CN110054153A - A kind of device of refinery factory refinery dry gas purification hydrogen manufacturing - Google Patents
A kind of device of refinery factory refinery dry gas purification hydrogen manufacturing Download PDFInfo
- Publication number
- CN110054153A CN110054153A CN201910311055.7A CN201910311055A CN110054153A CN 110054153 A CN110054153 A CN 110054153A CN 201910311055 A CN201910311055 A CN 201910311055A CN 110054153 A CN110054153 A CN 110054153A
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- Prior art keywords
- hydrogen
- unit
- gas
- refinery
- cryogenic separation
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000007789 gas Substances 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000000746 purification Methods 0.000 title claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 47
- 238000005057 refrigeration Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 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 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002737 fuel gas Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- C01B2203/048—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
- C01B2203/0495—Composition of the impurity the impurity being water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The present invention relates to a kind of devices of refinery factory refinery dry gas purification hydrogen manufacturing, including passing through the sequentially connected drying unit of pipeline, cryogenic separation unit, PSA Hydrogen Unit, the cryogenic separation unit is connect with refrigeration unit, is that the cryogenic separation unit freezes by refrigeration unit；The device is using technique after cryogenic separation and PSA combination, and under the premise of not increasing operating cost, the purity for obtaining hydrogen product is 99.9%, and the rate of recovery of hydrogen can improve；Secondly, hydrogen purity is much higher than original design parameter in unstripped gas after cryogenic system, the load and lighter hydrocarbons content of PSA device are reduced, is conducive to the smooth long term running of device, reduces maintenance and maintenance cost.
Description
Technical field
The present invention relates to the device for producing hydrogen field of petrochemical industry, specifically a kind of refinery factory refinery dry gas purifies the dress of hydrogen manufacturing
It sets.
Background technique
Crude oil is the lifeblood of modern industry, however is allowed to reserves because its is non-renewable and increasingly reduces, and exploitation difficulty is year by year
It increases and quality constantly reduces.The ratio of especially last decade, China's oil refining industry processing high-sulfur and heavy crude is increasingly
Greatly, the trend of crude oil heaviness and in poor quality is more obvious, but at the same time to pursue environmental benefit, country mentions oil quality
Higher requirement is gone out, therefore there is an urgent need to improve the level of crude oil processing to improve oil quality.
Hydrogen is that oil refining enterprise improves light oil yield, improves the essential raw material of product quality.Consumption in oil refining process
Hydrogen is concentrated mainly on catalytic reforming and hydrofining technology, the hydrogen consumption of whole process be typically in the range of crude quality 0.8%~
1.4%, if calculated according to 700,000,000 tons of estimated refining capacities of China in 2015, when hydrogen consumption takes the 1% of crude quality, consume hydrogen
Up to 7,000,000 tons of amount.
And face the fast development of hydrogen technique as refinery is various, hydrogenation plant quantity is increasing, and the requirement of hydrogen will
Further increase.Most of refinery factory reformer, hydrogenation of tar device, ethylbenzene hydrocarbonylation device, refinery factory be hydrogeneous to be had and contains
Hydrogen tail gas.Although hydrogen purity is different, these hydrogen containing tail gas require to carry out hydrogen recycling.Conventional method is at present
The purification that hydrogen is carried out using pressure swing adsorption, obtains the hydrogen of purity >=99.9%, hydrogen yield is generally 90% or so.
In practical startup procedure, due to unstripped gas fluctuation, device load variations etc., over time, PSA
Device operating parameter is gradually adjusted, it may appear that phenomena such as adsorption time shortens, and parses pressure rise, along with these situations
Occur, it is meant that the purity for recycling hydrogen gradually decreases, and the loss of hydrogen is gradually increased.This is mainly due to a small amount of hydro carbons point
Son is attached to molecular sieve inner surface, is not easy to parse, caused by causing molecular sieve to reduce hydro carbons adsorption effect after gradually accumulating.For
Change this state, the means used now are adsorbed first is that replacement adsorbent second is that repeatedly being purged parsing using hot nitrogen to improve
The activity of agent, both methods both increase the production cost of enterprise.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of devices of refinery factory refinery dry gas purification hydrogen manufacturing, to solve
Defect existing in the prior art.
The technical scheme to solve the above technical problems is that
A kind of refinery factory refinery dry gas purifies the device of hydrogen manufacturing, including passes through the sequentially connected drying unit of pipeline, deep cooling
Separative unit, PSA Hydrogen Unit, the cryogenic separation unit are connect with refrigeration unit, are the cryogenic separation by refrigeration unit
Unit freezes；The drying unit connects refinery factory reformer by pipeline, for receiving low point of big gas of humidity；Institute
Low point of gas is stated after dehumidifying, cryogenic separation unit is entered by pipeline with dry reformation hydrogen rich off gas；The cryogenic separation list
The condensation of C2, C3 heavy constituent, separation, condensed liquid in tail gas are delivered to fuel gas pipe network after passing through pipeline and rewarming by member,
Hydrogen-rich gas after separation is purified by pipeline to PSA Hydrogen Unit；
Further, the drying unit is internally provided with molecular sieve, using the principle of pressure-variable adsorption, is inhaled by molecular sieve
Tail gas dew point is down to -60 DEG C or less by the moisture in attached tail gas.
Further, the cryogenic separation unit includes rectifying column, gas-liquid separator and heat exchanger, by tail gas C2,
The heavy constituents such as C3 are condensed into liquid separation.
Further, in the hydrogen rich off gas that tail gas is sent out after cryogenic separation unit, hydrogen purity > 95%.
Further, the refrigeration unit can be using azeotrope refrigeration cycle, nitrogen swell refrigeration circulation and freon
Cryogen refrigeration circulation.
Further, the hydrogen-rich stripping gas that PSA Hydrogen Unit parses can be by entering in ice chest after compressor compresses
The methane that refrigerated separation contains, hydrogen rich gas after separation and to ice chest hydrogen rich off gas pipeline can reach the mesh of the recycling of hydrogen 100%
's.
The beneficial effects of the present invention are: the device is not increasing operating cost using technique after cryogenic separation and PSA combination
Under the premise of, the purity for obtaining hydrogen product is 99.9%, and the rate of recovery of hydrogen can improve；Secondly, after cryogenic system
Hydrogen purity is much higher than original design parameter in unstripped gas, reduces the load and lighter hydrocarbons content of PSA device, is conducive to fill
The smooth long term running set reduces maintenance and maintenance cost.
Detailed description of the invention
Fig. 1 is the device flow diagram that a kind of refinery factory refinery dry gas purifies hydrogen manufacturing；
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
As shown in Figure 1, a kind of device of refinery factory refinery dry gas purification hydrogen manufacturing,
Including passing through the sequentially connected drying unit of pipeline, cryogenic separation unit, PSA Hydrogen Unit, the cryogenic separation
Unit is connect with refrigeration unit, is that the cryogenic separation unit freezes by refrigeration unit；The drying unit passes through pipeline
Refinery factory reformer is connected, for receiving low point of big gas of humidity；The low point of gas is after dehumidifying, with dry reformation hydrogen-rich
Tail gas enters cryogenic separation unit by pipeline；C2, C3 heavy constituent in tail gas are condensed, are separated by the cryogenic separation unit, cold
For liquid after solidifying by being delivered to fuel gas pipe network after pipeline and rewarming, the hydrogen-rich gas after separation passes through pipeline to PSA
Hydrogen Unit is purified；
More specifically, the drying unit is internally provided with molecular sieve, using the principle of pressure-variable adsorption, is inhaled by molecular sieve
Tail gas dew point is down to -60 DEG C or less by the moisture in attached tail gas.
More specifically, the cryogenic separation unit includes rectifying column, gas-liquid separator and heat exchanger, by tail gas C2,
The heavy constituents such as C3 are condensed into liquid separation.
More specifically, in the hydrogen rich off gas that tail gas is sent out after cryogenic separation unit, hydrogen purity > 95%.
More specifically, the refrigeration unit can be using azeotrope refrigeration cycle, nitrogen swell refrigeration circulation and freon
Cryogen refrigeration circulation.
More specifically, the hydrogen-rich stripping gas that PSA Hydrogen Unit parses can be by entering in ice chest after compressor compresses
The methane that refrigerated separation contains, hydrogen rich gas after separation and to ice chest hydrogen rich off gas pipeline can reach the mesh of the recycling of hydrogen 100%
's.
Concrete operating principle:
To guarantee the purity and the rate of recovery of hydrogen, while the production cost of enterprise is reduced, using cryogenics and PSA technology
The hydrogen component in tail gas is reformed in the scheme recycling combined.Firstly, meeting the original of cryogenic purification index request after drying
Material gas enters cryogenic separation system, obtains hydrogen-rich product of the purity 95% or so and the fuel gas based on hydro carbons, and 95%
Hydrogen rich gas carry out hydrogen purification entering PSA device, obtain 99.9% hydrogen and utilized for owner.
Specifically, the device of a kind of refinery factory refinery dry gas of the invention purification hydrogen manufacturing, including drying unit, deep cooling point
From unit, PSA Hydrogen Unit, refrigeration unit.The big tail gas (such as low point of gas) of humidity that refinery factory reformer comes out and other
Refinery dry gas is removed water by drying unit, after dry tail gas (as reformed hydrogen rich off gas) is incorporated to drying unit by connecting pipe
Pipeline with it is dry after other tail gas converge, through pipeline to cryogenic separation unit, by tail gas in cryogenic separation unit
In the heavy constituents such as C2, C3 condense out separation, isolated liquid is after rewarming as fuel pneumatic transmission to fuel gas pipe network, hydrogen-rich
Tail gas enters the hydrogen that PSA Hydrogen Unit is made 99.9% or more by connecting pipe, and refrigeration unit is that cryogenic separation unit mentions
For cooling capacity required for cryogenic separation.
More specifically, hydrogeneous 40 DEG C of low point of temperature degree come out of refinery factory, pressure 2.55MPa, hydrogen purity 56%-
68%, by drying unit, by the moisture in molecular sieve absorption tail gas, dew point is down to -60 DEG C or less.Reform hydrogen-rich tail
40 DEG C of temperature degree, pressure 2.55MPa, hydrogen purity 90% enters ice chest after converging by low point of gas after pipeline and drying,
- 160--120 DEG C are cooled in ice chest, the C3 and C3+ in tail gas are condensed separation, and isolated liquid is after rewarming
As fuel pneumatic transmission to fuel gas pipe network；To 40 DEG C, pressure 2.50MPa, hydrogen purity is improved to 95% hydrogen rich off gas rewarming
More than, the hydrogen that PSA Hydrogen Unit is made 99.9% or more is entered by connecting pipe.PSA Hydrogen Unit desorbs normal
Stripping gas hydrogen content 56%-68% is pressed, may be incorporated into cryogenic separation unit after compressor compresses to 2.55MPa, is recycled, then
The recycling of hydrogen is close to 100%.Refrigeration unit provides cooling capacity required for cryogenic separation for cryogenic separation unit.
After group technology, the hydrogen purity into PSA device is not less than 95%, and fuel gas is most of in deep cooling part
Separate, compared with original PSA technology, increase the energy consumption for cooling of cryogenic separation, but save PSA resolution gas be pressurized into
Enter the energy consumption of fuel gas system.
After two kinds of process combinations, under the premise of not increasing operating cost, the purity for obtaining hydrogen product is 99.9%,
The rate of recovery of hydrogen can improve 5 percentage points or so, again return to cryogenic system entrance after the resolution gas compression that PSA mentions hydrogen and return
It receives, then the recycling of hydrogen is close to 100%.Secondly, hydrogen content is much higher than original in unstripped gas after cryogenic system
Design parameter reduces the load of PSA device and the inlet amount of lighter hydrocarbons, the more conducively smooth long term running of device, and reduces
Maintenance and maintenance cost.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of device of refinery factory refinery dry gas purification hydrogen manufacturing, it is characterised in that: including passing through the sequentially connected drying of pipeline
Unit, cryogenic separation unit, PSA Hydrogen Unit, the cryogenic separation unit are connect with refrigeration unit, are described by refrigeration unit
Cryogenic separation unit freezes；The drying unit connects refinery factory reformer by pipeline, big for receiving humidity
Low point of gas and other device hydrogen containing tail gas；The low point of gas and other device hydrogen containing tail gas are rich with dry reformation after dehumidifying
Hydrogen tail gas enters cryogenic separation unit by pipeline；C2, C3 heavy constituent in tail gas are condensed, are separated by the cryogenic separation unit,
For condensed liquid by being delivered to fuel gas pipe network after pipeline and rewarming, the hydrogen-rich gas after separation passes through pipeline extremely
PSA Hydrogen Unit is purified.
2. a kind of device of refinery factory refinery dry gas purification hydrogen manufacturing according to claim 1, it is characterised in that: the drying
Unit is internally provided with molecular sieve, using the principle of pressure-variable adsorption, by the moisture in molecular sieve absorption tail gas, by tail gas dew point
It is down to -60 DEG C or less.
3. a kind of device of refinery factory refinery dry gas purification hydrogen manufacturing according to claim 2, it is characterised in that: the deep cooling
Separative unit includes rectifying column, gas-liquid separator and heat exchanger, and C2, C3 heavy constituent in tail gas are condensed into liquid separation.
4. a kind of device of refinery factory refinery dry gas purification hydrogen manufacturing according to claim 3, it is characterised in that: the refrigeration
Unit is using azeotrope refrigeration cycle, nitrogen swell refrigeration circulation or freon cryogen refrigeration circulation.
5. a kind of device of refinery factory refinery dry gas purification hydrogen manufacturing according to claim 4, it is characterised in that: the PSA
The hydrogen-rich stripping gas that Hydrogen Unit parses can be by entering the first that refrigerated separation contains in ice chest after compressor again second compression
Alkane, hydrogen rich gas after separation and to ice chest hydrogen rich off gas pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910311055.7A CN110054153A (en) | 2019-04-18 | 2019-04-18 | A kind of device of refinery factory refinery dry gas purification hydrogen manufacturing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910311055.7A CN110054153A (en) | 2019-04-18 | 2019-04-18 | A kind of device of refinery factory refinery dry gas purification hydrogen manufacturing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110054153A true CN110054153A (en) | 2019-07-26 |
Family
ID=67319310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910311055.7A Pending CN110054153A (en) | 2019-04-18 | 2019-04-18 | A kind of device of refinery factory refinery dry gas purification hydrogen manufacturing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110054153A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115790078A (en) * | 2022-11-29 | 2023-03-14 | 北京恒泰洁能科技有限公司 | CO (carbon monoxide) 2 Liquefaction process and cold box |
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|---|---|---|---|---|
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-
2019
- 2019-04-18 CN CN201910311055.7A patent/CN110054153A/en active Pending
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|---|---|---|---|---|
| WO2006079025A1 (en) * | 2005-01-21 | 2006-07-27 | Exxonmobil Research And Engineering Company | Management of hydrogen in hydrogen-containing streams from hydrogen sources with rapid cycle pressure swing adsorption |
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| Title |
|---|
| 张卫东等: "石油石化300问", 中国石油大学出版社, pages: 255 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115790078A (en) * | 2022-11-29 | 2023-03-14 | 北京恒泰洁能科技有限公司 | CO (carbon monoxide) 2 Liquefaction process and cold box |
| CN115790078B (en) * | 2022-11-29 | 2023-09-29 | 北京恒泰洁能科技有限公司 | CO (carbon monoxide) 2 Liquefying process and cold box |
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