CN107164007A - A kind of method of non-stoichiometric isothermal synthetic natural gas - Google Patents
A kind of method of non-stoichiometric isothermal synthetic natural gas Download PDFInfo
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- CN107164007A CN107164007A CN201710340153.4A CN201710340153A CN107164007A CN 107164007 A CN107164007 A CN 107164007A CN 201710340153 A CN201710340153 A CN 201710340153A CN 107164007 A CN107164007 A CN 107164007A
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- 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
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Abstract
The invention discloses a kind of method of non-stoichiometric isothermal synthetic natural gas, belong to synthetic natural gas and technical field of coal chemical industry.Hydrogen-carbon ratio need not be adjusted by synthesis gas of this method from upstream, also without carbon dioxide removal, using the isothermal reactor series connection production natural gas of two-stage differential responses process, it is short, low without process gas circulation, energy consumption with applied widely, flow, small investment, operating condition are gentle, the controllable shifting heat of course of reaction, the features such as energy utilization efficiency is high.
Description
Technical field
The invention belongs to synthetic natural gas and technical field of coal chemical industry, and in particular to a kind of non-stoichiometric isothermal synthesis
The method of natural gas.
Background technology
The energy resource structure of China is " rich coal, oil-poor, few gas ", reinforcement and the strategy of sustainable development with environmental protection policy
Implement, China will be growing day by day to the demand of natural gas, it is contemplated that to the year two thousand twenty, demand reaches 200,000,000,000 m3, and the same period is natural
The m of the yield of gas about 1400~160,000,000,0003, therefore, natural gas imbalance between supply and demand will occurs in a few years from now on.At present, China has built
Large-scale natural gas from coal device into operation has 4 sets, is Datang gram flag, Liaoning Fuxin, Inner Mongol remittance energy, the magnificent coal system of Xinjiang celebrating respectively
Natural Gas Projects, scale amounts to 51,400,000,000 m3, in addition, currently carry out the natural gas from coal in previous work and planning
Project also has more than 10, and gross annual output can reach 1600 billion cubic meters.Coal synthetic natural gas is that one kind is readjusted the energy structure, delayed
One of effective behave of the market demand is solved, is also the demand for development as national strategy technological reserve.
In the technology of coal synthetic natural gas, main reaction is CO, CO2With H2Reaction generation CH4And H2O, belongs to strong
Exothermal reaction process.In current existing process unit, the content usually from CO in the crude synthesis gas of coal gasification is high, or even can
Up to 70% (butt), it is therefore desirable to first pass through sulphur-resistant conversion flow or from out-of-bounds introducing H2Adjust hydrogen-carbon ratio [(H2-CO2)/(CO+
CO2)], then by CO2、H2The synthesis gas that the acid gas purifying such as S unit is obtained meets the chemistry meter required for methanation reaction
Amount is than [(H2-CO2)/(CO+CO2)]=3, produce natural gas into synthesis gas.The technology of current international mature mainly has, moral
Strange (Lurgi) company methanation process in state Shandong, Top of Denmark rope (Topsoe) company's T REMPTMTechnology and Britain wear dimension (Davy)
The CRG technologies of company.They are all to use multi-stage fixed-bed adiabatic reactor connection in series-parallel, and hydrogen-carbon ratio is controlled in 3 or so, operation
Temperature is 250~700 DEG C, in intersegmental setting heat exchanger, reaction heat is removed, while byproduct steam.Have the disadvantage by substantial amounts of work
Skill gas circulates to obtain rational adiabatic temperature rise, and energy consumption is big；System flow is longer, it usually needs 4~5 stage reactors of series connection are obtained
High-purity natural gas.
In recent years, some domestic scholars are improved and studied to synthetic natural gas technique.Patent CN
102010284B is disclosed a kind of " method that coal base synthesizing methane metaplasia produces substitute natural gas ", synthesis gas need by conversion,
The stoichiometric proportion of purification regulation methanation reaction, system is using three sections of reactor series connection；Patent CN 103509618A are proposed
" a kind of coal based synthetic gas prepares the methanation process of synthetic natural gas ", the hydrogen-carbon ratio of synthesis gas is 2.8~3.1, using four sections
Adiabatic reactor, first paragraph outlet temperature is 450~550 DEG C, and second segment outlet temperature is 600~700 DEG C, the 3rd section of outlet temperature
Spend for 400~500 DEG C, the 4th section of outlet temperature is 250~350 DEG C, and flow is longer, need recycle compressor to add to circulating air
Pressure, system energy consumption is high.Patent CN 101649233 discloses " a kind of isothermal methanation process for producing synthetic natural gas ", at least
Two-stage above methanation reaction is needed, the wherein first order uses adiabatic methanation reactor, and subsequent stages use isothermal reactor
Carry out methanation.Adiabatic methanation reactor operation temperature is high, and equipment and pipe material require high, and catalyst life is short.
The content of the invention
It is an object of the invention to part in view of the shortcomings of the prior art, and provide a kind of non-stoichiometric synthesis
The method of natural gas, mainly by change furnace, methanation furnace, CH4Purifying plant, gas-liquid separator and the series connection of many heat exchangers etc.
Equipment is constituted.Synthesis gas into device need not adjust hydrogen-carbon ratio, using the isothermal reactor string of two-stage differential responses process
Connection production natural gas, heating efficiency high the features such as low with small investment, energy consumption.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method of non-stoichiometric isothermal synthetic natural gas, this method is by from upstream acid gas removal dress
The synthesis gas put enters the temperature shift reactions such as change furnace progress after being mixed after being heated up into synthesis hot-air heater with high steam, obtain
To hydrogen-rich process gas；Described hydrogen-rich process gas enters methanation furnace and occurs first after the cooling of the first boiler water heater
Alkylation reaction, gained methane rich process gas is cooled by synthesis hot-air heater, into after the cooling of the second boiler water heater, warp
Desalination water heater is crossed to be further cooled, it is cooled subsequently into cooler, enter after gas-liquid separator separates lime set, gas
Mutually remove CH4Purifying plant removes CO2Etc. foreign gas, the natural gas and high-purity CO of high-purity methane are obtained2Gas, liquid phase is gone
Out-of-bounds reuse.
In the above method：It is divided into two strands from HP boiler water out-of-bounds, one is gone after the heating of the first boiler water heater
Remove change furnace by-product high-pressure steam；Another stock-traders' know-how crosses demethanization stove by-product high-pressure steam after the heating of the second boiler water heater；
Two bursts of saturated high pressure steams of gained are sent to out-of-bounds after drum is mixed.In some preferred technical schemes：By-product high pressure is steamed
Steam pressure grade adjustable range is 2.5~6.5MPa.
In some preferred technical schemes：Mixed gas temperature control into change furnace between 200~300 DEG C,
Change furnace is isothermal reactor, and operation temperature is controlled at 250~350 DEG C.
In some preferred technical schemes：Process gas temperature control into methanation furnace is in 200~300 DEG C, methane
Change stove is isothermal reactor, and operation temperature is controlled at 280~350 DEG C.
In the above method, obtained from upstream synthesis gas by coal gasification into acid gas removal plants after recuperation of heat
, process does not need sulphur-resistant conversion procedure regulation hydrogen-carbon ratio, and acid gas removal plants only need desulfurization, without decarburization.
Described synthesis gas first with mixed from high steam out-of-bounds after, enter back into change furnace, the non-sulphur-resistant conversion of generation
Reaction.
In technical solution of the present invention：Described CH4Purify as complete goods supplying equipment, specifically using pressure-variable adsorption, deep cooling point
From technologies such as, UF membranes.
In technical solution of the present invention：The source of described synthesis gas includes coal water slurry gasification, recirculating fluidized bed gasification, fine coal
The devices such as gasification.
Beneficial effects of the present invention：Non-stoichiometric isothermal synthesis of natural gas method of the present invention, it is not necessary to adjust
Save synthesis gas stoichiometric proportion, using two-stage isothermal reactor connect, with applied widely, flow it is short, without process gas
Circulation, energy consumption are low, and small investment, operating condition are gentle, the controllable shifting heat of course of reaction, the features such as energy utilization efficiency is high.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention.
In figure：1- synthesizes hot-air heater, and 2- change furnaces, 3- the first boiler water heaters, 4- methanation furnaces, 5- second reacts
Stove, the reacting furnaces of 6- the 3rd, the waste heat boilers of 7- second, 8- gas-liquid separators, 9-CH4Purifying plant, 10- drums.
Embodiment
With reference to embodiment, the present invention will be further described, but protection scope of the present invention not limited to this：
A kind of system of non-stoichiometric isothermal synthetic natural gas, the system include change furnace (2), methanation furnace (4),
CH4The pipeline phase of input and high steam at the top of purifying plant (9) and gas-liquid separator (8), described change furnace (2)
Even, the pipeline of the synthesis gas from upstream acid gas removal plants is connected with the input of synthesis hot-air heater (1), synthesis gas
The output end of heater (1) by the pipeline of high steam with being connected at the top of change furnace (2), described change furnace (2) bottom
Output end is connected by the first boiler water heater (3) with the top input of methanation furnace (4), described methanation furnace (4)
The output end of bottom passes sequentially through synthesis hot-air heater (1), the second boiler water heater (5), desalination water heater (6), cooling
Device (7) is connected with gas-liquid separator (8)；The top output port and CH of described gas-liquid separator (8)4Purifying plant (9) is connected,
Described CH4(9) output ends of purifying plant are high-purity CO2Gas output end, another output end is high-purity methane
Natural gas output end, the bottom output end of described gas-liquid separator (8) goes out-of-bounds reuse for liquid phase.
The output channel of high pressure boiler water supply respectively with the second boiler water heater (5) and the first boiler water heater (3)
It is connected, the first described boiler water heater (3) is connected by change furnace (2) with drum (10), and the second described boiler water adds
Hot device (5) is also connected by methanation furnace (4) with drum (10), the output end of described drum (10) and the output of saturated vapor
End is connected.
A kind of method that non-stoichiometric isothermal synthetic natural gas is carried out using said system, specific steps such as example 1
~3.Example 1：
The raw gas that coal water slurry gasification is obtained obtains 22400Nm after waste heat recovery and acid gas removal plants3/h
Synthesis gas, temperature is 30 DEG C, and pressure is 3.6MPa, is constituted as CO：44.01%, H2:35.87%, CO2：19.5%, CH4：
0.03%, N2：0.46%, AR:0.12%, it is warming up into synthesis hot-air heater after 200 DEG C, and from 1200kg/h out-of-bounds
(280 DEG C, 4.0MPa) high steam is mixed, and enters back into the temperature shift reactions such as change furnace generation, the operation temperature control of change furnace
At 250 DEG C, obtain after being cooled to 220 DEG C through the first boiler water heater rich in density of hydrogen for 39.6% process gas, enter
Carry out isothermal methanation reaction to methanation furnace, the operation temperature of methanation furnace is controlled at 320 DEG C, obtain be rich in methane concentration
30% process gas is cooled to after 138 DEG C into the second boiler water heater after synthesizing hot-air heater cooling, enters desalination
Water heater is further cooled to 70 DEG C, is cooled to subsequently into cooler after 40 DEG C and is entered gas-liquid separator separates lime set
Afterwards, gas phase removes CH4Purifying plant removes CO2Etc. foreign gas, 4680Nm is obtained3/ h, purity for 96~99% natural gas and
9744Nm3/ h purity is more than 99% high-purity CO2Gas, liquid phase amounts to 433kg/h submittings and out-of-bounds recycled；From out-of-bounds
HP boiler water is divided into two strands, and one goes after the first boiler water heat temperature raising to go change furnace by-product 770kg/h saturated high pressure steams
(234 DEG C, 3.0MPa)；It is high that another stock-traders' know-how crosses demethanization stove by-product 18860kg/h saturations after the heating of the second boiler water heater
Press steam (234 DEG C, 3.0MPa)；Two bursts of saturated high pressure steams of gained amount to 19630kg/h after drum is mixed and sent to out-of-bounds.
Example 2：
The raw gas that recirculating fluidized bed gasification is obtained is obtained after waste heat recovery and acid gas removal plants
22400Nm3/ h synthesis gas, temperature is 30 DEG C, and pressure is 2.75MPa, is constituted as CO：38.42%, H2:29.41%, CO2：
29.94%, CH4：6.91%, N2：0.24%, AR:0.09%, it is warming up into synthesis hot-air heater after 200 DEG C, and from boundary
Outer 1200kg/h (280 DEG C, 4.0MPa) high steam mixing, enters back into the temperature shift reactions such as change furnace generation, change furnace
Operation temperature is controlled at 260 DEG C, obtains being cooled to through the first boiler water heater for 33.4% process gas rich in density of hydrogen
After 220 DEG C, enter methanation furnace and carry out isothermal methanation reaction, the operation temperature of methanation furnace is controlled at 330 DEG C, obtains richness
After being cooled down containing methane concentration for 32.7% process gas through synthesis hot-air heater, 138 are cooled into the second boiler water heater
After DEG C, enter desalination water heater and be further cooled to 70 DEG C, gas is entered after being cooled to 40 DEG C subsequently into cooler
After liquid/gas separator separation lime set, gas phase removes CH4Purifying plant removes CO2Etc. foreign gas, 5508Nm is obtained3/ h purity be 96~
99% natural gas and 10382Nm3/ h purity is high-purity CO more than 99%2Gas, liquid phase amounts to 346kg/h submittings and out-of-bounds returned
Receive and utilize；It is divided into two strands from HP boiler water out-of-bounds, one removes change furnace by-product after removing the first boiler water heat temperature raising
600kg/h saturated high pressure steams (224 DEG C, 2.5MPa)；Another stock-traders' know-how crosses demethanization stove after the heating of the second boiler water heater
By-product 15180kg/h saturated high pressure steams (224 DEG C, 2.5MPa)；Two bursts of saturated high pressure steams of gained are common after drum is mixed
Meter 19630kg/h is sent to out-of-bounds.
Example 3：
The raw gas that coal gasification is obtained obtains 22400Nm after waste heat recovery and acid gas removal plants3/ h is closed
Into gas, temperature is 30 DEG C, and pressure is 3.75MPa, is constituted as CO：70.03%, H2:23.54%, CO2：5.85%, CH4：
10ppM, N2：0.46%, AR:0.12%, it is warming up into synthesis hot-air heater after 200 DEG C, and from 5000kg/h out-of-bounds
(280 DEG C, 4.0MPa) high steam is mixed, and enters back into the temperature shift reactions such as change furnace generation, the operation temperature control of change furnace
At 280 DEG C, obtain after being cooled to 220 DEG C through the first boiler water heater rich in density of hydrogen for 40% process gas, enter
Methanation furnace carries out isothermal methanation reaction, and the operation temperature of methanation furnace is controlled at 350 DEG C, obtain be rich in methane concentration
28.7% process gas is cooled to after 138 DEG C into the second boiler water heater, entered de- after synthesizing hot-air heater cooling
Brine heater is further cooled to 70 DEG C, be cooled to subsequently into cooler after 40 DEG C enter gas-liquid separator separates coagulate
After liquid, gas phase removes CH4Purifying plant removes CO2Etc. foreign gas, 5476Nm is obtained3/ h purity for 96~99% natural gas and
11746Nm3/ h purity is more than 99% high-purity CO2Gas, liquid phase amounts to 769kg/h submittings and out-of-bounds recycled；From out-of-bounds
HP boiler water is divided into two strands, and one goes after the first boiler water heat temperature raising to go change furnace by-product 3960kg/h saturated high pressure steams
(250 DEG C, 4.0MPa)；It is high that another stock-traders' know-how crosses demethanization stove by-product 21300kg/h saturations after the heating of the second boiler water heater
Press steam (250 DEG C, 4.0MPa)；Two bursts of saturated high pressure steams of gained amount to 25260kg/h after drum is mixed and sent to out-of-bounds.
The principle for simply illustrating the invention described in above-described embodiment and specification, does not therefore limit this hair
Bright protection domain, on the premise of the invention spirit and scope are not departed from, this technology invention also have various change and
Improve, these changes and improvements all fall within the protetion scope of the claimed invention.Part that the present invention does not relate to is and prior art
It is identical or can be realized using prior art.
Claims (8)
1. a kind of method of non-stoichiometric isothermal synthetic natural gas, it is characterised in that：This method is will be acid from upstream
The synthesis gas of gas removal plants enters after being mixed after being heated up into synthesis hot-air heater (1) with high steam into change furnace (2)
The temperature shift reactions such as row, obtain hydrogen-rich process gas；Described hydrogen-rich process gas by the first boiler water heater (3) cooling after,
Enter methanation furnace (4) and occur methanation reaction, gained methane rich process gas is cooled by synthesis hot-air heater (1), entered
Enter after the cooling of the second boiler water heater (5), be further cooled by desalination water heater (6), subsequently into cooler (7)
It is cooled, enter after gas-liquid separator (8) separation lime set, gas phase removes CH4Purifying plant (9) removes CO2Etc. foreign gas, obtain
To the natural gas and high-purity CO of high-purity methane2Gas, liquid phase goes out-of-bounds reuse.
2. the method for non-stoichiometric isothermal synthetic natural gas according to claim 1, it is characterised in that：From out-of-bounds
HP boiler water be divided into two strands, one go the first boiler water heater (3) heat up after remove change furnace (2) by-product high-pressure steam；
Another stock-traders' know-how crosses demethanization stove (4) by-product high-pressure steam after the heating of the second boiler water heater (5)；Two bursts of saturation high pressures of gained
Steam is sent to out-of-bounds after drum (10) mixing.
3. a kind of method of non-stoichiometric isothermal synthetic natural gas according to claim 1, it is characterised in that：Come from
The synthesis gas of upstream enters acid gas removal unit after waste heat recovery by coal gasification and obtained, and the process needs not move through resistance to
Sulphur converter unit adjusts hydrogen-carbon ratio, and acid gas removal unit only needs desulfurization, without decarburization.
4. a kind of method of non-stoichiometric isothermal synthetic natural gas according to claim 1, it is characterised in that：By height
After pressure steam is mixed with synthesis gas, change furnace is entered back into, and occur non-sulfur-tolerant water gas shift.
5. the method for non-stoichiometric isothermal synthetic natural gas according to claim 2, it is characterised in that：By-product high pressure
Steam pressure grade adjustable range is 2.5~6.5MPa.
6. the method for non-stoichiometric isothermal synthetic natural gas according to claim 1, it is characterised in that：Into conversion
The mixed gas temperature control of stove (2) is between 200~300 DEG C, and change furnace (2) is isothermal reactor, and operation temperature control exists
250~350 DEG C.
7. the method for non-stoichiometric isothermal synthetic natural gas according to claim 1, it is characterised in that：Into methane
Change the process gas temperature control of stove (4) at 200~300 DEG C, methanation furnace (4) is isothermal reactor, and operation temperature is controlled 280
~350 DEG C.
8. the method for non-stoichiometric isothermal synthetic natural gas according to claim 1, it is characterised in that：Described CH4
Purify as complete goods supplying equipment, pressure-variable adsorption, cryogenic separation or membrane separation technique can be used.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384647A (en) * | 2018-10-25 | 2019-02-26 | 中石化南京工程有限公司 | A kind of transformation methanolizing integrated production equipment and method |
| CN109609221A (en) * | 2018-12-21 | 2019-04-12 | 惠生工程（中国）有限公司 | A kind of semi-coke furnace tail gas fine de-sulfur and isothermal methanation process |
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| CN1195020A (en) * | 1997-04-03 | 1998-10-07 | 湖南化学工业设计院 | Technique for producing city coal gas by using water gas |
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| CN109609221A (en) * | 2018-12-21 | 2019-04-12 | 惠生工程（中国）有限公司 | A kind of semi-coke furnace tail gas fine de-sulfur and isothermal methanation process |
| CN109609221B (en) * | 2018-12-21 | 2021-02-05 | 惠生工程（中国）有限公司 | Semi-coke furnace tail gas fine desulfurization and isothermal methanation process |
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Application publication date: 20170915 |