CN105861086B - Process method for co-producing liquefied natural gas, methanol and liquid ammonia by using gasified coal gas and coke oven gas - Google Patents
Process method for co-producing liquefied natural gas, methanol and liquid ammonia by using gasified coal gas and coke oven gas Download PDFInfo
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- CN105861086B CN105861086B CN201610305951.9A CN201610305951A CN105861086B CN 105861086 B CN105861086 B CN 105861086B CN 201610305951 A CN201610305951 A CN 201610305951A CN 105861086 B CN105861086 B CN 105861086B
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- 239000007789 gas Substances 0.000 title claims abstract description 243
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 126
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000003949 liquefied natural gas Substances 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 title claims abstract description 26
- 239000003034 coal gas Substances 0.000 title claims description 6
- 239000011335 coal coke Substances 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 171
- 239000001257 hydrogen Substances 0.000 claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 73
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 37
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000000571 coke Substances 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- 230000015572 biosynthetic process Effects 0.000 claims description 33
- 238000003786 synthesis reaction Methods 0.000 claims description 33
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 29
- 238000002309 gasification Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- WWYNJERNGUHSAO-XUDSTZEESA-N (+)-Norgestrel Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 WWYNJERNGUHSAO-XUDSTZEESA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 12
- 239000013589 supplement Substances 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- 125000001741 organic sulfur group Chemical group 0.000 claims description 7
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 claims description 6
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000003139 buffering effect Effects 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 230000009469 supplementation Effects 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 4
- 238000010521 absorption reaction Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229960004424 carbon dioxide Drugs 0.000 description 16
- 230000006978 adaptation Effects 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000005261 decarburization Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- HNBFUFIYQWYCDM-UHFFFAOYSA-N oxygen(2-) sulfane titanium(4+) Chemical compound [O--].[O--].S.[Ti+4] HNBFUFIYQWYCDM-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/046—Purification by cryogenic separation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Industrial Gases (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation By Low-Temperature Treatments (AREA)
Abstract
The process method for co-producing liquefied natural gas, methanol and liquid ammonia by using gasified gas and coke oven gas provided by the invention is characterized in that the liquefied natural gas, the methanol and the liquid ammonia are co-produced by using the coke oven gas, LNG is produced by using the coke oven gas, the methanol is produced by using the coke oven gas, the synthetic ammonia, cryogenic liquefaction separation, liquid nitrogen washing and the like are organically linked together through reasonable configuration, LNG is produced by using component methane in the coke oven gas, the methanol is produced by using component hydrogen and carbon monoxide in the coke oven gas, and the liquid ammonia is produced by using the hydrogen and nitrogen in the coke oven gas.
Description
Technical field
The invention belongs to coal chemical technology more particularly to a kind of utilization gasification gas and coke-stove gas co-production of liquefied are natural
The process of gas, methanol and liquefied ammonia.
Background technique
Coke-stove gas is also known as oven gas, refer to coal for coking in coke oven after high-temperature retorting, in output coke and coke
Generated a kind of imflammable gas while oil product, is the byproduct of coking industry.The calorific value of coke-stove gas is higher, usually
Fuel or town gas as high temperature industrial furnace.
As environmental requirement is gradually increased, the utilization rate of new coking industry permit standard clear stipulaties coke-stove gas is wanted
More than 98%, while coking industry recessed market, excess capacity is serious, and people come to realise the huge exploitation value of coke-stove gas
Value, therefore many coke-stove gas utilization technologies are had developed, such as coke-stove gas preparing liquefied natural gas, coke-stove gas methanol etc..
However, the main component of coke-stove gas is hydrogen (55-60%) and methane (23-27%), there are also an a small amount of oxidations
The components such as carbon, carbon dioxide, nitrogen have the characteristics that " hydrogen-rich lacks carbon ".It such as turns out a produce, can lead only with monotechnics
Cause constituent part that cannot make full use of, the tail gas containing hydrogen partial need to separately find a way out or can only be used as fuel.In addition, production
Single product faces the biggish market risk, and controllability is poor.
Therefore, the existing resource situation of comprehensive consideration coal chemical enterprise (exhaust gas gives up admittedly), by existing technology (coke-stove gas
LNG processed, coke-stove gas methanol, synthesis ammonia, cryogenic liquefying separation, liquid nitrogen washing) organic connections together, and take certain skill
Art means and regulating measure make each component reach suitable ratio, so that coproduction multiple product, on the one hand may be implemented resource
Efficiently make full use of, reduce pollution to environment, on the other hand can successfully manage production by adjusting the yield of each product
The influence that product price fluctuation is brought greatly improves the ability that coal chemical enterprise resists the market risk.
Summary of the invention
In view of this, in order to overcome the drawbacks of the prior art and problem, the present invention, which provides, a kind of utilizes gasification gas and coke
The process of producer gas co-production of liquefied natural gas, methanol and liquefied ammonia.
A kind of process using gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia, is successively wrapped
Include following step:
Step S10: the coke-stove gas is sent into gas holder buffering, stablizes its pressure；
Step S20: the coke-stove gas after in step S10 is pressurized to 2.0~2.2Mpa；
Step S30: being inorganic sulfur by the organic sulfur conversion in the coke-stove gas after step S20；
Step S40: continue the coke-stove gas after step S30 to be compressed to 2.5~3Mpa；
Step S50: sour gas of the removing in the coke-stove gas after step S40, the sour gas includes: titanium dioxide
Sulphur, hydrogen sulfide, carbon dioxide；
Step S60: its dew point is down to -65~-70 DEG C by moisture of the removing in the coke-stove gas after step S50；
Step S70: gas composition of the separation in the coke-stove gas after step S60 respectively obtains LNG, hydrogen and nitrogen gas, Fu Yi
Carbonoxide gas and hydrogen rich gas.
In some embodiments, further include following step:
Step S180: the hydrogen and nitrogen gas is sent to ammonia synthesis system, and the richness carbon monoxide gas and hydrogen rich gas are sent to methanol conjunction
At system.
In some embodiments, in step S10, methane volumetric score is 20~30% in the coke-stove gas, hydrogen
Fraction be 40~60%, carbon monoxide volume fraction be 8~15%, surplus be nitrogen, carbon dioxide, micro organic sulfur,
SO2, tar, dust and vapor.
In some embodiments, in step S40, continue the coke-stove gas after step S30 to be compressed to 2.5~3Mpa,
Specifically:
Coke-stove gas is continued to be compressed to 2.5~3MPa using reciprocating or centrifugal compressor.
In some embodiments, in step S50, the sour gas in the coke-stove gas after step S40 is removed, specifically
Are as follows:
Using the sour gas in wet processing removing coke-stove gas, the absorbent in the wet processing is that MDEA is molten
Liquid.
In some embodiments, in step S60, the moisture in the coke-stove gas after step S50 is removed, by its depoint depression
To -70 DEG C, specifically:
Using the moisture in molecular sieve absorbing process removing coke-stove gas, its dew point is down to -65~-70 DEG C.
In some embodiments, in step S70, the gas composition in the coke-stove gas after step S60 is separated, respectively
To LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas, specifically:
The gas composition point in coke-stove gas is realized using the technology that cryogenic liquefying, cryogenic rectification and liquid nitrogen washing combine
From obtaining LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas.
In some embodiments, coke-stove gas is realized using the technology that cryogenic liquefying, cryogenic rectification and liquid nitrogen washing combine
In gas composition separation, obtain LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas, include the following steps:
Cooling: the coke-stove gas after step S60 is cooled to -150~-165 DEG C；
Dehydrogenation: hydrogen and carbon monoxide, nitrogen are removed using the technique of cryogenic rectification, isolated methane rich logistics
Domethanizing column is sent to further to refine；Isolated hydrogen rich gas a part is sent to liquid nitrogen washing and is refined, and another part is sent to methanol
Synthesis system；
Demethanation: using the technique of cryogenic rectification by the impurity removal in methane rich logistics, methane tower tower bottom obtains pure
LNG product, demethanizer column overhead tail gas be carbon monoxide, the impurity includes hydrogen, nitrogen, carbon monoxide；
Liquid nitrogen washing: carbon monoxide, methane gas in liquid nitrogen washing removing process gas obtain pure hydrogen and nitrogen mixing
Gas-hydrogen and nitrogen gas, after liquid nitrogen washing is handled, hydrogen and nitrogen gas is sent to ammonia synthesis system hydrogen rich off gas；Liquid nitrogen washing tail-gas then imports demethanation
Tail gas is sent to system for methanol synthesis.
In some embodiments, before carrying out step S10, also successively include the following steps:
Rich carbon gas supplement: supplementing carbon-rich gas in the coke-stove gas, and the carbon-rich gas is coke gasification gas, converter
Coal gas, blast furnace gas, coal synthesis gas be one such or several mixing；
Nitrogen supplement: the nitrogen required supplementation with is sent to liquefaction separation device, after cooling liquefaction, then is sent to liquid nitrogen washing conduct
Absorbent uses, while importing the raw material in hydrogen and nitrogen gas as synthesis ammonia system；
Nitrogen fine tuning: the hydrogen and nitrogen gas obtained through liquid nitrogen washing supplements suitable nitrogen；
Carbon dioxide fine tuning: suitable carbon dioxide is supplemented in the rich CO gas that liquefaction separation device obtains.
Process provided by the invention using gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia
Using coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia, by reasonable disposition by coke-stove gas LNG, coke-stove gas system
Methanol synthesizes the organic connections such as ammonia, cryogenic liquefying separation, liquid nitrogen washing together, the component methane being utilized respectively in coke-stove gas
LNG is produced, using the component hydrogen and carbon monoxide production methanol in coke-stove gas, utilizes hydrogen gas in coke oven gas and nitrogen raw
Liquefied ammonia is produced, compared with the existing technology, the present invention has an advantage that
(1), the application comprehensively utilizes prior art technology, is not needing to be completely separated coke-stove gas all components
In the case where, it realizes maximally utilizing for coke-stove gas, greatly reduces operating cost.Meanwhile because prior art is whole
It is mature technology, this guarantees the feasibilities of process route.
(2), liquid nitrogen washing technology is introduced into deep cooling process for separating by the application, ensure that the purity of unstripped gas, is avoided one
The inert gases such as carbonoxide, methane bring ammonia synthesis system into.
(3), present applicant proposes multicomponents to supplement micro-tensioning system, enhances the controllability and adaptation of whole set process system
Property, adaptation range is extensive.
Detailed description of the invention
Fig. 1 is that low temperature provided by the invention utilizes gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia
Process step flow chart.
Fig. 2 is that low temperature provided by the invention utilizes gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia
Process process principle figure.
Fig. 3 is that the technology combined using cryogenic liquefying, cryogenic rectification and liquid nitrogen washing realizes the gas group in coke-stove gas
The step flow chart of part separation.
Fig. 4 is that Fig. 2 provided by the invention is deep cooling process for separating schematic diagram.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give better embodiment of the invention.The above is only a preferred embodiment of the present invention, is not intended to limit of the invention special
Sharp range, it is all using equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content, directly or
It connects and is used in other related technical areas, be included within the scope of the present invention.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more
Any and all combinations of relevant listed item.
Fig. 1 and Fig. 2 are please referred to, a preferred embodiment of the present invention provides a kind of utilization gasification gas and coke-stove gas coproduction liquid
The process for changing natural gas, methanol and liquefied ammonia, successively includes the following steps:
Step S10: the coke-stove gas is sent into gas holder buffering, stablizes its pressure；
Preferably, methane content (volume fraction) is 20~30% in the coke-stove gas, and hydrogen content is 40~60%,
Carbon monoxide content is 8~15%, and surplus is nitrogen, carbon dioxide, micro organic sulfur, SO2, tar, dust and vapor.
It is appreciated that coke-stove gas is sent into gas holder buffering, it is ensured that pressure is steady for the stabilization for guaranteeing subsequent handling
It is fixed, so that subsequent technique is reliable and stable；
Step S20: the coke-stove gas after in step S10 is pressurized to 2.0~2.2Mpa；
It is appreciated that the coke-stove gas after in step S10 can be pressurized to 2.0~2.2Mpa by compression process.
Step S30: being inorganic sulfur by the organic sulfur conversion in the coke-stove gas after step S20；
It is appreciated that can be realized the organic sulfur conversion in coke-stove gas by hydro-conversion is inorganic sulfur.
Step S40: continue the coke-stove gas after step S30 to be compressed to 2.5~3Mpa；
Preferably, coke-stove gas is continued to be compressed to 2.5~3MPa using reciprocating or centrifugal compressor.
Step S50: sour gas of the removing in the coke-stove gas after step S40, the sour gas includes: titanium dioxide
Sulphur, hydrogen sulfide, carbon dioxide；
Preferably, the sour gas in coke-stove gas is removed using wet processing, the absorbent in the wet processing is
MDEA solution.
Step S60: its dew point is down to -65~-70 DEG C by moisture of the removing in the coke-stove gas after step S50；
Preferably, using the moisture in molecular sieve absorbing process removing coke-stove gas, its dew point is down to -70 DEG C.
Step S70: gas composition of the separation in the coke-stove gas after step S60 respectively obtains LNG, hydrogen and nitrogen gas, Fu Yi
Carbonoxide gas and hydrogen rich gas.
It is appreciated that LNG obtained above is sold as product；Hydrogen and nitrogen gas is sent to ammonia synthesis system, for producing liquefied ammonia
Product；Rich carbon monoxide gas is first pressurized to 2.0~2.5MPa (pressure is matched with hydrogen rich gas), is sent after mixing with hydrogen rich gas to methanol
Synthesis system, for producing methanol product, methanol purge gas sends coke oven back to.
Preferably, the gas in coke-stove gas is realized using the technology that cryogenic liquefying, cryogenic rectification and liquid nitrogen washing combine
Component separation obtains LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas.
Specifically, referring to Fig. 3, realizing coke-oven coal using the technology that cryogenic liquefying, cryogenic rectification and liquid nitrogen washing combine
Gas composition separation in gas obtains LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas, includes the following steps:
Step S71: the coke-stove gas after step S60 cooling: is cooled to -150~-165 DEG C；
Step S72: dehydrogenation: hydrogen and carbon monoxide, nitrogen are removed using the technique of cryogenic rectification, isolated richness
Methane stream is sent to domethanizing column and further refines；Isolated hydrogen rich gas a part is sent to liquid nitrogen washing and is refined, another part
It send to system for methanol synthesis；
Step S73: demethanation: using the technique of cryogenic rectification by the impurity removal in methane rich logistics, methane tower tower bottom
Pure LNG product is obtained, demethanizer column overhead tail gas is carbon monoxide, and the impurity includes hydrogen, nitrogen, carbon monoxide；
Step S74: liquid nitrogen washing: carbon monoxide, methane gas in liquid nitrogen washing removing process gas, obtain pure hydrogen and
Nitrogen mixture-hydrogen and nitrogen gas, after liquid nitrogen washing is handled, hydrogen and nitrogen gas is sent to ammonia synthesis system hydrogen rich off gas；Liquid nitrogen washing tail-gas then converges
Enter demethanation tail gas to send to system for methanol synthesis.
Further, referring to Fig. 4, also successively including the following steps: before carrying out step S10
Rich carbon gas supplement: supplementing carbon-rich gas in the coke-stove gas, and the carbon-rich gas is coke gasification gas, converter
Coal gas, blast furnace gas, coal synthesis gas be one such or several mixing；It is appreciated that since coke-stove gas has, " hydrogen-rich is few
The characteristics of carbon ", the tail gas composition after removing methane tend not to meet the needs of methanol-fueled CLC, it is therefore desirable to which carbon system is mended in design
System.Carbon-rich gas can there are many source, such as coal gas of converter, blast furnace gas, coal synthesis gas, coke gasification gas etc..According to rich carbon
The impurity content of gas and pressure are different, and access system if pressure is lower fills into gas holder, such as pressure in place respectively
Before higher accessible secondary booster or before MDEA desulfurization and decarburization.Rich carbon gas can be coke gasification gas, coal synthesis gas, converter coal
Gas, blast furnace gas.
Nitrogen supplement: the nitrogen required supplementation with is sent to liquefaction separation device, after cooling liquefaction, then is sent to liquid nitrogen washing conduct
Absorbent uses, while importing the raw material in hydrogen and nitrogen gas as synthesis ammonia system；
It is appreciated that the nitrogen of supplement send to liquid nitrogen washing and uses as absorbent, while importing hydrogen again after cooling liquefaction
As the raw material of synthesis ammonia system in nitrogen, there are two the effects of aspect for tool.Nitrogen can be derived from air separation unit.
Nitrogen fine tuning: the hydrogen and nitrogen gas obtained through liquid nitrogen washing supplements suitable nitrogen；
It is appreciated that the hydrogen and nitrogen gas obtained through liquid nitrogen washing, composition cannot fully meet the optimal proportion of ammonia synthesis, need
A small amount of nitrogen is supplemented, for forming fine tuning.Nitrogen can be derived from air separation unit.
Carbon dioxide fine tuning: suitable carbon dioxide is supplemented in the rich CO gas that liquefaction separation device obtains.
It is appreciated that richness CO gas and hydrogen rich gas converge after unstripped gas as system for methanol synthesis, C/Hratio cannot be complete
The optimal proportion of full up foot methanol-fueled CLC, requires supplementation with a small amount of carbon dioxide, for forming fine tuning.Carbon dioxide can be derived from work
The decarbonization device of skill upstream.
Process provided by the invention using gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia
Using coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia, by reasonable disposition by coke-stove gas LNG, coke-stove gas system
Methanol synthesizes the organic connections such as ammonia, cryogenic liquefying separation, liquid nitrogen washing together, the component methane being utilized respectively in coke-stove gas
LNG is produced, using the component hydrogen and carbon monoxide production methanol in coke-stove gas, utilizes hydrogen gas in coke oven gas and nitrogen raw
Liquefied ammonia is produced, compared with the existing technology, the present invention has an advantage that
(1), the application comprehensively utilizes prior art technology, is not needing to be completely separated coke-stove gas all components
In the case where, it realizes maximally utilizing for coke-stove gas, greatly reduces operating cost.Meanwhile because prior art is whole
It is mature technology, this guarantees the feasibilities of process route.
(2), liquid nitrogen washing technology is introduced into deep cooling process for separating by the application, ensure that the purity of unstripped gas, is avoided one
The inert gases such as carbonoxide, methane bring ammonia synthesis system into.
(3), present applicant proposes multicomponents to supplement micro-tensioning system, enhances the controllability and adaptation of whole set process system
Property, adaptation range is extensive.
Embodiment
As shown in table 1, pressure is 1~5kPa (G) to typical coke-stove gas composition, and temperature is about 40 DEG C, and flow is
34000Nm3/h。
The volume of 1 coke-stove gas of table forms
| H2 | CO | CO2 | CH4 | CnHm | N2 |
| 53.82 | 10.74 | 4.68 | 22.57 | 3.15 | 4.63 |
| O2 | H2S | It is total | Tar and dust | Vapor | |
| 0.41 | It is micro | 100 | It is micro | Saturation |
Technique as shown in Figure 1, coke-stove gas is first fed into gas holder buffering, after pressure stabilisation to utilize compressor boost extremely
2.0MPa or so carries out hydro-conversion processing, then carries out secondary booster to 2.8MPa, is sent into MDEA desulfurization and decarburization device and carries out
Purified treatment, then give to drying device and remove moisture, it is then fed into cryogenic liquefying separator and carries out depth separation, each portion of gained
Gas is divided to be sent to ammonia synthesis system and system for methanol synthesis, while output LNG product respectively.In the feed conditions of the present embodiment
Under, hundred million Nm3/a of LNG0.858,12.34 ten thousand t/a of methanol, 10.16 ten thousand t/a of liquefied ammonia can be produced.
Hydrogen content in coke-stove gas is higher, and carbon monoxide, nitrogen equal size are lower, in the present embodiment, quasi- to adopt
Benefit carbon, pressure 3.0MPa are carried out with coke gasification gas, temperature is 40 DEG C, flow 82000Nm3/h, is formed such as 2 institute of table
Show.
The volume of 2 coke gasification gas of table forms
| H2 | CO | CO2 | CH4 | CnHm | N2 |
| 41.2 | 25.5 | 29 | 3.5 | - | 0.3 |
| O2 | H2S | It is total | Tar and dust | Vapor | |
| 0.3 | 0.2 | 100 | It is micro | Saturation |
After the pressurized gasification of coke obtains the processes processing such as gasification gas, then transformed, PSA decarburization, pressure is about
2.8MPa is merged together before MDEA desulfurization and decarburization device with coke-stove gas.
Pure nitrogen gas from air separation unit about 7800Nm3/h is sent into cryogenic separation device, and gradually cool down liquefaction through heat exchanger
Afterwards, liquid nitrogen washing tower is sent by the impurity such as carbon monoxide, methane and Hydrogen Separation, while ammonia synthesis system is sent into together with hydrogen.
In addition, 1500Nm3/h pure nitrogen gas need to be supplemented before ammonia synthesis system to adjust the feed composition of ammonia synthesis system.
For the feed composition for adjusting system for methanol synthesis, 900Nm3/h pure carbon dioxide need to be supplemented before system for methanol synthesis.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. a kind of process using gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia, feature exist
In successively including the following steps:
Step S10: the coke-stove gas is sent into gas holder buffering, stablizes its pressure；
Step S20: the coke-stove gas after in step S10 is pressurized to 2.0~2.2Mpa；
Step S30: being inorganic sulfur by the organic sulfur conversion in the coke-stove gas after step S20；
Step S40: continue the coke-stove gas after step S30 to be compressed to 2.5~3Mpa；
Step S50: sour gas of the removing in coke-stove gas after step S40, the sour gas include: sulfur dioxide,
Hydrogen sulfide, carbon dioxide；
Step S60: its dew point is down to -65~-70 DEG C by moisture of the removing in the coke-stove gas after step S50；
Step S70: gas composition of the separation in the coke-stove gas after step S60 respectively obtains LNG, hydrogen and nitrogen gas, richness one and aoxidizes
Carbon gas and hydrogen rich gas；
Before carrying out step S10, also successively include the following steps:
Rich carbon gas supplement: supplementing carbon-rich gas in the coke-stove gas, and the carbon-rich gas is coke gasification gas, converter coal
Gas, blast furnace gas, coal synthesis gas be one such or several mixing；
Nitrogen supplement: the nitrogen required supplementation with is sent to liquefaction separation device, after cooling liquefaction, then is sent to liquid nitrogen washing as absorption
Agent uses, while importing the raw material in hydrogen and nitrogen gas as synthesis ammonia system；
Nitrogen fine tuning: the hydrogen and nitrogen gas obtained through liquid nitrogen washing supplements suitable nitrogen；
Carbon dioxide fine tuning: suitable carbon dioxide is supplemented in the rich CO gas that liquefaction separation device obtains；
In step S70, the gas composition in the coke-stove gas after step S60 is separated, respectively obtains LNG, hydrogen and nitrogen gas, a rich oxygen
Change carbon gas and hydrogen rich gas, specifically:
Gas composition separation in coke-stove gas is realized using the technology that cryogenic liquefying, cryogenic rectification and liquid nitrogen washing combine, is obtained
To LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas；
Gas composition separation in coke-stove gas is realized using the technology that cryogenic liquefying, cryogenic rectification and liquid nitrogen washing combine, is obtained
To LNG, hydrogen and nitrogen gas, rich carbon monoxide gas and hydrogen rich gas, include the following steps:
Cooling: the coke-stove gas after step S60 is cooled to -150~-165 DEG C；
Dehydrogenation: hydrogen and carbon monoxide, nitrogen are removed using the technique of cryogenic rectification, isolated methane rich logistics is sent to
Domethanizing column further refines；Isolated hydrogen rich gas a part, which is sent, to be refined another part to liquid nitrogen washing and send to methanol-fueled CLC system
System；
Demethanation: using the technique of cryogenic rectification by the impurity removal in methane rich logistics, methane tower tower bottom obtains pure LNG
Product, demethanizer column overhead tail gas are carbon monoxide, and the impurity includes hydrogen, nitrogen, carbon monoxide；
Liquid nitrogen washing: carbon monoxide, methane gas in liquid nitrogen washing removing process gas obtain pure hydrogen and 0 nitrogen mixture-
Hydrogen and nitrogen gas, after liquid nitrogen washing is handled, hydrogen and nitrogen gas is sent to ammonia synthesis system hydrogen rich off gas；Liquid nitrogen washing tail-gas then imports demethanation tail gas
It send to system for methanol synthesis.
2. utilizing the technique of gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia as described in claim 1
Method, which is characterized in that further include following step:
Step S180: the hydrogen and nitrogen gas is sent to ammonia synthesis system, and the richness carbon monoxide gas and hydrogen rich gas are sent to methanol-fueled CLC system
System.
3. utilizing the technique of gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia as described in claim 1
Method, which is characterized in that in step S10, methane volumetric score is 20~30% in the coke-stove gas, and hydrogen volume score is
40~60%, carbon monoxide volume fraction be 8~15%, surplus be nitrogen, carbon dioxide, micro organic sulfur, SO2, tar,
Dust and vapor.
4. utilizing the technique of gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia as described in claim 1
Method, which is characterized in that in step S40, continue the coke-stove gas after step S30 to be compressed to 2.5~3Mpa, specifically:
Coke-stove gas is continued to be compressed to 2.5~3MPa using reciprocating or centrifugal compressor.
5. utilizing the technique of gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia as described in claim 1
Method, which is characterized in that in step S50, the sour gas in the coke-stove gas after step S40 is removed, specifically:
Using the sour gas in wet processing removing coke-stove gas, the absorbent in the wet processing is MDEA solution.
6. utilizing the technique of gasification gas and coke-stove gas co-production of liquefied natural gas, methanol and liquefied ammonia as described in claim 1
Method, which is characterized in that in step S60, remove the moisture in the coke-stove gas after step S50, its dew point is down to -65
~-70 DEG C, specifically:
Using the moisture in molecular sieve absorbing process removing coke-stove gas, its dew point is down to -70 DEG C.
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| CN106811238A (en) * | 2017-01-06 | 2017-06-09 | 河北中翔能源有限公司 | A kind of process of preparing LNG from coke oven tail gas and hydrogen rich off gas liquefied ammonia |
| CN107244651A (en) * | 2017-06-09 | 2017-10-13 | 杨皓 | A kind of blast furnace tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN107235473A (en) * | 2017-06-09 | 2017-10-10 | 杨皓 | A kind of carbon black tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN107215848A (en) * | 2017-06-09 | 2017-09-29 | 杨皓 | A kind of carbon black tail gas and calcium carbide stove exhaust combined production of ammonia alcohol synthesis gas process |
| CN107267706B (en) * | 2017-07-06 | 2019-02-15 | 中冶华天包头设计研究总院有限公司 | Coal gas of converter cooling system and its cooling means |
| CN109206295A (en) * | 2018-09-17 | 2019-01-15 | 陕西黑猫焦化股份有限公司 | A kind of synthesis ammonolysis gassing matches the method and system of coke-stove gas methanol |
| CN109595878B (en) * | 2018-12-10 | 2021-02-09 | 内蒙古博大实地化学有限公司 | Method for co-producing liquid carbon dioxide by synthetic ammonia and urea |
| CN111676069B (en) * | 2020-06-18 | 2021-05-04 | 中冶西北工程技术有限公司 | Coke oven gas purification system |
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