of fluidized bed heat-exchanger rig 5 all have many groups heat transfer tube in parallel.
In an operation of equipment, unstripped gas is imported in housing by bottom, catalyzer is with air-flow fluidisation in housing, major part catalyst converter is blocked in the solid particulate emulsion zone below gear gas fly-ash separator, gas carries out violent reaction herein, makes the heat exchange that emulsion zone heat-exchanger rig carries out inside and outside heat transfer tube; Catalyzer has component permeate gear gas fly-ash separator 3 to enter solid particulate freeboard of fluidized bed, and in this region, gas still carries out the reaction comparatively relaxed, now the gas temperature in this region about 400 DEG C.In heat-exchange system, the emulsion zone entrance of emulsion zone heat-exchanger rig flows into the water exported from the water outlet 61 of drum 6, water enters heat transfer tube and carries out heat exchange, become water vapor from emulsion zone outlet 42 input, enter the medial inlet 62 of drum 6, in drum, fall under water, water vapor rises, and the water vapor of rising inputs through drum air outlet 63, enters the freeboard of fluidized bed entrance of freeboard of fluidized bed heat-exchanger rig 5, the steam now entered is the saturation steam of 310 DEG C, after heat exchange, the steam of deriving from freeboard of fluidized bed outlet 52 is superheated vapour, temperature about 370 DEG C.
Embodiment 2
Preferred methanation fluidized bed plant main body is as embodiment 1.Wherein also be provided with gas-solid separation equipment 13 gas distributor and comprise a gas distributor and secondary air sparger.
Embodiment 3
Methanation fluidised bed system, has the main equipment as embodiment 1, and the reaction gas outlet 12 of fluidized bed plant connects hot-air filter 71, first preheater 72, first water cooler 73, first gas-liquid separator 74 further successively; First preheater 72 also has the pipeline being connected to methanation fluidized bed plant raw material gas inlet 11 simultaneously, and preheater unstripped gas entrance 721.
In an operation of system, unstripped gas from purification section inputs in the first preheater 72 by preheater unstripped gas entrance 721, carry out preheating, be delivered to the raw material gas inlet 11 of equipment again, after reacting in a device, become reaction gas to export (in order to be different from the methanation system of follow-up further optimization from reaction gas outlet 12, reaction gas herein becomes first step reaction gas), be delivered to hot-air filter 71, in hot-air filter 71, catalyst fines remaining in reaction gas is separated further, the reaction gas being now separated remaining catalyst fines is delivered to the first preheater 72 by another entrance again, because reaction gas temperature is higher, therefore in this preheater, can by the setting of heat exchanging pipe, make the heat conduction of reaction gas to the same unstripped gas through this preheater 72, the temperature of simultaneous reactions gas tentatively reduces, after this, reaction gas is delivered to the first water cooler 73 again, be delivered to the first gas-liquid separator 74 again, remaining moisture is separated, final output be gas product (in order to be different from the methanation system of follow-up further optimization, gas product herein becomes first step gas product).
Embodiment 4
Preferred methanation system, comprises methanation fluidised bed system as claimed in claim 3, except this, also comprises treatment system.
Treatment system comprises:
Isothermal low-temperature methanator 8, the second preheater 81 for heat exchange be connected with isothermal low-temperature methanator 8, the second water cooler 82 for cooling reaction gas be connected with the second preheater 81, the second gas-liquid separator 83 for separating of water be connected with the second water cooler 82.The mode of connection of this treatment system is: the first described gas-liquid separator 74 is connected with second preheater 81 with heat exchange function, second preheater 81 is connected with isothermal low-temperature methanator 8 in system one end, is connected successively with the second water cooler 82, second gas-liquid separator 83 at the other end.First gas-liquid separator 74 by after being connected with the second preheater 81, then is connected with isothermal low-temperature methanator 8 inlet mouth by the second preheater 81; And the second preheater 81 also has the pipeline being communicated with isothermal low-temperature methanator 8 air outlet simultaneously.
The second preheater 81 is first connected by the first gas-liquid separator 74, now first step gas product in the second preheater 81 after preheating, input to isothermal low-temperature methanator 8 again, second stage reaction gas is become after reacting in isothermal low-temperature methanator 8, and re-enter in the second preheater 81 alternatively, heat exchange is carried out with first step gas product in the second preheater 81, after preliminary reduction temperature, be delivered to the second water cooler 82, second gas-liquid separator 83 more further successively, become second stage gas product.
Embodiment 5
Methanation process example.
As shown in Figure 2, a kind of synthetic natural gas methanation process comprises methanation fluidized bed plant, and methanation fluidized bed plant comprises the raw material gas inlet 11 being located at bottom, for passing into unstripped gas.Catalyzer in equipment, after the first preheater 72 is preheated to 200 ~ 300 DEG C, through raw material gas inlet 11 access arrangement of bottom, is carried out fluidisation, and carries out methanation reaction by unstripped gas.CO and CO is carried out in methanation fluidized bed plant
2respectively with H
2the reaction of synthesizing methane, the temperature maintaining described reactor 300 ~ 450 DEG C, pressure is between 0.1 ~ 5.0MPa.Reaction gas outlet 12 is positioned at equipment top, for the reaction gas produced in output equipment, heat-exchanger rig I 4 and the heat-exchanger rig II 4 of emulsion zone lay respectively at reactor lower part, for removing reaction heat, freeboard of fluidized bed heat-exchanger rig 5 is positioned at reactor top, for the saturation steam of generation is become superheated vapour.
As shown in Figure 2, drum 6, is connected with methanation fluidized bed plant, for moisturizing, water cycle and generation steam.The rising pipe of drum 6 is connected with the water inlet of heat-exchanger rig I 4 and heat-exchanger rig II 4 respectively, the vapour outlet of heat-exchanger rig I 4 and heat-exchanger rig II 4 is connected with the steam inlet pipe of drum 6 respectively, water in drum 6 forms natural circulation by potential difference, the saturation steam produced is 10.0MPa through pressure regulator valve 91 control pressure, the temperature of saturation of its correspondence is 310 DEG C, overheated through freeboard of fluidized bed heat-exchanger rig 5 again, become 350 ~ 400 DEG C of superheated vapour transmitting systems.
Enter hot-air filter 71 from methanation fluidized bed plant top reaction gas out, a small amount of catalyst fines carried secretly in gas is crossed through hot-air filter 71 and is filtered.Hot-air filter 71 top is provided with rotary back-blowing device 92, and rotary back-blowing device 92 is connected by nitrogen pipeline with back-flushing valve 93.When the pressure reduction of hot-air filter 71 increases, start blowback program nitrogen and online blowback is carried out, with the pressure reduction of maintenance heat air filter 71 between 0.01 ~ 0.1MPa to hot-air filter 71.
From hot-air filter 71 top gas out, enter the first preheater 72, after the first preheater 72 cools, temperature is 100 ~ 200 DEG C, enters the first water cooler 73, through being cooled to about 30 ~ 40 DEG C, enter the first gas-liquid separator 74, the gas being separated water outlet later divides two-way:
1. when operational load fluctuates between 30 ~ 120%, belong to normal operating state, this gas is qualified gas product (CH
498%, CO
20.5%, H
21.5%, be more than butt gas composition) go to workshop section of dewatering.
2., when operational load fluctuates between 0 ~ 30%, upset operation state is belonged to,
CO and CO is carried out in methanation fluidized bed plant
2respectively with H
2the reaction of synthesizing methane.When operational load lower than 30% time, methanation fluidized bed plant inner catalyst fluidisation is bad, the temperature difference increase, mass-and heat-transfer decrease in efficiency.In order to maintain the normal fluidized state of methanation fluidized bed plant, the method adding steam in unstripped gas must be adopted, the temperature maintaining described reactor 300 ~ 450 DEG C, pressure is between 0.1 ~ 5.0MPa.
Owing to having added steam in the unstripped gas entering methanation fluidized bed plant, methanation reaction can be made like this to move to reverse direction, caused CO and CO
2transformation efficiency declines, CO, CO in namely for methane fluidized bed plant exit gas
2and H
2content is higher, and this gaseous constituent can not reach the requirement of gas product.
Enter hot-air filter 71 from methanation fluidized bed plant top reaction gas out, a small amount of catalyst fines carried secretly in gas is crossed through hot-air filter 71 and is filtered.Hot-air filter 71 top is provided with rotary back-blowing device 92, and rotary back-blowing device 92 is connected by nitrogen pipeline with back-flushing valve 93.When the pressure reduction of hot-air filter 71 increases, start blowback program nitrogen and online blowback is carried out, with the pressure reduction of maintenance heat air filter 71 between 0.01 ~ 0.1MPa to hot-air filter 71.
From hot-air filter 71 top gas out, enter the first preheater 72, after the first preheater 72 cools, temperature is 100 ~ 200 DEG C, enters the first water cooler 73, through being cooled to about 30 ~ 40 DEG C, enter the first gas-liquid separator 74, be separated CO+CO in the later gas of water outlet
2content is 3 ~ 10%.
This gas enters isothermal low-temperature methanator 8 after the second preheater 81 is preheated to 200 ~ 300 DEG C, in isothermal low-temperature methanator 8, carry out CO and CO
2respectively with H
2the reaction of synthesizing methane, the temperature maintaining described reactor 250 ~ 350 DEG C, pressure is between 0.1 ~ 5.0MPa.
Due to the gas flow entering isothermal low-temperature methanator 8 little (being about 20% of normal discharge), CO+CO in gas
2low (the CO+CO of content
2content is 3 ~ 10%), the operational load of this isothermal low-temperature methanator 8 is low (being about 10 ~ 20% of normal load), and therefore, the facility investment of this isothermal low-temperature methanator 8 is little.
As shown in Figure 1, the second drum 10, is connected with isothermal low-temperature methanator 8, for moisturizing, water cycle and generation steam.The rising pipe of the second drum 10 is connected with the upper water import of isothermal low-temperature methanator 8, the top vapour outlet of isothermal low-temperature methanator 8 is connected with the steam inlet pipe of the second drum 10, water in second drum 10 forms natural circulation by potential difference, the saturation steam produced is 5.0MPa through the second variable valve 101 control pressure, the temperature of saturation of its correspondence is 260 DEG C, this saturation steam transmitting system.
Bottom isothermal low-temperature methanator 8, reaction gas is out after the second preheater 81 cools, temperature is 100 ~ 150 DEG C, enters the second water cooler 82, through being cooled to about 30 ~ 40 DEG C, enter the second gas-liquid separator 83, the gas being separated water outlet later is qualified gas product (CH
498%, CO
20.5%, H
21.5%, be more than butt gas composition) go to workshop section of dewatering.
Claims (9)
1. a methanation fluidized bed plant, the gear gas fly-ash separator (3) comprising housing (1), be positioned at the raw material gas inlet (11) of housing (1) bottom, be positioned at the gas distributor (2) in housing (1) inner bottom part space, be positioned at gas distributor (2) top, is positioned at reaction gas outlet (12) on housing (1); Housing (1) inside forms the solid particulate freeboard of fluidized bed being in gear gas fly-ash separator (3) top, and is positioned at the solid particulate emulsion zone between gear gas fly-ash separator (3) and gas distributor (2); It is characterized in that, in described equipment, be also provided with heat-exchange system; Described heat-exchange system comprises at least one the emulsion zone heat-exchanger rig (4) being located at solid particulate emulsion zone, be located at least one freeboard of fluidized bed heat-exchanger rig (5) of solid particulate freeboard of fluidized bed, and be located at the drum (6) of housing (1) the outside described emulsion zone heat-exchanger rig (4) of connection and freeboard of fluidized bed heat-exchanger rig (5).
2. equipment as claimed in claim 1, is characterized in that described emulsion zone heat-exchanger rig (4) has an emulsion zone entrance (41) and emulsion zone outlet (42); Described freeboard of fluidized bed heat-exchanger rig (5) has a freeboard of fluidized bed entrance (51) and freeboard of fluidized bed outlet (52); Described emulsion zone entrance (41) is communicated with the drum water outlet (61) being located at drum (6) bottom, described emulsion zone outlet (42) is communicated with the medial inlet (62) being located at drum (6), and described freeboard of fluidized bed entrance (51) is communicated with the drum air outlet (63) being located at drum (6) top.
3. equipment as claimed in claim 1, is characterized in that described emulsion zone heat-exchanger rig (4) and freeboard of fluidized bed heat-exchanger rig (5) all have the heat transfer tube of a group or more; Preferably, described emulsion zone heat-exchanger rig (4) and freeboard of fluidized bed heat-exchanger rig (5) all have many groups heat transfer tube in parallel.
4. equipment as claimed in claim 2, is characterized in that the emulsion zone heat-exchanger rig (4) being provided with the parallel connection of two groups or more at described solid particulate emulsion zone.
5. equipment as claimed in claim 2, is characterized in that also being provided with gas-solid separation equipment (13) in described equipment; Further preferably, described gas distributor (2) comprises a gas distributor and secondary air sparger.
6. a methanation system, it is characterized in that reaction gas outlet (12) of fluidized bed plant connects hot-air filter (71), the first water cooler (73), the first gas-liquid separator (74) further successively containing, for example claim 1-5 arbitrary described methanation fluidized bed plant.
7. system as claimed in claim 6, it is characterized in that in this system, the first preheater (72) is also provided with between hot-air filter (71) and the first water cooler (73), and, first preheater (72) has the pipeline being connected to methanation fluidized bed plant raw material gas inlet (11) simultaneously, and preheater unstripped gas entrance (721).
8. system as claimed in claims 6 or 7, it is characterized in that this system also further containing treatment system, described treatment system comprises: isothermal low-temperature methanator (8), the second water cooler (82) be connected successively with isothermal low-temperature methanator (8), the second gas-liquid separator (83) be connected with the second water cooler (82); First gas-liquid separator (74) is connected with isothermal low-temperature methanator (8).
9. system as claimed in claim 7, it is characterized in that between described isothermal low-temperature methanator (8) and the second water cooler (82), being also provided with second preheater (81) with heat exchange function, first gas-liquid separator (74) by after being connected with the second preheater (81), then is connected with isothermal low-temperature methanator (8) inlet mouth by the second preheater (81); And the second preheater (81) also has the pipeline being communicated with isothermal low-temperature methanator (8) air outlet simultaneously.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789288A (en) * | 2015-04-30 | 2015-07-22 | 尹明大 | Synthesized natural gas methanation equipment and process |
| CN109404873A (en) * | 2018-09-19 | 2019-03-01 | 上海兖矿能源科技研发有限公司 | A method of utilizing the hot by-product superheated steam of high-temperature Fischer-Tropsch synthesis reaction |
-
2015
- 2015-04-30 CN CN201520275518.6U patent/CN204714766U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789288A (en) * | 2015-04-30 | 2015-07-22 | 尹明大 | Synthesized natural gas methanation equipment and process |
| CN109404873A (en) * | 2018-09-19 | 2019-03-01 | 上海兖矿能源科技研发有限公司 | A method of utilizing the hot by-product superheated steam of high-temperature Fischer-Tropsch synthesis reaction |
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