CN106520179A - Method for combined production of fuel oil with coke oven gas and carbon dioxide-enriched gas - Google Patents
Method for combined production of fuel oil with coke oven gas and carbon dioxide-enriched gas Download PDFInfo
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- CN106520179A CN106520179A CN201510582283.XA CN201510582283A CN106520179A CN 106520179 A CN106520179 A CN 106520179A CN 201510582283 A CN201510582283 A CN 201510582283A CN 106520179 A CN106520179 A CN 106520179A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 39
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000295 fuel oil Substances 0.000 title claims abstract description 13
- 239000000571 coke Substances 0.000 title abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000023556 desulfurization Effects 0.000 claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 120
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003009 desulfurizing effect Effects 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 25
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229960004424 carbon dioxide Drugs 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000000746 purification Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003034 coal gas Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method for combined production of fuel oil with coke oven gas and carbon dioxide-enriched gas; the coke oven gas and the carbon dioxide-enriched gas are subjected to dedusting and impurity removal treatment firstly, are mixed, then are compressed, enter a TSA pretreatment tower and a PSA pretreatment processing tower and are treated; the obtained gas is compressed again and then enters a pre-hydrogenation reactor, a hydrogenation reactor and a zinc oxide deep desulfurization reactor and is subjected to deep desulfurization and dechloridation; purified synthesis gas is mixed with 3.5 MPa medium-pressure steam and carbon dioxide recycle gas, and then the mixed gas enters a reformer, undergoes a reaction and then enters a PSA unit to remove carbon dioxide; the synthesis gas after treatment enters a Fischer-Tropsch synthesis reactor and is subjected to a reaction, to produce the qualified fuel oil. The method has the advantages of simple technological process, easy operation, stable operation for a long time, qualified product, low energy consumption, small equipment investment, less carbon dioxide emission, energy saving and environmental protection.
Description
Technical field
The present invention relates to steel mill's coking gas processing technology field, specifically one kind coke-stove gas combine life with carbon dioxide enriched gas
The method for producing fuel oil.
Background technology
China is the most country of world's coke output, accounts for the 60% of global coke output, and just often produce one ton of coke
The side-product coke-stove gas for having about 400Nm3 is produced, and yield is huge, has been increasingly becoming a kind of large-tonnage energy and chemical industry
Resource.
Coke-stove gas also known as oven gas, its composition slightly difference because coal for coking quality is different with coking condition, typically
Containing 55% or so hydrogen, 25% or so methane, 7% or so carbon monoxide, in addition also containing 5% or so nitrogen,
3% or so unsaturated hydrocarbons, 2% or so carbon dioxide, 1% or so oxygen and other gases.Traditional processing method pole
Which is limited, is primarily used to heating, town gas and the generating of coke-stove gas itself, and for the consideration of safety in production, it is rich
Remaining coke-stove gas is then directly discharged in air Jing after burning, has not only been polluted environment but also has been caused greatly waste, has also given people
The living environment of class brings greatly threat.Therefore, how efficiently, reasonably it is relation environmental protection, provides using coke-stove gas
Source comprehensive utilization, the key subjects of energy-saving and emission-reduction, have been obtained for everybody highest attention between nearest decades.Due to Jiao
Contain substantial amounts of hydrocarbon resource in producer gas, so far therefore occur in that the methods for much comprehensively utilizing with regard to which.
Existing Publication No. CN103804138A discloses " a kind of technique of coke-stove gas methanol ", and the technique is by Jiao
The isolated carbon dioxide mix Jing after conventional purification and in purification waste gas of producer gas, carries out CO 2 reforming reaction and obtains
Synthesis gas rich in carbon monoxide and hydrogen, is reacted hence into methanol synthesis reactor.The methanol and unreacted of generation
Gas obtains crude carbinol after gas-liquid separation, and unreacting gas are partly into recycling, a part of to produce two Jing after burning
Carbonoxide, the separated Posterior circle of this partial CO 2 using so as to reach mend carbon purpose.The technique efficiently solves coke oven
The problem of carbon and off-gas discharge is mended during coal gas synthesizing methanol, reduces the discharge of waste gas.But due to the methanol of China
Production capacity is superfluous, therefore is difficult popularization and application in a short time.
Existing Publication No. CN104154706A discloses " technique that a kind of coke-stove gas prepares liquefied natural gas ", the work
Skill is, by coke-stove gas Jing oil removings, after taking off the removal of impurity such as naphthalene and de- benzene, directly to carry out methanation on catalyst for methanation in presence of sulfur
React, then Jing low-temp methanols wash desulfurization and decarburization, and cryogenic separation removes the magazine such as nitrogen and hydrogen, so as to obtain methane content
Liquefied natural gas more than 97%.This technique avoids the multistage hydrogenation of complexity and Multistage desulfuration process, reduces purification technique
1/3, simplify flow process and reduce energy consumption and investment.But in methanation, the reacted life of substantial amounts of hydrogen
It is wasted into the water without economic benefit, and the coke-stove gas per 100Nm3 can only obtains the liquid of about 40Nm3 or so
Activating QI, the consumption of coke-stove gas are huge.
Existing Publication No. CN103992198A discloses " a kind of technique of coke-stove gas for raw material production sheet ", the technique
The methane that first coke-stove gas is obtained with methanation by cleaning system process, the methane gas obtained by PSA purifications
Gas, processes benzene of attaining the Way through recirculating fluidized bed aromatisation.Converting coke oven gas are the change with high added value by this technique first
Chemical product, has broken away from the limitation thinking of " fuel production fuel ".But the paper of correlation and relatively fewer, the industrialization of research
Road is also very very long.
Meanwhile, substantial amounts of carbon dioxide can be produced in oil, Coal Industrial, remove a small amount of carbon dioxide quilt
Outside as the purposes such as fire extinguishing, refrigeration, food industry, substantial amounts of carbon dioxide is directly discharged in air.Due to carbon dioxide
With insulation effect, therefore caused increasingly severe greenhouse effect, so as to cause global warming, Melting Glacierss,
The serious problem of some row of sea-level rise etc., brings great pressure to global environment protection.Also, titanium dioxide
Carbon can not burn, no any calorific value, so, how to process becomes urgently to be resolved hurrily one using excessive carbon dioxide
Hang-up.By taking blast furnace gas as an example, the blast furnace gas that one ton of ferrum can produce 2100-2200m3 is often refined, wherein containing about 13%
Carbon monoxide, 2% hydrogen, 55% nitrogen and up to 20% or so carbon dioxide.Due to containing substantial amounts of non-combustible
Gas, its calorific value are only 3500J/m3, it is impossible to enough directly to use as fuel.Therefore, find paths rationally to utilize
These rich carbonated gases can bring once big revolution for whole industrial quarters.
Through developing rapidly for last decade refining capacity, including the development and application of the new techniques such as coal liquifaction, shale oil, fuel
The production of oil can meet domestic demands.But due to the resource general layout of China " coal heavy wool is few ", about 40% crude oil
Need import, heavy dependence international market, therefore, the multi-party approach for expanding production fuel oil is to break existing general layout, progressively
Break away from the only way which must be passed for international market constraint.
The content of the invention
It is an object of the invention to provide a kind of method of use coke-stove gas and carbon dioxide enriched gas Joint Production fuel oil, to solve
The problem proposed in certainly above-mentioned background technology.
For achieving the above object, the present invention provides following technical scheme：
A kind of method of use coke-stove gas and carbon dioxide enriched gas Joint Production fuel oil, concrete production stage are as follows：
(1) coke-stove gas enters back into fixed bed desulfurization tower after first passing through dedusting, in the presence of desulfurizing agent remove inorganic sulfur and
Tar；
(2) CO 2 enriched gas first pass through dedusting into pretreater to remove tar, naphthalene and benzene；
(3) one stage of compression will be carried out into compressor after above two gas mixing, enters back into TSA pretreaters and PSA
Pretreater, temperature control at 120～160 DEG C, with except tar removing, naphthalene, benzene and nitrogen, H2S、HCN、NH3With
Hydrocarbon impurities, adsorbed hydrogen, methane, carbon monoxide, carbon dioxide, nitrogen are not discharged from tower top；
(4) by pretreated synthesis gas through compressor recompression, the temperature of gas at 220～300 DEG C, Ran Houjin
Enter hydrodesulfurizationunit unit, deep desulfuration and chlorine carried out by pre-hydrogenator, hydrogenation reactor and zinc oxide desulfurization reactor,
So that sulfur content is not more than 0.5ppm in synthesis gas after refined；
(5) synthesis gas after purifying is carried out instead into reburner after being mixed with 3.5MPa middle pressure steams, carbon dioxide recycle gas
Should, Partial Conversion is carried out by self-heating catalytic conversion reaction, temperature control at 490～500 DEG C, in the synthesis gas after conversion,
The ratio of hydrogen and carbon monoxide is 2:1；
(6) synthesis gas after conversion is entered into PSA unit, is processed to be separated off carbon dioxide, two for isolating
Carbonoxide can be continued with as circulating air；
(7) synthesis gas for isolating PSA unit is reacted into Fischer-Tropsch synthesis device, to produce qualified combustion
Material oil, then through multistage rectification.
As further scheme of the invention：Desulfurizing agent in step (1) is iron oxide solid desulfurating agent.
As further scheme of the invention：In step (5), controlled by the amount of control circulation air carbon dioxide
In synthesis gas after system conversion, the ratio of hydrogen and carbon monoxide is 2:1.
Compared with prior art, the invention has the beneficial effects as follows：
1st, coke-stove gas and carbon dioxide enriched gas can be passed through for raw material Joint Production fuel oil by the present invention, obtained combustion
Material oil needs not move through the desulfurization process of complexity, only just directly need to can sell as qualified products through simple rectification, be combustion
The production of material oil is there is provided a new approach.
2nd, carbon in coke-stove gas and carbon dioxide enriched gas, hydrogen resource is efficiently utilized, whole technical process only needs to mend
Fill part vapor and convert for methane, reduce energy expenditure and equipment investment.Meanwhile, carbon dioxide is used as circulation
Gas reduces the discharge of carbon dioxide to a certain extent controlling transformation efficiency, realizes the purpose of environmental protection.
3rd, this technological process is simple, it is easy to operate, the operation of energy long-time stable.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Fig. 2 is the technological process apparatus figure of the present invention.
In figure：1- desulfurizing towers；2- pretreaters；3- compressors；4-TSA pretreaters；5-PSA pretreaters；6- with plus
Hydrogen reactor；7- hydrogenation reactors；8- zinc oxide desulfurization reactors；9- reburners；10-PSA processing units；11- Fischer-Tropsch is closed
Into reactor.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearly and completely
Description, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based on this
Embodiment in invention, the every other reality obtained under the premise of creative work is not made by those of ordinary skill in the art
Example is applied, the scope of protection of the invention is belonged to.
Fig. 1～2 are referred to, in the embodiment of the present invention, carbon dioxide enriched gas is by taking blast furnace gas as an example.
As shown in drawings, this technique is divided into desulfurizing tower, blast furnace gas pretreatment, compressor, TSA pretreatment, PSA and locates in advance
Reason, pre- hydrogenation, hydrogenation, zinc oxide desulfurization, conversion, PSA, 11 units of F- T synthesis.
1st, desulfurizing tower unit
Coke-stove gas enters desulfurizing tower 1 from tower top, and desulfurization adopts fixed bed desulfurization by dry method, and ambient temperature desulfuration agent is with activity
New and effective iron oxide solid desulfurating agent of the iron oxides for main active component.Filling West China company exploitation in desulfurizing tower
HX-Z series solid desulfurating agents.The desulfurizing agent has very high desulphurizing activated and Sulfur capacity, wherein lives with desulfurization at normal temperatures
The main component of property is：α-Fe2O3·H2O and γ-Fe2O3·H2O。
When coal gas passes through bed, the hydrogen sulfide in coal gas generates iron sulfide with desulfurization agent reaction：Fe2O3·H2O+3H2S=
Fe2S3·H2O+3H2O；
Under conditions of in coal gas with the presence of oxygen, the iron sulfide of generation is generated ferrum oxide again and separates out sulfur with oxygen reaction.
React and be：Fe2S3·H2O+3/2O2=Fe2O3·H2O+3S；
As the O in coal gas2/H2During S >=3, this desulfurization ----regenerative process is constantly carried out, until desulfurizing agent space is blocked
And fail.In the process, active iron oxide hydrate solid desulfurating agent is effectively equivalent to the effect of catalyst；
The inorganic sulfur and a small amount of organic sulfur of the overwhelming majority is desulfurized the removing of agent reactive absorption, the coke-stove gas after desulfurization and tar
It is sent to lower operation；Desulfurizing tower is divided to two groups, when the 1st group of outlet H2S concentration is close to unstripped gas concentration, it is believed that the 1st group of desulfurization
Agent is failed, cuts off out flow process by the 1st group, and only with the 2nd group of operation, the 1st group of desulfurizing tower changes desulfurizing agent.
2nd, blast furnace gas pretreatment unit
Blast furnace gas from after blower is cooled to 40 DEG C, enters the tower adsorbed in pretreater 2 from bottom of towe.This
Unit is made up of 2 adsorption towers, has state of the adsorption tower in charging absorption, its technical process is by adsorbing, inverse side,
Rinse, boosting four steps is constituted, detailed process is as follows：
A) adsorption process
Unstripped gas enters adsorption tower from bottom of towe, under adsorptive pressure 0.05MPa (G), select absorption fall most of impurity, not by
The hydrogen of absorption, methane, nitrogen etc. are discharged from tower top as product, and when adsorbing, forward position (impurity forward position) arrival adsorbent is pre-
Stop absorption when staying the bottom of section.
B) inverse put pressure reduction
Preprocessor against absorption direction, i.e., towards arrival end pressure release to regeneration gas house steward.
C) rinsing desorption impurity
With the about 500Nm of the synthesis gas after purification3/ h, rinses adsorption layer against absorption direction long-time, makes the impurity composition of absorption
It is desorbed.Rinse stripping gas and be sent to regeneration gas house steward.
D) boost process
PSA preprocessors are forced into into adsorptive pressure with the pretreated synthesis gas of PSA against absorption direction, this pretreatment
Device proceeds to adsorption process next time.
Two pretreaters alternately more than absorption and regenerative process, so that it may realize the continuous purification of synthesis gas.
3rd, compression unit
Coke-stove gas after coke oven gas desulfurization tower desulfurization with mix from the pretreated blast furnace gas of blast furnace gas after
Into compressor, 2 one sections are pressurized to about 0.16MPa (G) afterwards into TSA pretreaters 3, PSA pretreaters 4, remove
Wherein component and the major part H such as the naphthalene of remnants, benzene, tar2S、HCN、NH3, the impurity composition such as hydro carbons, pretreatment
Synthesis gas afterwards delivers to hydrodesulfurizationunit unit below Jing after two, three sections of compressor is compressed to about 1.6MPa (G).
4th, TSA pretreatment units
Be about the gaseous mixture of 0.16MPa (G) from pressure after 3 one stage of compression of compressor, temp.-changing adsorption pretreatment is entered from bottom
Tower 4, wherein one is in absorption removing oil, naphthalene, de- benzene state, and one is in reproduced state.The regeneration of TSA pretreaters
Process includes：
A) inverse put pressure reduction
Pretreater, is sent to outside battery limit (BL) that is, towards arrival end pressure release to regeneration gas house steward against absorption direction.
B) thermal regeneration process
With PSA pretreaters regenerate and come stripping gas, Jing TSA heaters heating after, rinse regenerate TSA pretreatment
Tower.Until whole bed is heated to about 120-160 DEG C, till the impurity such as benzene, naphthalene, ammonia, alkene in bed desorption is clean.
C) cooling procedure
With PSA pretreaters stripping gas again from birth, the bed after thermal regeneration is cooled down, until being cooled to room temperature.
D) boost process
TSA pretreaters are slowly boosted to into adsorption pressure with through TSA pretreated decontaminating syngas against absorption direction
Power, afterwards this preprocessor proceed to adsorption process next time.
Two TSA pretreaters alternately more than absorption and regenerative process, so that it may realize the continuous purification of gas.
5th, PSA pretreatment units
Gas Jing after temp.-changing adsorption process is sent to PSA pretreaters 5, further removes the impurity composition in unstripped gas,
Unstripped gas-the decontaminating syngas of primary purification are obtained, PSA pretreaters therein are also adopted by the work of one regeneration of an absorption
Make mode, the regenerative process of PSA pretreaters includes：
A) inverse put pressure reduction
PSA pretreaters are against absorption direction, i.e., towards arrival end pressure release, regeneration of the expellant gas as TSA pretreatment
Gas.
B) rinsing desorption impurity
With the synthesis gas after purification, adsorption layer is rinsed against absorption direction long-time, be desorbed the impurity composition of absorption.
Rinse stripping gas TSA pretreatment is sent to as regeneration gas.
C) boost process
PSA pretreaters are forced into into adsorptive pressure with the pretreated decontaminating syngas of PSA against absorption direction, this is pre-
Processor proceeds to adsorption process next time.
Two PSA the pretreaters alternately absorption of the above and regenerative process, so that it may realize the continuous purification of gas.
Synthesis gas after being cleaned is sent to compressor and carries out two, three sections of compressions, enters hydrodesulfurization after pressure-raising to about 1.6MPa
Unit.
6th, pre- hydrogenation unit
The micro oily post-heating that synthesis gas is entered in synthesis gas oil removing pot removing gas after compression enters to 220～300 DEG C or so
Enter pre-hydrogenator 6, oxygen here in synthesis gas, organic sulfur, alkene etc. occur hydrogenation reaction, organic sulfur with hydrogen
Become inorganic sulfur.
7th, hydrogenation unit
Reacted synthesis gas enters hydrogenation reactor 7 after cooling, and organic sulfur continues to carry out adding with hydrogen here
Hydrogen reacts.
8th, zinc oxide desulfurization unit
The chlorine in raw material is removed from the synthesis gas out of hydrogenation reactor 7 into 8 dechlorination section of zinc oxide desulfurization reactor, finally
Into zinc oxide desulfurization section, there is desulphurization reaction in this Zinc Oxide with hydrogen sulfide, sulfur content is less than in the gas after refining
0.5ppm。
Reaction equation is as follows：
Alkene saturation C2H4+H2→C2H6
Mercaptan:RSH+H2→RH+H2S
Thioether:R1SR2+2H2→R1H+R2H+H2S
Disulfide:R1SSR2+3H2→R1H+R2H+2H2S
Thiophene:C4H4S+4H2→C4H10+H2S
Carbonyl sulfide:COS+H2→CO+H2S
Carbon bisulfide:CS2+4H2→CH4+2H2S
Oxygen：O2+2H2→2H2O
9th, conversion unit
Unstripped gas after refined was mixed with 3.5MPa water vapour and carbon dioxide recycle gas before into reburner 9, then
Inverted stove convection section is preheated to 500 DEG C, enters reburner radiant section by upper set pipe；Reformer tube is built with conversion catalyst
Agent, in the presence of catalyst, there is complicated conversion reaction with vapor in unstripped gas；Whole course of reaction shows as strong suction
Thermal response, the heat needed for reaction are provided by the gaseous fuel burner being located at the top of reburner；Go out the pyrolytic conversion gas of reburner
After (outlet temperature is 840 DEG C) inverted gas steam generator presses steam in occurring, temperature is down to 350 DEG C, into PSA
Unit.Specifically react and be：
CnHm+nH2O=nCO+ (n+m/2) H2 ①
CO+3H2=CH4+H2O △ Ho298=-206kJ/mol are 2.
CO+H2O=CO2+H2△ Ho298=-41kJ/mol are 3.
Reaction 3 is reversible reaction, therefore by controlling the amount of carbon dioxide in reaction gas controlling hydrogen and an oxygen in synthesis gas
Change the ratio of carbon so as to reach 2:1.
10th, PSA unit
From reburner synthesis gas from bottom of towe into adsorption tower in be in the tower (all the time while there is 1) of absorption working condition,
Wherein under the absorption of selection successively of various adsorbents, remove synthesis carbon dioxide therein and be transported to as circulating air
In reburner 9；Meanwhile, hydrogen is 2 with carbon monoxide ratio:1 synthesis gas enters F- T synthesis unit.
10th, F- T synthesis unit
Hydrogen and carbon monoxide ratio through purification, conversion, after separating is 2:1 synthesis gas enters Fischer-Tropsch synthesis
In device 11, funds support synthetic reaction generates the oil of the proper fuel containing many fractions.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and do not carrying on the back
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter from
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as and limit involved claim.
Claims (3)
1. a kind of method of use coke-stove gas and carbon dioxide enriched gas Joint Production fuel oil, it is characterised in that tool
Body production stage is as follows：
(1) coke-stove gas enters back into fixed bed desulfurization tower after first passing through dedusting, removes in the presence of desulfurizing agent
Inorganic sulfur and tar；
(2) CO 2 enriched gas first pass through dedusting into pretreater to remove tar, naphthalene and benzene；
(3) one stage of compression will be carried out into compressor after above two gas mixing, enters back into TSA pretreatment
Tower and PSA pretreaters, temperature control at 120～160 DEG C, with except tar removing, naphthalene, benzene and nitrogen,
H2S、HCN、NH3And hydrocarbon impurities, not adsorbed hydrogen, methane, carbon monoxide, carbon dioxide,
Nitrogen is discharged from tower top；
(4) by pretreated synthesis gas through compressor recompression, the temperature of gas at 220～300 DEG C,
Subsequently into hydrodesulfurizationunit unit, entered by pre-hydrogenator, hydrogenation reactor and zinc oxide desulfurization reactor
Row deep desulfuration and chlorine so that in the synthesis gas after refined, sulfur content is not more than 0.5ppm；
(5) synthesis gas after purifying is entered after being mixed with 3.5MPa middle pressure steams, carbon dioxide recycle gas and is turned
Change stove reacted, Partial Conversion is carried out by self-heating catalytic conversion reaction, temperature control at 490～500 DEG C,
In synthesis gas after conversion, the ratio of hydrogen and carbon monoxide is 2:1；
(6) synthesis gas after conversion is entered into PSA unit, is processed to be separated off carbon dioxide, point
The carbon dioxide for separating out can be continued with as circulating air；
(7) synthesis gas for isolating PSA unit is reacted into Fischer-Tropsch synthesis device, to produce
Proper fuel oil, then through multistage rectification.
2. the method for use coke-stove gas according to claim 1 and carbon dioxide enriched gas Joint Production fuel oil,
Characterized in that, the desulfurizing agent in step (1) is iron oxide solid desulfurating agent.
3. the method for use coke-stove gas according to claim 1 and carbon dioxide enriched gas Joint Production fuel oil,
Characterized in that, in step (5), by controlling the amount of circulation air carbon dioxide come after controlling to convert
In synthesis gas, the ratio of hydrogen and carbon monoxide is 2:1.
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