CN101704715B - Method for preparing synthesis gas after pure oxygen non-catalytic partial oxidation of purge gas in methanol synthesis loop to increase yield of methanol, and device therefor - Google Patents
Method for preparing synthesis gas after pure oxygen non-catalytic partial oxidation of purge gas in methanol synthesis loop to increase yield of methanol, and device therefor Download PDFInfo
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- CN101704715B CN101704715B CN200910195147A CN200910195147A CN101704715B CN 101704715 B CN101704715 B CN 101704715B CN 200910195147 A CN200910195147 A CN 200910195147A CN 200910195147 A CN200910195147 A CN 200910195147A CN 101704715 B CN101704715 B CN 101704715B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for preparing synthesis gas after pure oxygen non-catalytic partial oxidation of purge gas in the methanol synthesis loop to increase yield of methanol, which is characterized in that methane-containing gas is compressed by a synthesis gas compressor, is mixed with recycle gas which exits the methanol synthesis loop and separates the methanol and is compressed and preheated by a recycle compressor, and then the mixed gas enters the methanol synthesis loop to synthesize methanol; the methane-containing gas which exits the methanol synthesis loop is condensed into crude methanol liquid, thus being separated; the purge gas separating the methanol enters a hydrogen recovery device after being washed; and hydrogen rich gas and tail gas are obtained after recovery of the hydrogen recovery device, wherein the hydrogen rich gas returns to be mixed with the methane-containing gas and then enters the synthesis gas compressor or is output as a hydrogen product, and the tail gas is sent to a pure oxygen non-catalytic partial oxidation device to undergo non-catalytic oxidation reaction, and the obtained converted gas returns to be mixed with the methane-containing gas and then enters the synthesis gas compressor or the recycle compressor, or is directly sent to the methanol synthesis loop. The invention also discloses a device used in the method.
Description
Technical field
The present invention relates to the comprehensive utilization technique field of gasification gas; Be particularly related to (waste gas) treatment process of tail gas in the methanol synthesis loop and device, relate in particular to the methanol synthesis loop off-gas behind pure oxygen non-catalytic partial oxidation (from thermal transition) preparing synthetic gas with the method and the device of increase yield of methanol.
Background technology
Get into the virgin gas (fresh synthesis gas) of methanol synthesis loop, because source difference or coal generating gas method are different, methane content wherein exists evident difference, sometimes maybe be very high.As reaching 3～4% (V) with methane content in the gas production acetylene tail gas; Be that methane can reach 17～20% (V) in the virgin gas after the gas purification of raw material, the production of lurgi gasifier coal generating gas with the broken coal.But CO in the above-mentioned raw materials gas
2Content is 2～4% (V) only.
The tail gas that with the Sweet natural gas is raw material production acetylene at present is following through pretreated typical component:
H
2 65.1％(V)
CO 26.6％(V)
CO
2 3.7％(V)
CH
4 3.1％(V)
N
2+Ar 0.6％(V)
C
2H
6 0.5％(V)
H
2O 0.4％(V)。
Virgin gas typical component after the gas purification that the lurgi gasifier coal generating gas is produced is following:
H
2 38.53％(V)
CO 17.13％(V)
CO
2 29.6％(V)
CH
4 13.18％(V)
N
2+Ar 0.2％(V)
C
nH
m 0.637％(V)
O
2 0.4％(V)
H
2S 0.323％(V)。
As everyone knows, exist the methane can be unfavorable in the virgin gas of synthesizing methanol, can reduce Synthesis conversion, increase the discharging of off-gas, reduce methanol output the methyl alcohol building-up reactions.The off-gas of methanol synthesis loop is after hydrogen reclaims in addition, and wherein methane, nitrogen and argon component are concentrated, and adopts the torch or act as a fuel of setting fire to burn then, and such treatment process will increase raw material, power consumption, and increases investment etc.For large-scale plant, adopt such treatment process will cause considerable methanol output loss, energy consumption increases, and raw material availability is low.
In order to overcome above problem, the someone proposes following scheme:
1, referring to Fig. 1, the unstripped gas that contains methane is at first passed through low-temperature rectisol, transforms through pure oxygen partially oxidation conversion system then, and sending into the methyl alcohol synthesizing section after the conversion, to carry out methyl alcohol synthetic, methyl alcohol synthesizing section discharging off-gas.This method need be brought up to very high temperature (about 1000 ℃) to whole H2, CO and a large amount of water vapors in order to transform a small amount of methane, therefore will consume a large amount of steam, oxygen, hydrogen and fuel, and can not regulate the H/C of synthesizing methanol virgin gas; Adopt full tolerance through the partially oxidation system, exist that the partially oxidation system loading is big, resistance is high, investment is big; Complex technical process, long flow path; Crude fuel, power consumption are big, problems such as product cost height; And pure oxygen partially oxidation conversion system is before methyl alcohol is synthetic, and safety reduces.
2, referring to Fig. 2; This method is that the unstripped gas that contains methane is at first passed through low-temperature rectisol; Subzero fractionation methane then; Send into pure oxygen partially oxidation conversion system after the compression of isolating methyl alcohol and transform, transform the back and send into the methyl alcohol synthesizing section with methyl methanol syngas to carry out methyl alcohol synthetic, methyl alcohol synthesizing section discharging off-gas.CO content is high in the methane fraction of such method condensation, needs quadratic transformation just can advance to transform, and forms quadratic transformation; Not separated in addition methane is brought in the methyl methanol syngas, and the rare gas element in the synthetic gas is increased, and reduces the CO transformation efficiency, increases to discharge tolerance; Also have such method can not regulate the H/C of synthesizing methanol virgin gas equally; Moreover the ice chest investment is big, and methane fraction needs recompression, and power consumption is big; Pure oxygen partially oxidation conversion system is before methyl alcohol is synthetic, and safety reduces.
3, referring to Fig. 3; This method is that the unstripped gas that contains methane is at first passed through low-temperature rectisol; Send into pure oxygen partially oxidation conversion system then and transform, after the conversion through low-temperature rectisol decarburization send into the methyl alcohol synthesizing section to carry out methyl alcohol synthetic, methyl alcohol synthesizing section discharging off-gas.Such method will be brought up to very high temperature (about 1000 ℃) to whole H2, CO, CO2 and a large amount of water vapors in order to transform a small amount of methane, therefore needs to consume a large amount of steam, oxygen, hydrogen and fuel; Equally also be that full tolerance is passed through pure oxygen partially oxidation system, cause the partially oxidation system loading big, resistance is big, and investment is high; Complex technical process, long flow path, crude fuel, power consumption are big, and product cost is high; This method technical process exists serious temperature " malaria " and pressure " height is sick ", causes energy consumption to increase, and working cost increases; Be exactly pure oxygen partially oxidation conversion system in addition before methyl alcohol is synthetic, safety reduces.
4, referring to Fig. 4, this method is that the unstripped gas that contains methane is at first passed through low-temperature rectisol, passes through transformation CO absorption and H again
2, CH
4Send into pure oxygen partially oxidation conversion system after the compression and transform, sending into the methyl alcohol synthesizing section after the conversion, to carry out methyl alcohol synthetic, methyl alcohol synthesizing section discharging off-gas.This method relates to the compression of multiply PSA stripping gas, and therefore the for example compression of CO component, methane component exists serious pressure " height is sick ", and power consumption is big; Be exactly the fluctuation of PSA transformation absorption tolerance in addition, unfavorable to centrifugal synthesic gas compressor stable operation; The PSA organic efficiency is low, and the component separation cuts is not obvious, still has methane to exist in the synthetic gas; Moreover pure oxygen partially oxidation conversion system is before methyl alcohol is synthetic, and safety reduces.This method CO component compressor and the operation of methane component compressor parallel are then with centrifugal synthesic gas compressor series operation, poor reliability; Two cover pressure-swing absorption apparatus series operations, front workshop section goes wrong and causes back workshop section can't move poor reliability; Extensive single stage method CO extracts PSA device (greater than 11000Nm3/h), does not also have achievement both at home and abroad.
Summary of the invention
The objective of the invention is that energy consumption is big, flow process is complicated, investment is high, the present situation of safe reliability difference to exist the methane recovery underutilization in the methane-containing gas or methane recovery are utilized of prior art; And the off-gas that proposes a kind of methanol synthesis loop preparing synthetic gas behind pure oxygen non-catalytic partial oxidation (from thermal transition) is pressed the purpose of superheated vapour with the method and the device of increase yield of methanol in simultaneously can by-product to reach increase yield of methanol; The present invention can accomplish steam, fuel balance.The present invention is also synthetic with methyl alcohol, hydrogen reclaims, pure oxygen non-catalytic partial oxidation transforms three kinds of devices, heat energy utilizations and organically combines, and accomplishes to make the best use of everything, and reaches that reduced investment, energy-conserving and environment-protective, consumption are low, output increase, profitable purpose.
Technical scheme to be solved by this invention can realize through following technical scheme:
The methanol synthesis loop off-gas behind pure oxygen non-catalytic partial oxidation preparing synthetic gas with the method for increase yield of methanol; It is characterized in that methane-containing gas is pressurized to 5.0～10.0MPa through the fresh synthesis gas that obtains after purifying through synthesic gas compressor; Then with go out the methanol synthesis loop separation of methanol after circulation gas mix; Through the recycle compressor compression, mixed gas gets into the methanol synthesis loop synthesizing methanol through after the preheating; The methyl alcohol air cooling that contains that goes out methanol synthesis loop is congealed into liquid crude methanol and is separated; The off-gas that goes out behind the separation of methanol of methanol synthesis loop gets into hydrogen recovery unit after washing; After off-gas reclaims through hydrogen recovery unit; Obtain hydrogen rich gas and tail gas; Wherein hydrogen rich gas returns and is mixed into synthesic gas compressor with methane-containing gas or exports as hydrogen product; Tail gas is sent into the pure oxygen non-catalytic partial oxidation device and is carried out the non-catalytic oxidation reaction, and the reforming gas that the non-catalytic oxidation reaction obtains returns with methane-containing gas and is mixed into synthesic gas compressor or recycle compressor or directly is admitted to methanol synthesis loop.
Press saturation steam in said methanol synthesis loop and the pure oxygen non-catalytic partial oxidation device by-product, both are seen off by overheated one-tenth superheated vapour in said pure oxygen non-catalytic partial oxidation device.
Described tail gas carries out the non-catalytic oxidation reaction or carries out the non-catalytic oxidation reaction through sending into the pure oxygen non-catalytic partial oxidation conversion system after the tail-gas compressor compression through sending into the pure oxygen non-catalytic partial oxidation conversion system after the preheating.
Obtain tail gas through hydrogen recovery unit, wherein inert fractions such as CH4, N2, Ar obtain further concentrating.In order to discharge inerts es such as wherein N2, Ar; Described tail gas has at least a part and described hydrogen rich gas to have at least some to mix the gas that acts as a fuel and be admitted to the pure oxygen non-catalytic partial oxidation conversion system, in order to press saturation steam in overheated described methanol synthesis loop and the pure oxygen non-catalytic partial oxidation conversion system by-product.
Press saturation steam to can also be used to tail gas and the BW that the pure oxygen non-catalytic partial oxidation device is sent in preheating in said.
Tail gas of the present invention reacts below in the pure oxygen non-catalytic partial oxidation device, taking place:
H
2+0.5O
2＝H
2O
CO+0.5O
2＝CO
2
CH
4+0.5O
2＝CO+2H
2
CH
4+2O
2＝CO
2+2H
2O
CO+H
2O＝CO
2+H
2。
The tolerance (or recycle ratio) that discharges of the present invention confirms that according to the total inert gas content in the methane-containing gas (for example CH4, N2, Ar etc.) wherein the volume ratio between circulation gas and the fresh synthesis gas is 0-10.
Hydrogen recovery unit of the present invention adopts film way of recycling or PSA transformation suction type to obtain hydrogen rich gas.
Going out in the reforming gas of pure oxygen non-catalytic partial oxidation conversion system POX mainly is H2, CO, and the reforming gas that the non-oxide reaction of catalysis of the present invention obtains returns after recovery of heat with methane-containing gas and is mixed into synthesic gas compressor or recycle compressor or directly is admitted to methanol synthesis loop.
Press saturation steam all to carry out in the process furnace in being arranged at the pure oxygen non-catalytic partial oxidation device in methanol synthesis loop of the present invention and the pure oxygen non-catalytic partial oxidation device by-product, the used fuel of described process furnace is described fuel gas.
Because the tail gas H/C of hydrogen recovery unit is less than 2; And hydrogen rich gas H/C is greater than 2; Tail gas and the ratio between the hydrogen rich gas of therefore regulating hydrogen recovery unit can be regulated H/C ratio in the synthetic gas of methanol synthesis loop into, H in the fresh synthesis gas that advances methanol synthesis loop of the present invention
2/ C ratio is 2.05～2.1.
Methane-containing gas of the present invention is the methane-containing gas that contains methane 3～50%.Described methane-containing gas (virgin gas) can be methane-containing gas such as natural gas act acetylene tail gas, moving-bed crushed coal pressure gasifying coal gas (lurgi gasifier or BGL stove), PC-FB pressure gasifying gas (HT-L stove), gasification synthetic oil tail gas, coke-oven gas.
Circulation gas of the present invention (recycle ratio) is regulated according to methane nitrogen argon gas equal size in the methane-containing gas, and wherein the volume ratio between circulation gas and the fresh synthesis gas is 0-10.
The tail gas of entering pure oxygen non-catalytic partial oxidation conversion system of the present invention and oxygen are through a POX pure oxygen burner combustion, and burning back gas does not have catalyzed conversion in the receiver of pure oxygen non-catalytic partial oxidation conversion system, to reduce methane content.
Methanol synthesis loop off-gas preparing synthetic gas behind pure oxygen non-catalytic partial oxidation comprises with the device of increase yield of methanol:
The synthesic gas compressor of series operation and recycle compressor; Said synthetic compressor is provided with the fresh synthesis gas inlet pipe in order to the input fresh synthesis gas, and said recycle compressor is provided with in order to the circulation gas import of input circulation gas, in order to the reforming gas import of input reforming gas and in order to export the syngas outlet of synthetic gas;
One carries the methane-containing gas inlet pipe of methane-containing gas, and described methane-containing gas inlet pipe is connected with described fresh synthesis gas inlet pipe;
Methanol synthesis loop; This methanol synthesis loop has in the thick methyl alcohol outlet pipe, an output of the thick methyl alcohol of an output presses the middle pressure saturation steam outlet of saturation steam, the gas output tube of the gas behind the output separation of methanol, synthetic gas input aperture, the reforming gas import of an input synthetic gas; Described synthetic gas input aperture is connected with syngas outlet on the described recycle compressor through synthetic gas line of pipes and preheater; Described gas output tube is told two-way; Leading up to circulation gas transfer lime and circulation gas valve connects the circulation gas import on the described recycle compressor, and another road connects off-gas transfer lime and off-gas valve;
Hydrogen recovery unit; Described hydrogen recovery unit has the off-gas import of an input off-gas, the tail gas outlet of output tail gas and the hydrogen rich gas outlet of output hydrogen rich gas; Described off-gas import is connected with described off-gas transfer lime; Two-way is told in described hydrogen rich gas outlet; One the tunnel connects hydrogen rich gas return tube and hydrogen rich gas return control valve or hydrogen rich gas delivery pipe and hydrogen rich gas exhaust-control valve, and another road connects through hydrogen rich gas distribution piping and hydrogen rich gas distribution valve and connects the fuel gas transfer lime, and described hydrogen rich gas return tube connects the fresh synthesis gas inlet pipe on the described synthetic compressor; Two-way is told in described tail gas outlet, and one the tunnel connects exhaust pipe and tail gas conveying valve, and another road connects the fuel gas transfer lime through tail gas distribution piping and tail gas distribution valve;
The pure oxygen non-catalytic partial oxidation conversion system; Described pure oxygen non-catalytic partial oxidation conversion system is made up of process furnace and receiver; Said process furnace has in the methanol synthesis loop to press presses saturation steam inlet, superheated vapour outlet and in order to the fuel gas inlet of input fuel gas in saturation steam inlet, the pure oxygen non-catalytic partial oxidation conversion system; Said receiver has presses the saturation steam outlet in the outlet of POX pure oxygen burner and reforming gas, the by-product; Press the saturation steam inlet to be connected with the middle pressure saturation steam outlet of described methanol synthesis loop in the methanol synthesis loop through pressing the saturation steam line of pipes in the methanol synthesis loop; Press in the described pure oxygen non-catalytic partial oxidation conversion system in the by-product of saturation steam inlet and described receiver and press the saturation steam outlet to be connected, described superheated vapour exports exports superheated vapour; Described POX pure oxygen burner connects the exhaust pipe of described hydrogen recovery unit, and the outlet of described reforming gas connects the circulation gas import on described fresh synthesis gas inlet pipe, the recycle compressor, the reforming gas import on the methanol synthesis loop respectively through reforming gas transfer lime and the first conversion gas control valve, the second conversion gas control valve, the 3rd conversion gas control valve.
The described exhaust pipe of the present invention is provided with preheater or tail-gas compressor.
Hydrogen recovery unit of the present invention is Membrane recovery unit MRU or pressure-swing absorption apparatus.
Compared with prior art, the pure oxygen non-catalytic partial oxidation before the present invention has avoided methyl alcohol synthetic has been avoided whole off-gas or hydrogen recovery unit tail gas to act as a fuel and has been burnt, and has increased methanol output.The methyl alcohol off-gas synthetic and methanol synthesis loop that the present invention has initiated the nitrogenous argon noble gas of high methane concentrates methane, nitrogen, argon etc.; Utilize hydrogen recovery unit that methane, nitrogen, argon etc. are carried out further concentrating; Small portion hydrogen reclaims the tail gas accumulation of gas with nitrogen, argon in the equilibrium system that act as a fuel; All the other hydrogen reclaim tail gas and transform the joint process technology that obtains synthetic gas through the pure oxygen non-catalytic partial oxidation conversion system; Methanol synthesis loop, hydrogen recovery unit and pure oxygen non-catalytic partial oxidation conversion system, heat energy utilization are organically combined; Accomplish to make the best use of everything, reached reduced investment, energy-conserving and environment-protective, consume low, output increases, profitable purpose.
The present invention also has following beneficial effect:
(1) methanol synthesizer in front, hydrogen recovery unit and pure oxygen non-catalytic partial oxidation conversion system can guarantee methyl alcohol synthetic stability and safety operation in the back to greatest extent.
(2) resistance drop is little before synthesic gas compressor and the recycle compressor;
(3) the present invention only adopts a synthesic gas compressor group that is made up of synthesic gas compressor and recycle compressor, and safe reliability improves greatly.And prior art has increased CO component compressor and methane component compressor, has increased moving equipment, has increased the complexity of system, has reduced safety.
(4) adopt the pure oxygen non-catalytic partial oxidation conversion system, make full use of tail gas and act as a fuel, simplify flow process, safe and reliable, reduce investment.
(5) hydrogen recovery unit, the pure oxygen non-catalytic partial oxidation conversion system of the present invention's employing all are the technology of mature and reliable.
Description of drawings
Fig. 1 is the structural representation of existing methanol synthesizer scheme one.
Fig. 2 is the structural representation of existing methanol synthesizer scheme two.
Fig. 3 is the structural representation of existing methanol synthesizer scheme three.
Fig. 4 is the structural representation of existing methanol synthesizer scheme four.
Fig. 5 is the structural representation of the embodiment of the invention 1.
Fig. 6 is the structural representation of the embodiment of the invention 2.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect and be easy to understand and understand, below in conjunction with concrete diagram, further set forth the present invention.
Embodiment 1
Referring to Fig. 5; The methanol synthesis loop off-gas of this embodiment behind pure oxygen non-catalytic partial oxidation preparing synthetic gas with the device of increase yield of methanol; The synthesic gas compressor 100 and recycle compressor 200 that comprise series operation; Synthetic compressor 100 is provided with the fresh synthesis gas inlet pipe 110 in order to the input fresh synthesis gas, and recycle compressor 200 is provided with in order to the circulation gas import 210 of input circulation gas, in order to the reforming gas import 220 of input reforming gas and in order to export the syngas outlet 230 of synthetic gas; Carry the methane-containing gas inlet pipe 300 of methane-containing gas to be connected with fresh synthesis gas inlet pipe 110.
Methanol synthesis loop SYN400 has the gas output tube 430 of the gas behind middle pressure saturation steam outlet 420, the one output separation of methanol of pressing saturation steam in the thick methyl alcohol outlet pipe 410, an output of the thick methyl alcohol of an output, synthetic gas input aperture 440, the reforming gas import 450 of an input synthetic gas; Synthetic gas input aperture 440 is connected with syngas outlet 230 on the recycle compressor 200 through synthetic gas line of pipes 240 and preheater 250; Gas output tube 430 is told two-way; The circulation gas import 210 that circulation gas transfer lime 260 and the circulation gas valve 261 of leading up to connects on the recycle compressors 200, another road connects off-gas transfer lime 460 and off-gas valve 461.
Pure oxygen non-catalytic partial oxidation conversion system POX600 is made up of process furnace 610 and receiver 620; Process furnace 610 has in the methanol synthesis loop to press presses saturation steam inlet 612, superheated vapour outlet 613 and in order to the fuel gas inlet 614 of input fuel gas in saturation steam inlet 611, the pure oxygen non-catalytic partial oxidation conversion system; Receiver 620 has presses saturation steam outlet 624 in POX pure oxygen burner 622 and reforming gas outlet 623, the by-product; Press saturation steam inlet 614 to be connected with the middle pressure saturation steam outlet 420 of methanol synthesis loop in the methanol synthesis loop through pressing saturation steam line of pipes 615 in the methanol synthesis loop; Press in the pure oxygen non-catalytic partial oxidation conversion system in the by-product of saturation steam inlet 612 and receiver 620 and press saturation steam outlet 624 to be connected, superheated vapour exports 613 and exports superheated vapours; POX pure oxygen burner 622 connects the exhaust pipe 570 of hydrogen recovery unit, and reforming gas outlet 623 connects the circulation gas import 220 on fresh synthesis gas inlet pipe 110, the recycle compressor 200, the reforming gas import 450 on the methanol synthesis loop 400 respectively through reforming gas transfer lime 630 and the first conversion gas control valve 631, the second conversion gas control valve 632, the 3rd conversion gas control valve 633.
The principle of work of this embodiment is: the methane-containing gas (H that contains methane 3～50%
2, CO, CO
2, CH
4) be pressurized to 5.0～10.0MPa through the fresh synthesis gas that obtains after purifying through synthesic gas compressor 100; Then with go out methanol synthesis loop 400 separation of methanol after circulation gas mix; Through recycle compressor 200 compressions; Mixed gas gets into the methyl alcohol synthetic reactor synthesizing methanol in the methanol synthesis loop 400 after being heated to 200 ℃ through preheater 250.Go out methyl alcohol synthetic reactor contain methyl alcohol gas and inlet tower gas heat exchange after, through air cooling (water-cooled) the most at last temperature be cooled to about 40 ℃, methyl alcohol is condensed into liquid crude methanol and is separated by thick methyl alcohol outlet pipe 410; Go out off-gas behind the separation of methanol of methanol synthesis loop 400 after the washing of washing tower (not shown), get into hydrogen recovery units 500 by off-gas transfer lime 460; Off-gas obtains hydrogen rich gas and tail gas after reclaiming through hydrogen recovery unit, and wherein hydrogen rich gas is returned with methane-containing gas by hydrogen rich gas return tube 540 and mixes, and gets into synthesic gas compressor 100 by fresh synthesis gas inlet pipe 110.Discharging tolerance (or recycle ratio) confirms according to the total inert gas content in the methane-containing gas (for example CH4, N2, Ar etc.); Inert fractions such as CH4, N2, Ar are concentrated in the off-gas, and it is 0-10 that present embodiment can come the volume ratio between Control Circulation gas and the virgin gas through off-gas valve 461 and circulation gas valve 261.
Through the tail gas that hydrogen recovery unit 500 obtains, wherein inert fractions such as CH4, N2, Ar obtain further concentrating.In order to discharge inerts es such as wherein N2, Ar; Small portion tail gas is delivered to fuel tube 560 through tail gas distribution piping 550; The pneumatic transmission that acts as a fuel is gone in the process furnace 610; The middle pressure saturation steam that is used for receiver 620 by-products of overheated methanol synthesis loop 400 and pure oxygen non-catalytic partial oxidation conversion system 600, most of tail gas are sent into the pure oxygen non-catalytic partial oxidation device after through exhaust pipe 570 and preheater 573 preheatings and are carried out the non-catalytic oxidation reaction.Tail gas is blown into receiver 623 together with oxygen during reaction, and gas carries out non-catalytic oxidation and transforms in the receiver 620 of pure oxygen non-catalytic partial oxidation conversion system 600, to reduce methane content.
Tail gas reacts below in the pure oxygen non-catalytic partial oxidation device, taking place:
H
2+0.5O
2＝H
2O
CO+0.5O
2＝CO
2
CH
4+0.5O
2＝CO+2H
2
CH
4+2O
2＝CO
2+2H
2O
CO+H
2O＝CO
2+H
2。
Because the tail gas H/C of hydrogen recovery unit 500 is less than 2; And hydrogen rich gas H/C is greater than 2; Therefore present embodiment can carry valve 541, tail gas transfer valve 571, tail gas distribution valve 581 to regulate the tail gas of hydrogen recovery unit and the ratio between the hydrogen rich gas through hydrogen rich gas; Thereby regulate H/C ratio in the synthetic gas of methanol synthesis loop, H in the fresh synthesis gas that advances methanol synthesis loop of present embodiment
2/ C ratio is 2.05～2.1.
The reforming gas that goes out the reforming gas outlet 623 of the receiver 620 in the pure oxygen non-catalytic partial oxidation conversion system 600 mainly is H
2, CO, reforming gas returns the circulation gas import 220 on fresh synthesis gas inlet pipe 110, the recycle compressor 200, the reforming gas import 450 on the methanol synthesis loop 400 respectively through reforming gas transfer lime 630 and the first conversion gas control valve 631, the second conversion gas control valve 632, the 3rd conversion gas control valve 633.Present embodiment is the second conversion gas control valve the 632, the 3rd to be changed gas control valve 633 close, and the first conversion gas control valve 631 is opened, and reforming gas just can return methane-containing gas and get into synthesic gas compressor 100 like this.
The methane-containing gas of present embodiment (virgin gas) can be methane-containing gas such as natural gas act acetylene tail gas, moving-bed crushed coal pressure gasifying coal gas (lurgi gasifier or BGL stove), PC-FB pressure gasifying gas (HT-L stove), gasification synthetic oil tail gas, coke-oven gas.
Adopt methane-containing gas (acetylene tail gas) condition of embodiment 1 following:
The methane gas condition that contains of employing embodiment 1 is (lurgi gasifier coal generating gas) as follows:
Embodiment 2
Referring to Fig. 6; The methanol synthesis loop off-gas of this embodiment behind pure oxygen non-catalytic partial oxidation preparing synthetic gas with the device of increase yield of methanol; The synthesic gas compressor 100 and recycle compressor 200 that comprise series operation; Synthetic compressor 100 is provided with the fresh synthesis gas inlet pipe 110 in order to the input fresh synthesis gas, and recycle compressor 200 is provided with in order to the circulation gas import 210 of input circulation gas, in order to the reforming gas import 220 of input reforming gas and in order to export the syngas outlet 230 of synthetic gas; Carry the methane-containing gas inlet pipe 300 of methane-containing gas to be connected with fresh synthesis gas inlet pipe 110.
Methanol synthesis loop SYN400 has the gas output tube 430 of the gas behind middle pressure saturation steam outlet 420, the one output separation of methanol of pressing saturation steam in the thick methyl alcohol outlet pipe 410, an output of the thick methyl alcohol of an output, synthetic gas input aperture 440, the reforming gas import 450 of an input synthetic gas; Synthetic gas input aperture 440 is connected with syngas outlet 230 on the recycle compressor 200 through synthetic gas line of pipes 240 and preheater 250; Gas output tube 430 is told two-way; The circulation gas import 210 that circulation gas transfer lime 260 and the circulation gas valve 261 of leading up to connects on the recycle compressors 200, another road connects off-gas transfer lime 460 and off-gas valve 461.
Pure oxygen non-catalytic partial oxidation conversion system POX600 is made up of process furnace 610 and receiver 620; Process furnace 610 has in the methanol synthesis loop to press presses saturation steam inlet 612, superheated vapour outlet 613 and in order to the fuel gas inlet 614 of input fuel gas in saturation steam inlet 611, the pure oxygen non-catalytic partial oxidation conversion system; Receiver 620 has presses saturation steam outlet 624 in POX pure oxygen burner 622 and reforming gas outlet 623, the by-product; Press saturation steam inlet 614 to be connected with the middle pressure saturation steam outlet 420 of methanol synthesis loop in the methanol synthesis loop through pressing saturation steam line of pipes 615 in the methanol synthesis loop; Press in the pure oxygen non-catalytic partial oxidation conversion system in the by-product of saturation steam inlet 612 and receiver 620 and press saturation steam outlet 624 to be connected, superheated vapour exports 613 and exports superheated vapours; POX pure oxygen burner 622 connects the exhaust pipe 570 of hydrogen recovery unit, and reforming gas outlet 623 connects the circulation gas import 220 on fresh synthesis gas inlet pipe 110, the recycle compressor 200, the reforming gas import 450 on the methanol synthesis loop 400 respectively through reforming gas transfer lime 630 and the first conversion gas control valve 631, the second conversion gas control valve 632, the 3rd conversion gas control valve 633.
The principle of work of this embodiment is: the methane-containing gas (H that contains methane 3～50%
2, CO, CO
2, CH
4) be pressurized to 5.0～10.0MPa through the fresh synthesis gas that obtains after purifying through synthesic gas compressor 100; Then with go out methanol synthesis loop 400 separation of methanol after circulation gas mix; Through recycle compressor 200 compressions; Mixed gas gets into the methyl alcohol synthetic reactor synthesizing methanol in the methanol synthesis loop 400 after being heated to 200 ℃ through preheater 250.Go out methyl alcohol synthetic reactor contain methyl alcohol gas and inlet tower gas heat exchange after, through air cooling (water-cooled) the most at last temperature be cooled to about 40 ℃, methyl alcohol is condensed into liquid crude methanol and is separated by thick methyl alcohol outlet pipe 410; Go out off-gas behind the separation of methanol of methanol synthesis loop 400 after the washing of washing tower (not shown), get into hydrogen recovery units 500 by off-gas transfer lime 460; Off-gas obtains hydrogen rich gas and tail gas after reclaiming through hydrogen recovery unit, wherein hydrogen rich gas by hydrogen rich gas delivery pipe 540 directly with hydrogen product.Discharging tolerance (or recycle ratio) confirms according to the total inert gas content in the methane-containing gas (for example CH4, N2, Ar etc.); Inert fractions such as CH4, N2, Ar are concentrated in the off-gas, and it is 0-10 that present embodiment can come the volume ratio between Control Circulation gas and the fresh synthesis gas through off-gas valve 461 and circulation gas valve 261.
Through the tail gas that hydrogen recovery unit 500 obtains, wherein inert fractions such as CH4, N2, Ar obtain further concentrating.In order to discharge inerts es such as wherein N2, Ar; Small portion tail gas is delivered to fuel tube 560 through tail gas distribution piping 550; The pneumatic transmission that acts as a fuel is gone in the process furnace 610; Send into the pure oxygen non-catalytic partial oxidation device after the middle pressure saturation steam that is used for receiver 620 by-products of overheated methanol synthesis loop 400 and pure oxygen non-catalytic partial oxidation conversion system 600, most of tail gas compress through exhaust pipe 570 and tail-gas compressor 574 and carry out catalytic oxidation.Tail gas is blown into through ATR pure oxygen burner 622 together with middle pressure saturation steam and carries out the non-catalytic oxidation conversion in the receiver 623 during reaction, to reduce methane content.
Tail gas reacts below in the pure oxygen non-catalytic partial oxidation device, taking place:
H
2+0.5O
2＝H
2O
CO+0.5O
2＝CO
2
CH
4+0.5O
2＝CO+2H
2
CH
4+2O
2＝CO
2+2H
2O
CO+H
2O＝CO
2+H
2。
Because the tail gas H/C of hydrogen recovery unit 500 is less than 2; And hydrogen rich gas H/C is greater than 2; Therefore present embodiment can carry valve 541, tail gas transfer valve 571, tail gas distribution valve 581 to regulate the tail gas of hydrogen recovery unit and the ratio between the hydrogen rich gas through hydrogen rich gas; Thereby regulate H/C ratio in the synthetic gas of methanol synthesis loop, the H2/C ratio is 2.05～2.1 in the fresh synthesis gas that advances methanol synthesis loop of present embodiment.
The reforming gas that goes out the reforming gas outlet 623 of the receiver 620 in the pure oxygen non-catalytic partial oxidation conversion system 600 mainly is H
2, CO, reforming gas returns the circulation gas import 220 on fresh synthesis gas inlet pipe 110, the recycle compressor 200, the reforming gas import 450 on the methanol synthesis loop 400 respectively through reforming gas transfer lime 630 and the first conversion gas control valve 631, the second conversion gas control valve 632, the 3rd conversion gas control valve 633.Present embodiment is the second conversion gas control valve the 632, the 3rd to be changed gas control valve 633 close, and the first conversion gas control valve 631 is opened, and reforming gas just can return methane-containing gas and get into synthesic gas compressor 100 like this.
The methane-containing gas of present embodiment (virgin gas) can be methane-containing gas such as natural gas act acetylene tail gas, moving-bed crushed coal pressure gasifying coal gas (lurgi gasifier or BGL stove), PC-FB pressure gasifying gas (HT-L stove), gasification synthetic oil tail gas, coke-oven gas.
The coal gas condition of employing embodiment 2 is (lurgi gasifier coal generating gas) as follows:
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (16)
- The methanol synthesis loop off-gas behind pure oxygen non-catalytic partial oxidation preparing synthetic gas with the method for increase yield of methanol; It is characterized in that methane-containing gas is pressurized to 5.0～10.0MPa through the fresh synthesis gas that obtains after purifying through synthesic gas compressor; Then with go out the methanol synthesis loop separation of methanol after circulation gas mix; Through the recycle compressor compression, mixed gas gets into the methanol synthesis loop synthesizing methanol through after the preheating; The methyl alcohol air cooling that contains that goes out methanol synthesis loop is congealed into liquid crude methanol and is separated; The off-gas that goes out behind the separation of methanol of methanol synthesis loop gets into hydrogen recovery unit after washing; After off-gas reclaims through hydrogen recovery unit; Obtain hydrogen rich gas and tail gas; Wherein hydrogen rich gas returns and is mixed into synthesic gas compressor with methane-containing gas or exports as hydrogen product; Tail gas is sent into the pure oxygen non-catalytic partial oxidation conversion system and is carried out the non-catalytic oxidation reaction, and the reforming gas that the non-catalytic oxidation reaction obtains returns with methane-containing gas and is mixed into synthesic gas compressor or recycle compressor or directly is admitted to methanol synthesis loop;Press saturation steam in said methanol synthesis loop and the pure oxygen non-catalytic partial oxidation conversion system by-product, both are seen off by overheated one-tenth superheated vapour in said pure oxygen non-catalytic partial oxidation conversion system.
- 2. the method for claim 1; It is characterized in that described tail gas carries out the non-catalytic oxidation reaction or carries out the non-catalytic oxidation reaction through sending into the pure oxygen non-catalytic partial oxidation conversion system after the tail-gas compressor compression through sending into the pure oxygen non-catalytic partial oxidation conversion system after the preheating.
- 3. method as claimed in claim 2; It is characterized in that; Described tail gas has at least a part and described hydrogen rich gas to have at least some to mix the gas that acts as a fuel and be admitted to the pure oxygen non-catalytic partial oxidation conversion system, in order to press saturation steam in overheated described methanol synthesis loop and the pure oxygen non-catalytic partial oxidation conversion system by-product.
- 4. method as claimed in claim 3 is characterized in that, the said middle saturation steam of pressing can also be used to tail gas and the BW that the pure oxygen non-catalytic partial oxidation device is sent in preheating.
- 5. the method for claim 1 is characterized in that, wherein the volume ratio between circulation gas and the fresh synthesis gas is 0-10.
- 6. the method for claim 1 is characterized in that, described hydrogen recovery unit adopts film way of recycling or PSA transformation suction type to obtain hydrogen rich gas.
- 7. the method for claim 1 is characterized in that, the reforming gas that described non-catalytic oxidation reaction obtains returns after recovery of heat with methane-containing gas and is mixed into synthesic gas compressor or recycle compressor or directly is admitted to methanol synthesis loop.
- 8. the method for claim 1; It is characterized in that; Press saturation steam all to carry out in the process furnace in being arranged at the pure oxygen non-catalytic partial oxidation conversion system in described methanol synthesis loop and the pure oxygen non-catalytic partial oxidation conversion system by-product, the used fuel of described process furnace is fuel gas.
- 9. the method for claim 1 is characterized in that, the H2/C ratio is 2.05～2.1 in the described fresh synthesis gas that advances methanol synthesis loop.
- 10. the method for claim 1 is characterized in that, described methane-containing gas is the methane-containing gas that contains methane 3～50%.
- 11. method as claimed in claim 10; It is characterized in that described methane-containing gas is the methane-containing gas of natural gas act acetylene tail gas, moving-bed crushed coal pressure gasifying coal gas, PC-FB pressure gasifying gas, gasification synthetic oil tail gas or coke-oven gas.
- 12. method as claimed in claim 10 is characterized in that, the volume ratio between described circulation gas and the fresh synthesis gas is 0-10.
- 13. method as claimed in claim 10; It is characterized in that; The tail gas of described entering pure oxygen non-catalytic partial oxidation conversion system and oxygen are through a POX pure oxygen burner combustion; Gas carries out non-oxide catalyzed conversion in the receiver of pure oxygen non-catalytic partial oxidation conversion system, to reduce methane content.
- 14. methanol synthesis loop off-gas preparing synthetic gas behind pure oxygen non-catalytic partial oxidation is characterized in that with the device of increase yield of methanol, comprising:The synthesic gas compressor of series operation and recycle compressor; Said synthetic compressor is provided with the fresh synthesis gas inlet pipe in order to the input fresh synthesis gas, and said recycle compressor is provided with in order to the circulation gas import of input circulation gas, in order to the reforming gas import of input reforming gas and in order to export the syngas outlet of synthetic gas;One carries the methane-containing gas inlet pipe of methane-containing gas, and described methane-containing gas inlet pipe is connected with described fresh synthesis gas inlet pipe;Methanol synthesis loop; This methanol synthesis loop has in the thick methyl alcohol outlet pipe, an output of the thick methyl alcohol of an output presses the middle pressure saturation steam outlet of saturation steam, the gas output tube of the gas behind the output separation of methanol, synthetic gas input aperture, the reforming gas import of an input synthetic gas; Described synthetic gas input aperture is connected with syngas outlet on the described recycle compressor through synthetic gas line of pipes and preheater; Described gas output tube is told two-way; Leading up to circulation gas transfer lime and circulation gas valve connects the circulation gas import on the described recycle compressor, and another road connects off-gas transfer lime and off-gas valve;Hydrogen recovery unit; Described hydrogen recovery unit has the off-gas import of an input off-gas, the tail gas outlet of output tail gas and the hydrogen rich gas outlet of output hydrogen rich gas; Described off-gas import is connected with described off-gas transfer lime; Two-way is told in described hydrogen rich gas outlet; One the tunnel connects hydrogen rich gas return tube and hydrogen rich gas return control valve or hydrogen rich gas delivery pipe and hydrogen rich gas exhaust-control valve, and another road connects through hydrogen rich gas distribution piping and hydrogen rich gas distribution valve and connects the fuel gas transfer lime, and described hydrogen rich gas return tube connects the fresh synthesis gas inlet pipe on the described synthetic compressor; Two-way is told in described tail gas outlet, and one the tunnel connects exhaust pipe and tail gas conveying valve, and another road connects the fuel gas transfer lime through tail gas distribution piping and tail gas distribution valve;The pure oxygen non-catalytic partial oxidation conversion system; Described pure oxygen non-catalytic partial oxidation conversion system is made up of process furnace and receiver; Said process furnace has in the methanol synthesis loop to press presses saturation steam inlet, superheated vapour outlet and in order to the fuel gas inlet of input fuel gas in saturation steam inlet, the pure oxygen non-catalytic partial oxidation conversion system; Said receiver has presses the saturation steam outlet in the outlet of POX pure oxygen burner and reforming gas, the by-product; Press the saturation steam inlet to be connected with the middle pressure saturation steam outlet of described methanol synthesis loop in the methanol synthesis loop through pressing the saturation steam line of pipes in the methanol synthesis loop; Press in the described pure oxygen non-catalytic partial oxidation conversion system in the by-product of saturation steam inlet and described receiver and press the saturation steam outlet to be connected, described superheated vapour exports exports superheated vapour; Described POX pure oxygen burner connects the exhaust pipe of described hydrogen recovery unit, and the outlet of described reforming gas connects the circulation gas import on described fresh synthesis gas inlet pipe, the recycle compressor, the reforming gas import on the methanol synthesis loop respectively through reforming gas transfer lime and the first conversion gas control valve, the second conversion gas control valve, the 3rd conversion gas control valve.
- 15. device according to claim 14 is characterized in that, described exhaust pipe is provided with preheater or tail-gas compressor.
- 16. device according to claim 14 is characterized in that, described hydrogen recovery unit is Membrane recovery unit MRU or pressure-swing absorption apparatus.
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| CN101191084A (en) * | 2007-11-16 | 2008-06-04 | 清华大学 | Multi-coproduction energy method and system by using coal gasification heat with methane reforming manner |
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