CN106967463A - A kind of raw material desulfurization and hydrogenation system and technique for oven gas preparing liquefied natural gas - Google Patents
A kind of raw material desulfurization and hydrogenation system and technique for oven gas preparing liquefied natural gas Download PDFInfo
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- CN106967463A CN106967463A CN201710255507.5A CN201710255507A CN106967463A CN 106967463 A CN106967463 A CN 106967463A CN 201710255507 A CN201710255507 A CN 201710255507A CN 106967463 A CN106967463 A CN 106967463A
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- intersegmental
- thermosistor
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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Abstract
The present invention relates to a kind of raw material desulfurization and hydrogenation system and technique for oven gas preparing liquefied natural gas, the system includes：Oil strain groove, steam heater, pre- hydrogenation converter, first intersegmental thermosistor, second intersegmental thermosistor, one-level hydro-conversion device, moderate temperature desulphurization groove, secondary hydrogenation converter, zinc oxide desulfurization groove, product heat exchanger, raw material feed channel connection oil strain groove import from upstream, oil strain groove outlet conduit sequentially enters steam heater, first intersegmental thermosistor, product heat exchanger, second intersegmental thermosistor, then pre- hydrogenation converter import is connected, pre- hydrogenation converter outlet pipeline enters the first intersegmental thermosistor, then it is sequentially connected one-level hydro-conversion device, moderate temperature desulphurization groove, moderate temperature desulphurization groove outlet conduit enters the second intersegmental thermosistor, secondary hydrogenation converter import is connected afterwards, secondary hydrogenation converter outlet connects zinc oxide desulfurization groove, the outlet conduit of zinc oxide desulfurization groove enters product heat exchanger, then downstream section is connected.
Description
Technical field
The present invention relates to a kind of raw material desulfurization and hydrogenation system and technique for oven gas preparing liquefied natural gas.
Background technology
Desulfurization and hydrogenation flow for the raw material desulfurization and hydrogenation technique of oven gas preparing liquefied natural gas is generally such as Fig. 1
It is shown, unstripped gas (normal temperature) is heated to 200 into heating furnace F0201 after oil strain groove V0201 oil strains, pre- desulfurizer R0201~
260 DEG C, into pre- about 300~320 DEG C of hydrogenation converter R0202, R0202 outlet temperature, into one-level hydro-conversion device
380~400 DEG C of R0203, R0203 outlet temperature, sequentially enters moderate temperature desulphurization groove R0204, secondary hydrogenation converter R0205, goes out
420~440 DEG C of temperature of mouth, into zinc oxide desulfurization groove R0206,420~440 DEG C of outlet temperature enters downstream section.The heating
The shortcoming of stove flow：1. being influenceed greatly by feed gas composition, each temperature of reactor of system should not be controlled；2. heating furnace consumes fuel gas
(unstripped gas), virtually reduces yield, adds operating cost；3. it is high to enter downstream section temperature, increase downstream section operation
Cost；4. increase is taken up an area, do not allow advancing equipment in the range of circle, 15m centered on heating furnace.
It is intersegmental to change
The content of the invention
It is used for oven gas system liquefaction day there is provided one kind present invention aim to address above-mentioned problems of the prior art
The raw material desulfurization and hydrogenation system and technique of right gas.
In order to solve the above-mentioned technical problem the present inventor, has made intensive studies, as a result it was unexpectedly found that, by setting
Count the intersegmental heat-exchange system and flow of a kind of raw material desulfurization for oven gas preparing liquefied natural gas and hydrogenation, it is possible to achieve aobvious
Write energy-saving and production-increase, reduce the purpose of cost, this completes the present invention.
The present invention is by using intersegmental heat-exchange system and flow, compared to prior art heating furnace flow, can control every
The reaction temperature of individual reactor, the fuel that heating furnace can be saved again changes into target finished product, reduces equipment and once invests, and increases
Adding system benefit.
Therefore, the invention provides a kind of raw material desulfurization and hydrogenation system for oven gas preparing liquefied natural gas, its
Including：Oil strain groove, in advance steam heater, hydrogenation converter, the first intersegmental thermosistor, the second intersegmental thermosistor, one-level hydrogenation turn
Change device, moderate temperature desulphurization groove, secondary hydrogenation converter, zinc oxide desulfurization groove, product heat exchanger,
Raw material feed channel connection oil strain groove import wherein from upstream, oil strain groove outlet conduit sequentially enters steam heating
Device, the first intersegmental thermosistor, product heat exchanger, the second intersegmental thermosistor, then connect pre- hydrogenation converter import, and pre- hydrogenation turns
Change device outlet conduit and enter the first intersegmental thermosistor, then connect one-level hydro-conversion device import, the outlet of one-level hydro-conversion device
Moderate temperature desulphurization groove import is connected, moderate temperature desulphurization groove outlet conduit enters the second intersegmental thermosistor, gone out after the second intersegmental thermosistor
Connect secondary hydrogenation converter import, secondary hydrogenation converter outlet connection zinc oxide desulfurization groove, the outlet of zinc oxide desulfurization groove
Pipeline enters product heat exchanger, then connects downstream section.
Further, upstream is gas holder and/or compression section, and downstream section is methane synthesizing section.
Invention further provides a kind of raw material desulfurization for oven gas preparing liquefied natural gas and the raw material of hydrogenation
Desulfurization and hydrogenation technique, comprise the following steps：
Unstripped gas from gas holder and compression section, including H255~60 volumes %, CH420~27 volumes %, CO 4~
8 volumes %, CO21.5~3 volumes %, N23~8 volume %, volume %, O of more than C2 unsaturated hydrocarbons 2~42<0.8 volume %,
Inorganic sulfur≤50mg/Nm3(rate and inorganic sulphur content scope such as 20-50mg/Nm3), organic sulfur≤300mg/Nm3(organic sulfur content model
Enclose such as 100-300mg/Nm3) 35~45 DEG C of temperature, such as 38-42 DEG C or about 40 DEG C, it is heated to about respectively through steam heater
100-150 DEG C, preferably 110-140 DEG C, the first intersegmental thermosistor be heated to about 100-180 DEG C, preferably 120-170 DEG C, product changes
Hot device is heated to about 150-250 DEG C, preferably 170-230 DEG C, the second intersegmental thermosistor be warming up to 200~260 DEG C, preferably 210-
250 DEG C, pre-hydrotreating, pre- hydrogenation converter outlet temperature about 295- are carried out into pre- hydrogenation converter (iron-molybdic catalyst)
325 DEG C, preferably from about 300~320 DEG C, through the first intersegmental 280-320 DEG C of temperature adjustment of thermosistor heat exchange, enter after preferably 290-310 DEG C
One-level hydro-conversion device (iron-molybdic catalyst) carries out hydrotreating, and 330~380 DEG C of one-level hydro-conversion device outlet temperature enters one
Such as 340-370 DEG C of step, conversion ratio >=97% of organic sulfur is (so that inorganic sulfur is close to 290mg/Nm3), it is de- subsequently into middle temperature
Inorganic sulfur is absorbed in sulphur groove (Zinc oxide desulfurizer) desulfurization, gas, and inorganic sulfur is down to 30mg/Nm3Hereinafter, through the second intersegmental tune
Warm device exchanges heat temperature adjustment to entering secondary hydrogenation converter (nickel molybdenum catalyst) after 300~350 DEG C, 330~380 DEG C of outlet temperature,
Conversion ratio >=99% of organic sulfur, into zinc oxide desulfurization groove, total sulfur content is below 0.1ppm, temperature in the oven gas after desulfurization
About 330~380 DEG C of degree, exchanges heat through product heat exchanger to entering methane synthesizing section after 190~280 DEG C.
In the present invention, it is iron commonly used in the art that the catalyst used in converter, one-level hydro-conversion device is hydrogenated with advance
Used catalyst is nickel molybdenum catalyst commonly used in the art in molybdenum catalyst, secondary hydrogenation converter, is used in moderate temperature desulphurization groove
Desulfurizing agent be Zinc oxide desulfurizer.
It is in hydrogenation converter, one-level hydro-conversion device, secondary hydrogenation converter typical reaction formula in advance：
R-SH+H2=RH+H2S
R-S-R'+2H2=R'H+RH+H2S
C4H4S+4H2=C4H10+H2S
COS+H2=CO+H2S
CS2+4H2=2H2S+CH4
O2+2H2=2H2O
Zinc oxide desulfurizer absorbs H2S reaction equation is：
ZnO+H2S=ZnS+H2O(g)
Had the advantage that using the intersegmental heat exchange process of the present invention：
(1) present invention saves the fuel gas needed for heating furnace, target product yield is increased；
(2) investment of device is reduced；
(3) device land used is saved；
(4) it is energy-saving；
(5) intersegmental heat exchange process can preferably control the temperature of each reactor.
Brief description of the drawings
Fig. 1 is the desulfurization of the raw material desulfurization and hydrogenation technique for oven gas preparing liquefied natural gas of prior art and added
Hydrogen flow chart.
Fig. 2 is the raw material desulfurization and desulfurization and the hydrogenation of hydrogenation technique for oven gas preparing liquefied natural gas of the invention
Flow chart.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing.
As shown in Fig. 2 the present invention relates to a kind of raw material desulfurization and hydrogenation system for oven gas preparing liquefied natural gas,
Including：Oil strain groove V0201, steam heater E0205, pre- hydrogenation converter R0202, the first intersegmental thermosistor E0201, second segment
Between thermosistor E0203, one-level hydro-conversion device R0203, moderate temperature desulphurization groove R0204, secondary hydrogenation converter R0205, zinc oxide
Desulfurizer R0206, product heat exchanger E0202,
Raw material feed channel connection oil strain groove V0201 imports wherein from upstream, oil strain groove outlet conduit sequentially enters steaming
Vapour heater E0205, the first intersegmental thermosistor E0201, product heat exchanger E0202, the second intersegmental thermosistor E0203, Ran Houlian
Pre- hydrogenation converter R0202 imports are connect, pre- hydrogenation converter outlet pipeline enters the first intersegmental thermosistor E0201, then connected
One-level hydro-conversion device R0203 imports, one-level hydro-conversion device R0203 outlets connection moderate temperature desulphurization groove R0204 imports, middle temperature takes off
Sulphur groove R0204 outlet conduits enter the second intersegmental thermosistor E0203, and two grades of connection adds after going out the second intersegmental thermosistor E0203
Hydrogen converter R0205 imports, secondary hydrogenation converter R0205 outlets connection zinc oxide desulfurization groove R0206, zinc oxide desulfurization groove
R0206 outlet conduit enters product heat exchanger E0202, then connects downstream section, namely for methane synthesizing section.
Comprised the following steps using the raw material desulfurization and hydrogenation technique of said system：
Unstripped gas from gas holder and compression section, including H255~60 volumes %, CH420~27 volumes %, CO 4~
8 volumes %, CO21.5~3 volumes %, N23~8 volume %, volume %, O of more than C2 unsaturated hydrocarbons 2~42<0.8 volume %,
Inorganic sulfur≤50mg/Nm3(rate and inorganic sulphur content scope such as 20mg-50mg/Nm3), organic sulfur≤300mg/Nm3(organic sulfur content
Scope such as 100-300mg/Nm3) 35~45 DEG C of temperature, e.g., from about 40 DEG C, by oil strain groove V0201, then heated through steam
Device E0205 is heated to about 100-150 DEG C, preferably 110-140 DEG C, the first intersegmental thermosistor E0201 be heated to about 100-180 DEG C,
120-170 DEG C, product heat exchanger E0202 be heated to about 150-250 DEG C, preferably 170-230 DEG C, the second intersegmental thermosistor E0203
200~260 DEG C are warming up to, preferably 210-250 DEG C, is carried out into pre- hydrogenation converter R0202 (iron-molybdic catalyst) at pre- hydrogenation
Reason, pre- about 295-325 DEG C of hydrogenation converter outlet temperature, exchanges heat through the first intersegmental thermosistor E0201 by preferably from about 300~320 DEG C
280-320 DEG C of temperature adjustment, one-level hydro-conversion device R0203 (iron-molybdic catalyst) is entered after preferably 290-310 DEG C and carries out hydrotreating,
330~380 DEG C of one-level hydro-conversion device outlet temperature, further such as 340-370 DEG C, conversion ratio >=97% of organic sulfur, so
Enter inorganic sulfur in moderate temperature desulphurization groove R0204 (Zinc oxide desulfurizer) desulfurization, gas afterwards to be absorbed, inorganic sulfur is down to 30mg/Nm3
Hereinafter, temperature adjustment is exchanged heat through the second intersegmental thermosistor E0203 to entering secondary hydrogenation converter R0205 (nickel molybdenums after 300~350 DEG C
Catalyst), 330~380 DEG C of outlet temperature, conversion ratio >=99% of organic sulfur, into zinc oxide desulfurization groove R0206, through desulfurization
Total sulfur content is below 0.1ppm in oven gas afterwards, and temperature is about 330~380 DEG C, is exchanged heat through product heat exchanger to 190~280
Enter methane synthesizing section after DEG C.
Embodiment 1
Raw material desulfurization and hydrogenation are carried out using present system, with 30000Nm3Exemplified by/h coke-stove gas LNG projects,
The heating furnace flow of prior art as shown in Figure 1 about consumes fuel 2000Nm3/ h, using the intersegmental heat exchange process of the present invention,
This part of fuel can 2000 yuan/t of fecund LNG 3600t/a, LNG calculate, 7,200,000 yuan can be increased income every year.
In addition, reducing 1 heating furnace apparatus compared with Fig. 1 of prior art, in apparatus of the present invention, increase by 4 heat exchange
Device, one-time investment reduces about 2,000,000 yuan.
Do not allowed after advancing equipment, Optimizing Flow in the range of circle, 15m centered on heating furnace, the present invention removes heating furnace,
1 mu of device land used has been saved compared with prior art.
During normal production, unstripped gas is heated to catalyst light-off temperature using self heat, present invention saves heating
Fuel gas needed for stove, reaches energy-saving purpose.
In addition, intersegmental heat exchange process of the invention can preferably control the temperature of each reactor.
Claims (4)
1. a kind of raw material desulfurization and hydrogenation system for oven gas preparing liquefied natural gas, it includes：Oil strain groove, steam heating
Device, in advance hydrogenation converter, the first intersegmental thermosistor, the second intersegmental thermosistor, one-level hydro-conversion device, moderate temperature desulphurization groove, two grades
Hydro-conversion device, zinc oxide desulfurization groove, product heat exchanger,
Wherein from upstream raw material feed channel connection oil strain groove import, oil strain groove outlet conduit sequentially enter steam heater,
First intersegmental thermosistor, product heat exchanger, the second intersegmental thermosistor, then connect pre- hydrogenation converter import, pre- hydro-conversion
Device outlet conduit enters the first intersegmental thermosistor, then connects one-level hydro-conversion device import, and the outlet of one-level hydro-conversion device connects
Connect moderate temperature desulphurization groove import, moderate temperature desulphurization groove outlet conduit enters the second intersegmental thermosistor, go out after the second intersegmental thermosistor and connect
Connect secondary hydrogenation converter import, secondary hydrogenation converter outlet connection zinc oxide desulfurization groove, the outlet of zinc oxide desulfurization groove
Road enters product heat exchanger, then connects downstream section.
2. the raw material desulfurization and hydrogenation system according to claim 1 for oven gas preparing liquefied natural gas, wherein on
It is methane synthesizing section to swim as gas holder and/or compression section, and downstream section.
3. a kind of raw material desulfurization and hydrogenation technique for oven gas preparing liquefied natural gas, comprises the following steps：
The unstripped gas from gas holder and compression section of 35~45 DEG C of temperature, including H255~60vol%, CH420~
4~8vol% of 27vol%, CO, CO21.5~3vol%, N22~4vol% of 3~8vol%, more than C2 unsaturated hydrocarbons, O2<
0.8vol%, inorganic sulfur≤50mg/Nm3, organic sulfur≤300mg/Nm3, after oil strain groove, heated respectively through steam heater
To 100-150 DEG C, the first intersegmental thermosistor be heated to 100-180 DEG C, product heat exchanger be heated to 150-250 DEG C, it is second intersegmental
Thermosistor is warming up to 210-250 DEG C, and pre-hydrotreating, pre- hydrogenation converter outlet temperature 295- are carried out into pre- hydrogenation converter
325 DEG C, enter the progress hydrotreating of one-level hydro-conversion device, one-level after the first intersegmental 280-320 DEG C of temperature adjustment of thermosistor heat exchange
330~380 DEG C of hydro-conversion device outlet temperature, conversion ratio >=97% of organic sulfur, subsequently into moderate temperature desulphurization groove desulfurization, gas
Middle inorganic sulfur is absorbed, and inorganic sulfur is down to 30mg/Nm3Hereinafter, temperature adjustment is exchanged heat through the second intersegmental thermosistor to after 300~350 DEG C
Into secondary hydrogenation converter, 330~380 DEG C of outlet temperature, conversion ratio >=99% of organic sulfur, into zinc oxide desulfurization groove,
Total sulfur content is below 0.1ppm in oven gas after desulfurization, and temperature is 330~380 DEG C, exchange heat to 190 through product heat exchanger~
Enter methane synthesizing section after 280 DEG C.
4. raw material desulfurization according to claim 3 and hydrogenation technique, wherein：
The unstripped gas from gas holder and compression section of 38-42 DEG C of temperature through steam heater by being heated to respectively after oil strain groove
110-140 DEG C, the first intersegmental thermosistor be heated to 120-170 DEG C, product heat exchanger be heated to 170-230 DEG C, second it is intersegmental adjust
Warm device is warming up to 210-250 DEG C, and pre-hydrotreating is carried out into pre- hydrogenation converter, and pre- hydrogenation converter outlet temperature 300~
320 DEG C, enter the progress hydrotreating of one-level hydro-conversion device, one-level after the first intersegmental 290-310 DEG C of temperature adjustment of thermosistor heat exchange
340-370 DEG C of hydro-conversion device outlet temperature.
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Cited By (4)
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| CN107699296A (en) * | 2017-10-25 | 2018-02-16 | 山西潞安煤基精细化学品有限公司 | A kind of one-level hydrogenation pre-converter for setting up heating pipeline |
| CN110203884A (en) * | 2018-09-10 | 2019-09-06 | 西安华江环保科技股份有限公司 | Reactive hydrogen fine de-sulfur device and technique in a kind of catalysis reaction |
| CN110684570A (en) * | 2019-10-13 | 2020-01-14 | 内蒙古恒坤化工有限公司 | Process for online adding cold shock pipeline for fine desulfurization pre-hydrogenation catalyst |
| CN110804468A (en) * | 2019-11-27 | 2020-02-18 | 浙江天禄环境科技有限公司 | Dry desulfurization process for synthesis gas |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699296A (en) * | 2017-10-25 | 2018-02-16 | 山西潞安煤基精细化学品有限公司 | A kind of one-level hydrogenation pre-converter for setting up heating pipeline |
| CN110203884A (en) * | 2018-09-10 | 2019-09-06 | 西安华江环保科技股份有限公司 | Reactive hydrogen fine de-sulfur device and technique in a kind of catalysis reaction |
| CN110684570A (en) * | 2019-10-13 | 2020-01-14 | 内蒙古恒坤化工有限公司 | Process for online adding cold shock pipeline for fine desulfurization pre-hydrogenation catalyst |
| CN110804468A (en) * | 2019-11-27 | 2020-02-18 | 浙江天禄环境科技有限公司 | Dry desulfurization process for synthesis gas |
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