CN106609143A - Fischer-Tropsch synthesis method and heavy oil and light oil production method - Google Patents
Fischer-Tropsch synthesis method and heavy oil and light oil production method Download PDFInfo
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- 239000003921 oil Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- 239000000295 fuel oil Substances 0.000 title claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 111
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 110
- 238000000034 method Methods 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003245 coal Substances 0.000 claims abstract description 25
- 238000002309 gasification Methods 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 66
- 238000000926 separation method Methods 0.000 claims description 33
- 238000003763 carbonization Methods 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 17
- 238000005261 decarburization Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 241000555293 Bassariscus astutus Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 29
- 238000005265 energy consumption Methods 0.000 abstract description 11
- 239000002351 wastewater Substances 0.000 abstract description 11
- 239000013505 freshwater Substances 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 121
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 241000772415 Neovison vison Species 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003034 coal gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
The present invention relates to a Fischer-Tropsch synthesis method, which comprises that coal gasification synthesis gas enters a Fischer-Tropsch synthesis reactor and is subjected to a Fischer-Tropsch synthesis reaction under the action of an iron-based catalyst, wherein a volume ratio of H2 to CO in the coal gasification synthesis gas is 0.4-1.2:1, the Fischer-Tropsch synthesis catalyst is an iron-based catalyst, and the CO2 selectivity of the iron-based catalyst is 35-50%. The invention further relates to a heavy oil and light oil production method. Compared to the method in the prior art, the method of the present invention has the following advantages that the Fischer-Tropsch synthesis wastewater treatment capacity can be reduced by more than 50%, the fresh water consumption can be saved by about 10-20%, and the energy source conversion efficiency can be increased by about 2-3%. According to the present invention, the Fischer-Tropsch synthesis reaction and the water gas conversion reaction are highly coupled by using the iron-based catalyst having the CO2 selectivity of 35-50% through the volume ratio of H2 to CO in the coal gasification synthesis gas of 0.4-1.2:1 so as to significantly reduce the energy consumption, the water consumption and the wastewater emission during the Fischer-Tropsch synthesis process and improve the energy efficiency of the whole system.
Description
Technical field
The present invention relates to ICL for Indirect Coal Liquefaction field, in particular it relates to a kind of Fischer-Tropsch synthesis method, Yi Jiyi
Plant the production method of heavy and light oil.
Background technology
ICL for Indirect Coal Liquefaction process converts coal into the liquid fuel of cleaning, but while and highly energy-consuming,
Highly water intensive process, its efficient energy conversion are about 42%, and fresh water consume is about 10t/t products.Fischer-Tropsch is closed
Into the core cell for being ICL for Indirect Coal Liquefaction process, as disclosed in patent application 201110268041.5,
In Fischer-Tropsch synthesis system under ferrum-based catalyst effect, in addition to the primary response of production hydro carbons, also exist
Water gas shift reaction and methane reaction of formation.Wherein the hydrogen release in water can be put by water gas shift reaction
Out, to reaction system supplemental hydrogen source, but when water gas shift reaction selectivity is too high, can cause
CO2Selectivity is too high, makes inertia CO in system2Gas is excessive, not only consumes CO, and reduces
Device effective volume, increases running cost.Therefore, water gas shift reaction is that system suppresses as far as possible
Side reaction.
On the other hand, hydrogen/carbon monoxide ratio (hydrogen-carbon ratio) in synthesis gas from coal gasification typically smaller than 1,
And the Fischer-Tropsch synthesis method of ferrum-based catalyst usually requires that the hydrogen-carbon ratio of the synthesis gas for adding reactor is
1.4-1.8, the Fischer-Tropsch synthesis method of cobalt-base catalyst require that the hydrogen-carbon ratio of synthesis gas is 1.8-2.2, therefore need
Fresh synthesis gas from coal gasification is processed, its hydrogen-carbon ratio be brought up to into suitable numerical value rear and is passed through
Fischer-Tropsch synthesis are carried out in reactor.For example, patent application 200580045288.3 discloses a kind of profit
The method that hydrogen/carbon monoxide ratio in synthesis air-flow is improved with water gas shift reaction.
Patent application 201010511286.1 discloses a kind of method for synthesizing Fischer Tropsch of slurry bed, specifically discloses
Invention method for synthesizing Fischer Tropsch of slurry bed includes：Hydrogen and carbon monoxide are from slurry bed ft synthetic reactor
Entrance is entered, and enters reaction system by gas distributor, is urged with F- T synthesis under the conditions of F- T synthesis
In the presence of agent, hydrogen and CO (carbon monoxide converter) gas carry out Fischer-Tropsch synthesis in paste state bed reactor, instead
After answering, gas phase effluent includes the light hydrocarbon and water of F- T synthesis generation, and gas phase effluent is from reaction system
The upper space of reactor is diffused into, is entered from reactor outlet through the upper space of paste state bed reactor
Separate System of Water-jet, described gas phase effluent are warming up to higher than anti-in the upper space of paste state bed reactor
Temperature 1-30 DEG C heel row is answered to go out paste state bed reactor.Wherein, the catalyst of Fischer-Tropsch synthesis is urged for cobalt-based
Agent, and the CO of the cobalt-base catalyst2Selectivity is relatively low.
By above description it will be seen that, existing F- T synthesis technology mainly focus on suppress Fischer-Tropsch synthesis
Middle water gas shift reaction (reduces CO2Selectivity), while by Fischer-Tropsch synthesis and Water gas shift/WGS
Reaction separates as far as possible, thus its energy consumption, water consume and discharge of wastewater are higher.In becoming greatly for current energy-saving and emission-reduction
Under gesture, energy consumption, water consume and discharge of wastewater in Fischer-Tropsch synthesis how is significantly reduced, improve F- T synthesis
Process environment effect, receives common concern.
The content of the invention
The invention aims to overcome in prior art energy consumption, water consume and waste water in Fischer-Tropsch synthesis
A kind of higher problem of discharge, there is provided the production method of novel Fischer Tropsch synthesis method and heavy and light oil.
The present inventor has found under study for action, makes synthesis gas from coal gasification enter Fischer-Tropsch synthesis device,
Fischer-Tropsch synthesis, H in the synthesis gas from coal gasification are carried out in the presence of ferrum-based catalyst2And CO
Volume ratio is 0.4-1.2:1, the catalyst of the F- T synthesis is ferrum-based catalyst, the ferrum-based catalyst
CO2Selectivity is 35-50%, so as to help lend some impetus to water gas shift reaction, F- T synthesis are anti-
Should highly couple with water gas shift reaction, so significantly reduce energy consumption in Fischer-Tropsch synthesis, water consume and
Discharge of wastewater.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of Fischer-Tropsch synthesis method,
The method includes：Synthesis gas from coal gasification is made to enter Fischer-Tropsch synthesis device, in the presence of ferrum-based catalyst
Carry out Fischer-Tropsch synthesis, H in the synthesis gas from coal gasification2It is 0.4-1.2 with CO volume ratios:1, it is described
The catalyst of F- T synthesis be ferrum-based catalyst, the CO of the ferrum-based catalyst2Selectivity is 35-50%.
On the other hand, present invention also offers the production method of a kind of heavy and light oil, the method includes：
Fischer-Tropsch synthesis are carried out according to above-mentioned method, the mixed gas that reaction is obtained are carried out into the first gas then
Liquid is separated, and obtains liquid heavy oil, then the gas that gas-liquid separation is obtained carries out the second gas-liquid separation, and
The liquid for obtaining is entered into water-filling separating of oil, obtain light oil and water.
The method of the present invention can reduce F- T synthesis wastewater treatment capacity more than 50% compared with prior art, save
Fresh water consumption about 10-20%, efficient energy conversion improve about 2-3%.The method of the present invention passes through coal gas
It is combined to H in gas2It is 0.4-1.2 with CO volume ratios:1, and adopt CO2Ferrum of the selectivity for 35-50%
Base catalyst, Fischer-Tropsch synthesis are highly coupled with water gas shift reaction, are deleted in traditional handicraft
It is self-existent for improving H in synthesis gas2With the processing step of CO volume ratios such that it is able to significantly
Energy consumption, water consume and discharge of wastewater in reduction Fischer-Tropsch synthesis, and the efficiency of whole system is improved, reduce
The manufacturing cost and control cost of system.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the heavy of a kind of preferred implementation of the invention and the production equipment of light oil and artwork.
Description of reference numerals
1 fine de-sulfur reactor, 23 second heat exchanger of Fischer-Tropsch synthesis device, 4 high temperature
5 First Heat Exchanger of gas-liquid separator, 6 cooler, 7 low temperature gas-liquid separator 8
9 circulating air compressor of decarburization unit, 10 water and oil separator.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of Fischer-Tropsch synthesis method, the method includes：It is combined to coal gas
Gas enters Fischer-Tropsch synthesis device, and Fischer-Tropsch synthesis, the coal are carried out in the presence of ferrum-based catalyst
H in gasification synthesis gas2It is 0.4-1.2 with CO volume ratios:1, the catalyst of the F- T synthesis is urged for iron-based
Agent, the CO of the ferrum-based catalyst2Selectivity is 35-50%.
Preferably, H in the synthesis gas from coal gasification2It is 0.6-1.0 with CO volume ratios:1 such that it is able to enter
One step reduces energy consumption, water consume and discharge of wastewater in Fischer-Tropsch synthesis.
In the present invention, synthesis gas from coal gasification contains H2、CO、N2、CO2And CH4, wherein, except
H2Have outside aforementioned proportion requirement, to N with CO volume ratios2、CO2And CH4Amount do not specially require,
Preferably, CO in synthesis gas from coal gasification2Volume content be less than 5%, it is possible to increase CO conversion ratios and
CO2Selectivity.
According to method of the present invention, wherein, the condition of Fischer-Tropsch synthesis can be conventional reaction
Condition, for example, the condition of Fischer-Tropsch synthesis can include that reaction temperature is 230-270 DEG C, reaction pressure
Power is 2-4MPa, and reactor inlet gas empty tower gas velocity is 0.2-0.4m/s, reactor inlet gas volume
Flow is 9000-18000 with the ratio of catalyst quality:1Nm3/h/t；It is highly preferred that reactor inlet gas
Middle CO2Volume content be less than 5%.
According to method of the present invention, wherein, the ferrum-based catalyst contains Fe, Cu and K, Fe,
The mass ratio of Cu and K is 100:6-10:6-10, preferably 100:7-8:8-9.
In the present invention, Fischer-Tropsch synthesis are carried out in Fischer-Tropsch synthesis device.
According to method of the present invention, wherein, synthesis gas from coal gasification is before into Fischer-Tropsch synthesis device
Preheating desulfurization process can also be carried out.Wherein, it is at the conventional pre- thermally desulfurizing in this area to preheat desulfurization process
Reason, for example, can be hydrodesulfurization or ZnO desulfurization, as long as so that into the gas of Fischer-Tropsch synthesis device
In body, the content of sulfur is less than 40ppm.
On the other hand, present invention also offers the production method of a kind of heavy and light oil, the method includes：
Fischer-Tropsch synthesis are carried out according to above-mentioned method, the mixed gas that reaction is obtained are carried out into the first gas then
Liquid is separated, and obtains liquid heavy oil, then the gas that gas-liquid separation is obtained carries out the second gas-liquid separation, and
The liquid for obtaining is entered into water-filling separating of oil, obtain light oil and water.
According to method of the present invention, wherein, for energy efficient, reduce water consume, it is preferable that should
Method also includes：A part in the gas that second gas-liquid separation is obtained does carbonization treatment, will be remaining
Exchange heat as recycled offgas after the gas mixing that the gas and carbonization treatment that second gas-liquid separation is obtained is obtained
Part material as Fischer-Tropsch synthesis afterwards, will the gas that obtains of carbonization treatment with do not carry out at decarburization
The gas mixing that obtains of second gas-liquid separation of reason is simultaneously anti-as F- T synthesis are used as after recycled offgas heat exchange
The part material answered.Wherein, the gas that carbonization treatment is obtained can part can also all with the second gas-liquid
Isolated gas mixing is made as circulating air, the gas mixing obtained with the second gas-liquid separation when part
For circulating air when, remaining portion gas as tail gas discharge system, wherein discharge tail gas be used as circulation
The part carbonization treatment of gas obtains the ratio of gas and does not specifically limit, for example, can be 0.01-0.1:1.
According to method of the present invention, wherein, the method can also include：After recycled offgas is compressed
Heat exchange process is carried out, wherein, the temperature of the recycled offgas after compression can be 40-70 DEG C.
According to method of the present invention, wherein, it is highly preferred that recycled offgas after compression with the first gas
The isolated gas of liquid carries out the first heat exchange process so that the gas temperature drop that the first gas-liquid separation is obtained
To 100-120 DEG C.Wherein, being cooled to gas that 100-120 DEG C of the first gas-liquid separation obtain can be cold with Jing
But device 6 is further reduced to less than 60 DEG C, then carries out the second gas-liquid separation again.
According to method of the present invention, wherein, it is highly preferred that the recycled offgas that the heat exchange of Jing first is processed
Second heat exchange process can be carried out with the hybrid reaction gas obtained with Fischer-Tropsch synthesis so that hybrid reaction
Temperature degree is down to 140-160 DEG C, and being cooled to 140-160 DEG C of hybrid reaction gas carries out the first gas-liquid separation again.
According to method of the present invention, wherein it is preferred to, the method also includes：By at least part of
The gas that two gas-liquid separations are obtained is used as the part material of the Fischer-Tropsch synthesis after carrying out carbonization treatment,
It is 50-70% that the gas of the carbonization treatment accounts for the second gas-liquid separation and obtains the volume ratio (decarburization ratio) of gas,
So as to further reduce energy consumption in Fischer-Tropsch synthesis, water consume and discharge of wastewater.
The volume ratio that the gas that the second gas-liquid separation is obtained is accounted for by controlling the gas of carbonization treatment is
50-70%, can cause H in recycled offgas2It is 0.4-1.2 with CO volume ratios:1, preferably 0.6-1.0:1,
So as to be recycled recycled offgas as the raw material of Fischer-Tropsch synthesis, reduce further
The cost of production.
In the present invention, Fischer-Tropsch synthesis can also produce heavy wax.
In the present invention, the equipment for producing heavy and light oil can be the conventional equipment in this area, for example：
As shown in figure 1, pre- thermally desulfurizing can be carried out in fine de-sulfur reactor 1, Fischer-Tropsch synthesis are in Fischer-Tropsch
Carry out in synthesis reactor 2, the first gas-liquid separation is carried out in high temperature gas-liquid separator 4, the second gas-liquid
Separation is carried out in low temperature gas-liquid separator 7, and the first heat exchange is processed and carried out in First Heat Exchanger 5, the
Two heat exchange are processed and are carried out in the second heat exchanger 3, and water is separating of oil to be carried out in water and oil separator 10, are taken off
Carbon process is carried out in decarburization unit 8, and compression is processed and carried out in circulating air compressor 9.
The present invention need not arrange the hydrogen-carbon ratio modulating equipment (such as water-gas shift) of isolated operation,
Fresh synthesis gas are sent directly into Fischer-Tropsch synthesis device after the process steps such as necessary dedusting, sulphur removal are carried out
In reacted, advantageously reduce the complexity of technique, reduce the manufacturing cost and control cost of system.
Embodiment
Embodiment 1
The present embodiment is used for the production method of the Fischer-Tropsch synthesis method and heavy and light oil for illustrating the present invention.
As shown in figure 1, the production process of heavy and light oil is a cyclic process, concrete cyclic process
For：By 81.7 ten thousand Nm3/ h synthesis gas from coal gasification (H2Content is that 37.2%, CO contents are 62.0%,
N2Content is 0.776%, CO2Content is 0.001% and CH4Content is that 0.023%) to be passed through fine de-sulfur anti-
Preheating desulfurization process are carried out in answering device 1, and (sulfur content is controlled to<40ppm), then enter as unstripped gas
In Fischer-Tropsch synthesis device 2, in ferrum-based catalyst (CO2Selectivity is 50%, the composition of catalyst with
Weight is calculated as Fe:Cu:K=100:7:9), in the presence of, controlling reaction temperature is 255 DEG C, reaction pressure
For 3.0MPa, reactor inlet volumetric flow of gas is 12000 with the ratio of catalyst quality:1Nm3/ h/t,
Reactor inlet empty tower gas velocity is 0.35m/s, carries out Fischer-Tropsch synthesis, and weight is discharged from the middle part of reactor
Then the mixed gas that reaction is obtained are passed through in the second heat exchanger 3 and First Heat Exchanger by matter wax 71t/h
The recycled offgas of middle discharge carries out the second heat exchange process so that hybrid reaction temperature degree is reduced to 155 DEG C,
Then the hybrid reaction gas that temperature is reduced to 155 DEG C is passed through in high temperature gas-liquid separator 4 carries out the first gas
Liquid is separated, and discharges mink cell focus 23.4t/h from 4 bottom of high temperature gas-liquid separator, from high temperature gas-liquid separator 4
Reaction mixture gas are discharged at top, the reaction mixture gas are passed through in First Heat Exchanger and are compressed with Jing recycled offgas
The recycled offgas of the compression of machine 9 carries out the first heat exchange process so that hybrid reaction temperature degree is reduced to 110 DEG C,
55 DEG C are further reduced in then passing to cooler 6, then the gaseous mixture for being cooled to 55 DEG C is passed through
The second gas-liquid separation is carried out in low temperature gas-liquid separator 7, from 7 bottom drain of low temperature gas-liquid separator,
The mixing liquid carries out oil-water separation in being passed through water and oil separator 10, obtains light oil 47.6t/h and water
11.0t/h, meanwhile, by 65.4 ten thousand Nm in 7 top expellant gas of low temperature gas-liquid separator3/ h is direct
It is circulated in tail-gas compressor 9 as recycled offgas, 152.5 ten thousand Nm3/ h gases are passed through decarburization unit
Carbonization treatment is carried out in 8, it is 70% to control decarburization ratio, then 2.5 ten thousand in the gas of Jing carbonization treatments
Nm3Used as tail gas discharge system, remaining then enters in recycled offgas compressor 9/h as recycled offgas,
(temperature is 60 DEG C to the recycled offgas of the compression of Jing recycled offgas compressor 9, H2Volume ratio with CO is
0.6:1) mix with fresh synthesis gas after above-mentioned second heat exchange process F- T synthesis are passed through as unstripped gas
In reactor 2, circulating air and fresh synthesis gas mixed volume ratio are 2.5:1.
Embodiment 2
The present embodiment is used for the production method of the Fischer-Tropsch synthesis method and heavy and light oil for illustrating the present invention.
As shown in figure 1, the production process of heavy and light oil is a cyclic process, concrete cyclic process
For：By 81.7 ten thousand Nm3/ h synthesis gas from coal gasification (H2Content is that 49.6%, CO contents are 49.6%,
N2Content is 0.776%, CO2Content is 0.001% and CH4Content is that 0.023%) to be passed through fine de-sulfur anti-
Preheating desulfurization process are carried out in answering device 1, and (sulfur content is controlled to<40ppm), it is anti-subsequently into F- T synthesis
In answering device 2, in ferrum-based catalyst (CO2Selectivity is 35%, and the composition of catalyst is by weight
Fe:Cu:K=100:7:9), in the presence of, controlling reaction temperature is 230 DEG C, and reaction pressure is 4.0MPa,
Reactor inlet volumetric flow of gas is 18000 with the ratio of catalyst quality:1Nm3/ h/t, reactor inlet
Empty tower gas velocity is 0.4m/s, carries out Fischer-Tropsch synthesis, discharges heavy wax 71t/h, so from the middle part of reactor
Afterwards the mixed gas that reaction is obtained are passed through in the second heat exchanger 3 and the loop tail discharged in First Heat Exchanger
Gas carries out the second heat exchange process so that hybrid reaction temperature degree is reduced to 160 DEG C, then reduces temperature
Being passed through in high temperature gas-liquid separator 4 to 160 DEG C of hybrid reaction gas carries out the first gas-liquid separation, from high temperature
Mink cell focus 23.4t/h is discharged in 4 bottom of gas-liquid separator, discharges reaction mixed from the top of high temperature gas-liquid separator 4
Gas is closed, the reaction mixture gas are passed through in First Heat Exchanger the circulation compressed with Jing recycled offgas compressor 9
Tail gas carries out the first heat exchange process so that hybrid reaction temperature degree is reduced to 100 DEG C, then passes to cooling
55 DEG C are further reduced in device 6, then the gaseous mixture for being cooled to 55 DEG C is passed through into low temperature gas-liquid separation
The second gas-liquid separation is carried out in device 7, from 7 bottom drain of low temperature gas-liquid separator, the mixing liquid
Oil-water separation is carried out in being passed through water and oil separator 10, light oil 47.6t/h and water 11.0t/h is obtained, meanwhile,
By 109.0 ten thousand Nm in 7 top expellant gas of low temperature gas-liquid separator3/ h is directly used as recycled offgas
It is circulated in tail-gas compressor 9,109.0 ten thousand Nm3/ h gases are passed through in decarburization unit 8 and carry out decarburization
Process, it is 50% to control decarburization ratio, then 2.5 ten thousand Nm in the gas of Jing carbonization treatments3/ h is used as tail
Gas discharge system, remaining is then entered in recycled offgas compressor 9 as recycled offgas, Jing recycled offgas
(temperature is 60 DEG C to the recycled offgas of the compression of compressor 9, H2Volume ratio with CO is 1:1) through upper
State to mix with fresh synthesis gas after the second heat exchange is processed and be passed through in Fischer-Tropsch synthesis device 2 as unstripped gas,
Circulating air and fresh synthesis gas mixed volume ratio are 2.5:1.
Embodiment 3
The present embodiment is used for the production method of the Fischer-Tropsch synthesis method and heavy and light oil for illustrating the present invention.
As shown in figure 1, the production process of heavy and light oil is a cyclic process, concrete cyclic process
For：By 81.7 ten thousand Nm3/ h synthesis gas from coal gasification (H2Content is that 44.1%, CO contents are 55.1%,
N2Content is 0.776%, CO2Content is 0.001% and CH4Content is that 0.023%) to be passed through fine de-sulfur anti-
Preheating desulfurization process are carried out in answering device 1, and (sulfur content is controlled to<40PPM), it is anti-subsequently into F- T synthesis
In answering device 2, in ferrum-based catalyst (CO2Selectivity is 42%, and the composition of catalyst is by weight
Fe:Cu:K=100:8:9), in the presence of, controlling reaction temperature is 270 DEG C, and reaction pressure is 2.0MPa,
Reactor inlet volumetric flow of gas is 9000 with the ratio of catalyst quality:1Nm3/ h/t, reactor inlet are empty
Tower gas speed is 0.2m/s, carries out Fischer-Tropsch synthesis, discharges heavy wax 71t/h, then from the middle part of reactor
The mixed gas that reaction is obtained are passed through in the second heat exchanger 3 and the recycled offgas discharged in First Heat Exchanger
Carry out the second heat exchange process so that hybrid reaction temperature degree is reduced to 140 DEG C, is then reduced to temperature
140 DEG C of hybrid reaction gas carries out the first gas-liquid separation in being passed through high temperature gas-liquid separator 4, from High Temperature Gas
Mink cell focus 23.4t/h is discharged in 4 bottom of liquid/gas separator, and reaction mixing is discharged from the top of high temperature gas-liquid separator 4
Gas, the reaction mixture gas are passed through in First Heat Exchanger the loop tail compressed with Jing recycled offgas compressor 9
Gas carries out the first heat exchange process so that hybrid reaction temperature degree is reduced to 120 DEG C, then passes to cooler
55 DEG C are further reduced in 6, then the gaseous mixture for being cooled to 55 DEG C is passed through into low temperature gas-liquid separator 7
In carry out the second gas-liquid separation, from 7 bottom drain of low temperature gas-liquid separator, the mixing liquid is passed through
Oil-water separation is carried out in water and oil separator 10, light oil 47.6t/h and water 11.0t/h is obtained, meanwhile, will
87.2 ten thousand Nm in 7 top expellant gas of low temperature gas-liquid separator3/ h is directly used as recycled offgas and enters
In row recycled offgas compressor 9,130.7 ten thousand Nm3/ h gases are passed through in decarburization unit 8 and carry out at decarburization
Reason, it is 60% to control decarburization ratio, then 2.5 ten thousand Nm in the gas of Jing carbonization treatments3/ h is used as tail gas
Discharge system, remaining is then entered in recycled offgas compressor 9 as recycled offgas, Jing loop tail air pressure
(temperature is 60 DEG C to the recycled offgas of the compression of contracting machine 9, H2It is 0.8 with CO volume ratios:1) through above-mentioned
Mix with fresh synthesis gas after second heat exchange process and be passed through in Fischer-Tropsch synthesis device 2 as unstripped gas, follow
Ring gas and fresh synthesis gas mixed volume ratio are 2.5:1.
Embodiment 4
The present embodiment is used for the production method of the Fischer-Tropsch synthesis method and heavy and light oil for illustrating the present invention.
Method according to embodiment 1 carries out F- T synthesis and production heavy and light oil, except for the difference that, H2
It is 1.5 with CO volumes:1.
Embodiment 5
The present embodiment is used for the production method of the Fischer-Tropsch synthesis method and heavy and light oil for illustrating the present invention.
Method according to embodiment 1 carries out F- T synthesis and production heavy and light oil, except for the difference that, control
It is 20% that the gas of carbonization treatment processed accounts for the volume ratio (decarburization ratio) of the gas that the second gas-liquid separation is obtained.
Comparative example 1
Method according to embodiment 1 carries out F- T synthesis and production heavy and light oil, except for the difference that, H2
It is 1.6 with CO volumes:1.
Comparative example 2
Method according to embodiment 1 carries out F- T synthesis and production heavy and light oil, except for the difference that, ferrum
The CO of base catalyst2Selectivity is 15%.
Comparative example 3
Method according to embodiment 1 carries out F- T synthesis and production heavy and light oil, except for the difference that, H2
It is 1.6 with CO volumes:1, the CO of ferrum-based catalyst2Selectivity is 15%, controls decarburization ratio for 20%.
Table 1
The method of the present invention can reduce F- T synthesis wastewater treatment capacity more than 50% compared with prior art, save
Fresh water consumption about 10-20%, efficient energy conversion improve about 2-3%.The method of the present invention passes through coal gas
It is combined to H in gas2It is 0.4-1.2 with CO volume ratios:1, and adopt CO2Ferrum of the selectivity for 35-50%
Base catalyst, Fischer-Tropsch synthesis are highly coupled with water gas shift reaction such that it is able to significantly reduced
Energy consumption, water consume and discharge of wastewater in Fischer-Tropsch synthesis, and improve the efficiency of whole system.
Embodiment 1 is compared with embodiment 4 as can be seen that as H in synthesis gas from coal gasification2With CO bodies
Product is than being 0.6-1.0:1 such that it is able to further reduce energy consumption, water consume and waste water row in Fischer-Tropsch synthesis
Put, and can further improve system energy efficiency.
By embodiment 1 compare with embodiment 5 as can be seen that when carbonization treatment decarburization ratio be 50-70%,
So as to further reduce energy consumption in Fischer-Tropsch synthesis, water consume and discharge of wastewater, and further can carry
High system energy efficiency.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of Fischer-Tropsch synthesis method, it is characterised in that the method includes：Enter synthesis gas from coal gasification
Enter Fischer-Tropsch synthesis device, Fischer-Tropsch synthesis, the coal gasification are carried out in the presence of ferrum-based catalyst
H in synthesis gas2It is 0.4-1.2 with CO volume ratios:1, the catalyst of the F- T synthesis is ferrum-based catalyst,
The CO of the ferrum-based catalyst2Selectivity is 35-50%.
2. method according to claim 1, wherein, H in the synthesis gas from coal gasification2And CO
Volume ratio is 0.6-1.0:1.
3. method according to claim 1, wherein, the condition of the Fischer-Tropsch synthesis includes：
Reaction temperature is 230-270 DEG C, and reaction pressure is 2-4MPa, and reactor inlet gas empty tower gas velocity is
0.2-0.4m/s, reactor inlet volumetric flow of gas with the ratio of catalyst quality is
9000-18000:1Nm3/h/t。
4. method according to claim 1, wherein, the ferrum-based catalyst contains Fe, Cu
And K, the mass ratio of Fe, Cu and K is 100:6-10:6-10, preferably 100:7-8:8-9.
5. method according to claim 3, wherein, CO in reactor inlet gas2Volume
Content is less than 5%.
6. the production method of a kind of heavy and light oil, it is characterised in that the method includes：According to power
Profit requires that the method in 1-5 described in any one carries out Fischer-Tropsch synthesis, then by reaction obtain it is mixed
Closing gas carries out the first gas-liquid separation, obtains liquid heavy oil, then the gas that gas-liquid separation is obtained is carried out
Second gas-liquid separation, and it is separating of oil that the liquid for obtaining entered water-filling, obtains light oil and water.
7. method according to claim 6, wherein, the method also includes：By at least part of
The gas that two gas-liquid separations are obtained is used as the part material of the Fischer-Tropsch synthesis after carrying out carbonization treatment,
The gas of the carbonization treatment account for the second gas-liquid separation obtain gas volume ratio be 50-70%.
8. the method according to claim 6 or 7, wherein, the method also includes：At decarburization
The gas mixing conduct that the gas that reason is obtained is obtained with the second gas-liquid separation for not carrying out carbonization treatment is followed
It is used as the part material of Fischer-Tropsch synthesis after the heat exchange of ring tail gas.
9. method according to claim 8, wherein, H in the recycled offgas2With CO volumes
Than for 0.4-1.2:1.
10. method according to claim 9, wherein, H in the recycled offgas2With CO bodies
Product is than being 0.6-1.0:1.
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