CN103911196A - Method and apparatus for utilizing plant waste gas to prepare natural gas - Google Patents
Method and apparatus for utilizing plant waste gas to prepare natural gas Download PDFInfo
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- CN103911196A CN103911196A CN201310015903.2A CN201310015903A CN103911196A CN 103911196 A CN103911196 A CN 103911196A CN 201310015903 A CN201310015903 A CN 201310015903A CN 103911196 A CN103911196 A CN 103911196A
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- gas
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- natural gas
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Abstract
The invention discloses a method for utilizing plant waste gas to prepare natural gas, and one or more plant waste gases are purified for removing substances harmful to catalysts and a reaction is performed for generating methane and further for preparing an artificial natural gas product. The invention also discloses an apparatus applied to the method. According to the technical scheme, coal gas is not needed for synthesizing methane, but industrial waste gas is utilized, so that national resource is saved, CO2 discharge is reduced and environment is protected; by utilizing the technology of water-cooling heat-exchanging low-temperature methanation, the methanation reaction conditions are optimized, the methane synthetic rate is improved, the flow is simplified, equipment is reduced, a circulator is cancelled, and power consumption is reduced; and a by-product high-pressure steam of the methane synthetic reaction is utilized as the drive power of a steam turbine and a water pump needed by compressing natural gas, and therefore energy is saved and consumption is reduced.
Description
Technical field
The present invention relates to technical field of chemical engineering, relate in particular to a kind of method and device that utilizes plant gas synthetic natural gas processed.
Background technology
Sweet natural gas is a kind of clean energy, China's natural gas at domestic energy proportion far below international average level, National Development and Reform Committee " 12 " natural gas development planning clearly takes year increasing amount of natural gas 50,000,000,000 sides, coal preparing natural gas can gasify or the methanation of steam catalyzed conversion single stage method with coal direct hydrogenation, but the gasification extensively adopting at present makes synthetic gas again by H wherein
2, CO, CO
2carry out methanation reaction, produce synthetic natural gas, no matter above be single stage method methanation or gasification again methanation all to consume a large amount of coal resources, and the H that China has multiple plant gas or industrial tail gas to contain above-mentioned synthesizing methane
2, CO, CO
2, for example ammonia factory off-gas has H Shang Xia 70%
2with about 10%CH
4decarburization stripping gas has CO more than 90%
2, Methanol Plant off-gas has the H of high-content
2, CO, CO
2, coke-oven plant's coke(oven)gas has CH4 and H Shang Xia 20%
2, CO, CO
2, steel mill's blast furnace gas and converter gas have 10% above CO
2and 20-55%CO, furnace of calcium carbide and Yellow phosphorus furnace have 75-90%CO, and above-mentioned industrial gaseous waste all can utilize the raw material as synthetic Artificial Natural Gas.
The feature of the methane of at present domestic and international synthetic gas Artificial Natural Gas processed, the one, synthetic technology substantially all adopts many adiabatic methanation reactors, for example use the high-temperature methanation (seeing Fig. 1) of rope company of Top of Denmark, take three methanator series connection, before and after two intersegmentally have a heat exchange cooler, reduce temperature and enter again hypomere methanation, the First methanator part gas of giving vent to anger in addition loops back import and reacts, this class methanation exists easy the mistake in heat inactivation and methanation of methanation catalyst to occur that knot carbon affects normal production, and heat recovery efficiency is low, energy consumption is large.The 2nd, synthesizing methane synthetic gas used is mainly CO hydrogenation reaction, and for example Top's rope company is H
2/ CO=3 (SNG), presses CO+3H
2=CH
4+ H
2o reaction, Dai Wei company is with containing CO=19.2% and H
2reaction, CO in synthetic gas
2=0.8%.
CO
2add H
2methanation reaction is a strong exothermal reaction:
CO
2+4H
2=CH
4+2H
2O
In above-mentioned adiabatic reactor, along with reaction heat discharges, reaction gas temperature raises, and the equilibrium constant that generates methane declines to a great extent, and affects CO
2synthesizing methane transformation efficiency.CO
2add H
2synthetic CH
4the equilibrium constant
during by 280 DEG C 1.486 × 10
6drop to 600 DEG C 0.76,0.51 × 10 while only having 280 DEG C
-6doubly.
Summary of the invention
For the problems referred to above, the object of this invention is to provide a kind of method of utilizing plant gas Artificial Natural Gas processed and device of energy-conserving and environment-protective.
For achieving the above object, the present invention takes following technical scheme:
Utilize a method for plant gas Artificial Natural Gas processed, contain CO by one
2and/or CO and H
2plant gas, or the multiple CO that contains separately
2and/or CO and/or H
2plant gas, remove objectionable impurities to catalyzer through purifying, pass through CO
2add H
2generate methane and/or CO and add H
2artificial Natural Gas product is produced in the reaction that generates methane, and when described plant gas is multiple, wherein at least one contains H
2.
Preferred as one, pressure-variable adsorption or membrane separation process or Deep Cooling Method concentrate from gas product for the methane of generation.
Preferred as one, when described plant gas is a kind of, adopt the coke(oven)gas of synthesizing methanol factory off-gas or coking plant.
Preferred as one, when described plant gas is multiple, adopt synthesis ammonia plant containing H
2off-gas, synthesis ammonia plant decarburization containing CO
2stripping gas, synthesizing methanol factory off-gas, coking plant coke(oven)gas, blast furnace gas, converter gas, calcium carbide stove exhaust, yellow phosphoric tail gas or silicon carbide gas in several.
Described ammonia factory off-gas also can purify removes after ammonia separation of nitrogen again, uses H
2with CO
2hydrogenation reaction CH processed
4.
The reaction of described generation methane is carried out in the water-cooled heat exchange type fixed-bed reactor of in-built Ni-based methanation catalyst.
The reaction of described generation methane is carried out in tubular reactor in water-cooled.
A kind of device for the above-mentioned method of utilizing plant gas Artificial Natural Gas processed, comprise drum, boiler water pump, interchanger, the well heater that goes into operation, water cooler, water separator, methane concentration unit, compressor and steam turbines before methanation synthesis reactor, tower, the described front interchanger of methanation synthesis reactor, tower, the well heater that goes into operation, water cooler, water separator, methane concentration unit, compressor are connected successively with steam turbines, described methanator is also circumscribed with drum and water pump, and described drum is connected with steam turbines.
The described well heater that goes into operation is steam injector or electric heater (being arranged on while selecting electric heater between the front interchanger of tower and methanation synthesis reactor).
Described methanation synthesis reactor is that water-cooled heat exchange type fixed-bed reactor or water-cooled are around tubular reactor.
Interchanger and the synthetic gas heat exchange that goes out methanation synthesis reactor before the advanced tower of industrial gaseous waste after purification, enter again methanation synthesis reactor and carry out methanation reaction, the synthetic gas that goes out methanation synthesis reactor is through isolating water of condensation through water cooler, water separator successively again after interchanger cooling before tower, sends to methane concentration unit and compressor concentrate, compression obtains Artificial Natural Gas.The drum being connected with methanation synthesis reactor produces high pressure steam, sends to steam turbines with being used as power or going generator generating.
This technology with existing be that raw material Lurgi furnace gas or coal water slurry gasification make synthetic gas H with coal
2, CO, CO
2, adopt Lurgi or DAVY or
relatively there is significant advantage etc. external adiabatic high-temperature methanation Artificial Natural Gas processed:
1. this technology is without gas maked coal synthesizing methane, and utilizes industrial gaseous waste, saved national resources;
2. utilize industrial gaseous waste, particularly utilize CO
2synthetic natural gas, reduces CO
2discharge, protection of the environment;
3. with the methanation of water-cooled heat exchange low temperature, optimize methanation reaction condition, improved methane synthetic ratio, available separate unit methanator replaces high-temperature heat insulation methanation needs 3-4 platform methanator and intermediate heat, simple flow, minimizing equipment, cancel circulator, reduce power consumption;
4. utilize methane synthesising reacting heat by-product high-pressure steam, the steam turbines that need use for drive compression Sweet natural gas and water pump power, energy-saving and cost-reducing.
Brief description of the drawings
The high-temperature methanation process flow sheet of rope company of Top of Tu1Shi Denmark.
Fig. 2 is a kind of implementing process FB(flow block) of the inventive method, wherein adopts a kind of containing CO
2and H
2industrial gaseous waste, for example Methanol Plant off-gas.
Fig. 3 is the another kind of implementing process FB(flow block) of the inventive method, wherein adopts multiple containing CO
2and/or H
2industrial gaseous waste, for example ammonia factory decarburization stripping gas CO
2contain H with ammonia synthesis
2off-gas.
Fig. 4 is the schematic diagram of apparatus of the present invention.
Fig. 5 is that the water-cooled of the methanator employing in apparatus of the present invention is around the schematic diagram of tubular reactor.
Embodiment
Be described in detail of the present invention below in conjunction with drawings and Examples.
Embodiment 1
Adopt technical process as shown in Figure 3, by plant gas 1, (synthesis ammonia plant is containing H
2, N
2off-gas) purify except ammonia, be equipped with plant gas 2 after purification (containing CO
2decarburization stripping gas), total tolerance 1000Kmol/h, under pressure 2MPa the vertical around pipe water-cooled reactor of the Ni-based TiO of having carrier methanation catalyst is housed, at air speed 3000h
-1under carry out CO
2hydrogenation methanation reaction must contain CH after cooling de-watering
4approximately 50%, N
240% gas product 4959Kmol/h, separates to obtain CH through pressure-variable adsorption
488% gas product, recompression, to 25MPa, obtains 2580Kmol/h compressed natural gas used as vehicle fuel.
Embodiment 2
Apparatus of the present invention as shown in Figure 4, comprise drum 101, water pump 102, methanation synthesis reactor 103, interchanger 104 before tower, well heater 105 goes into operation, water cooler 106, water separator 107, methane concentration unit 108, compressor 1010 and steam turbines 109, described methanation synthesis reactor 103, interchanger 104 before tower, water cooler 106, water separator 107, methane concentration unit 108, compressor 1010 is connected successively with steam turbines 109, described methanator 103 is also circumscribed with drum 101, water pump 102 and the well heater 105 that goes into operation, described drum 101 is also connected with steam turbines 109.
The described well heater 105 that goes into operation can be selected steam injector, or selects the electric heater in the inlet line being arranged between the front interchanger 104 of tower and methanation synthesis reactor 103.
Interchanger 104 and the synthetic gas heat exchange that goes out methanation synthesis reactor 103 before the advanced tower of industrial gaseous waste after purification, enter again methanation synthesis reactor 103 and carry out methanation reaction, the synthetic gas that goes out methanation synthesis reactor 103 is isolated water of condensation through water cooler 106, water separator 107 successively again after 104 coolings of interchanger before tower, sends to methane concentration unit 108 and compressor 1010 concentrates, compression obtains Artificial Natural Gas.The drum 101 being connected with methanation synthesis reactor 103 produces high pressure steam, sends to steam turbines 109 use and is used as power or goes generator generating, also can be for process steam.
Embodiment 3
Fig. 5 adopts water-cooled (Fig. 5 is other equipment in display unit not as methanation synthesis reactor around tubular reactor, all the other equipment composition and connect with embodiment 2) schematic diagram, this water-cooled is the patent of invention (application number 201210033806.1 that the applicant has applied for around tubular reactor, February 14 2012 applying date) in a kind of reactor, comprise housing 1 and heat exchanging piece, described housing 1 top is provided with inlet mouth 3 and manhole 4, inlet mouth 3 is furnished with gas distribution grid 81, lower housing portion is provided with a pair of header with tube sheet: inlet header 9a and outlet header 9b.Internal and external cycle or connected by inverted U-shaped elbow with the top of circle footpath adjacent two heat transfer tubes 2, in forming, the up heat transfer tube of logical heat transferring medium and descending heat transfer tube are arranged, up heat transfer tube is connected with inlet header 9a, descending heat transfer tube is connected with outlet header 9b.
Each layer of heat transfer tube located by longitudinal register plate 19.Housing 1 inside center is also provided with around tubular axis core 7, the up heat transfer tube that same return bend connects and descending heat transfer tube are along arranging by counter clockwise direction or clockwise direction helically separately respectively around tubular axis core 7, at the bottom of being bearing in by supporting member 23 around tubular axis core 7 bottoms tin, around the top of tubular axis core 7 retractable.The up heat transfer tube that same return bend connects is contrary with the winding direction of descending heat transfer tube.Housing bottom is provided with air outlet 5 and catalyzer unloads outlet 6, and air outlet 5 is furnished with porous gas collection plate 82.Heat transferring medium adopts water.
When above-mentioned heat transfer reactor uses, catalyst loading is between pipe, and outlet header 9b connects drum by steam outlet pipe, and drum connects recycle pump by rising pipe, and recycle pump also connects supplementary water pipe, and inlet header 9a connects recycle pump by heat transferring medium circulation tube.Reaction gas enters from inlet mouth 3, heat transferring medium enters into each heat transfer tube 2 from inlet header 9a, up with volution along up heat transfer tube, proceed to descending heat transfer tube through return bend again, descending with the volution direction contrary with up direction, with the axially reaction gas heat exchange through catalyst layer, in pipe, part water vapor is steam, removes the drum with variable valve through outlet header 9b during this time.
Above-mentioned water-cooled is walked coolant water in tubular type methanation reaction organ pipe, can adopt the pipe with small pipe diameter pipe of for example 12mm diameter, significantly improves heat interchanging area, up to every 1M
3catalyzer 200M
2up and down, around pipe synthetic tower gas with around pipe cross-flow heat exchange, than inside and outside straight tube pipe and to flow heat exchange heat transfer coefficient much higher, significantly improve heat exchange efficiency, effectively realize low temperature and samming methanation.
Embodiment 4
Produce 1000000 tons of Methanol Plant off-gas per year and reclaim and remove after methyl alcohol through washing, off-gas 2000Kmol, under pressure 3MPa, is equipped with the water-cooled of nickel type methanation catalyst around tubular type methanator, at air speed 5000h
-1under carry out methanation reaction, after refrigerated separation water 625.7Kmol containing CH
473.46% gas product, separates to obtain CH with pressure swing adsorption process
490% gas product recompresses 25MPa, obtains the compressed natural gas used as vehicle fuel CNG of 5200Kmol/h.
Claims (9)
1. a method of utilizing plant gas Artificial Natural Gas processed, is characterized in that: contain CO by one
2and/or CO and H
2plant gas, or the multiple CO that contains separately
2and/or CO and/or H
2plant gas, remove objectionable impurities to catalyzer through purifying, pass through CO
2add H
2generate methane and/or CO and add H
2artificial Natural Gas product is produced in the reaction that generates methane, and when described plant gas is multiple, wherein at least one contains H
2.
2. the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1, is characterized in that: when described plant gas is a kind of, adopt the coke(oven)gas of synthesizing methanol factory off-gas or coking plant.
3. the method for utilizing plant gas Artificial Natural Gas processed as claim 1, is characterized in that: when described plant gas is multiple, adopt synthesis ammonia plant containing H
2off-gas, synthesis ammonia plant decarburization containing CO
2stripping gas, synthesizing methanol factory off-gas, coking plant coke(oven)gas, blast furnace gas, converter gas, calcium carbide stove exhaust, yellow phosphoric tail gas or silicon carbide gas in several.
4. the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1, is characterized in that: the methane of described generation pressure-variable adsorption or membrane separation process or Deep Cooling Method concentrate from gas product.
5. the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1, is characterized in that: the reaction of described generation methane is carried out in the water-cooled heat exchange type fixed-bed reactor of in-built Ni-based methanation catalyst.
6. the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1, is characterized in that: the reaction of described generation methane is carried out in tubular reactor in water-cooled.
7. the device for the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1, comprise drum, boiler water pump, methanation synthesis reactor, interchanger before tower, well heater goes into operation, water cooler, water separator, methane concentration unit, compressor and steam turbines, it is characterized in that: described methanation synthesis reactor, interchanger before tower, well heater goes into operation, water cooler, water separator, methane concentration unit, compressor is connected successively with steam turbines, described methanator is also circumscribed with drum, water pump and the well heater that goes into operation, described drum is also connected with steam turbines.
8. the device for the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1 as claimed in claim 7, is characterized in that: described methanation synthesis reactor is that Horizontal water cooling heat exchange type fixed-bed reactor or water-cooled are around tubular reactor.
9. the device for the method for utilizing plant gas Artificial Natural Gas processed as claimed in claim 1 as claimed in claim 7, is characterized in that: the described well heater that goes into operation is steam injector or electric heater.
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CN105463048A (en) * | 2015-03-26 | 2016-04-06 | 高节义 | Method for preparing methane from coal combustion exhaust and device thereof |
CN105947981A (en) * | 2016-05-06 | 2016-09-21 | 南京昊安科技工程有限公司 | High pressure water-cooling phase change heat transfer methanolization and methanation refining technology |
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Application publication date: 20140709 |