CN103740426B - The method substituting Sweet natural gas is produced in synthetic gas methanation - Google Patents
The method substituting Sweet natural gas is produced in synthetic gas methanation Download PDFInfo
- Publication number
- CN103740426B CN103740426B CN201210392935.XA CN201210392935A CN103740426B CN 103740426 B CN103740426 B CN 103740426B CN 201210392935 A CN201210392935 A CN 201210392935A CN 103740426 B CN103740426 B CN 103740426B
- Authority
- CN
- China
- Prior art keywords
- reactor
- gas
- temperature
- logistics
- methanation reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of synthetic gas methanation and produce the method substituting Sweet natural gas, mainly solve prior art and there is high-temperature methanation reaction cycle gas consumption greatly, energy consumption of compressor is high, H in products substitution Sweet natural gas
2or CO
2the problem that component exceeds the quata.The present invention is comprised the following steps by employing: a) provide high-temperature methanation reaction zone, and described high-temperature methanation reaction zone comprises the reactor of n level series connection; B) raw material of synthetic gas is divided into n section to enter the entrance of each stage reactor in high-temperature methanation reaction zone respectively; The logistics Vn flowed out from last step reactor outlet is divided into Vn ' and Vn ", logistics Vn ' is circulated to first step reactor inlet after compression; C) provide low temperature methanation reaction district, described low temperature methanation reaction district comprises the reactor of m level series connection; D) add containing CO in the arbitrary stage reactor of low temperature methanation unit
2logistics I, the technical scheme obtaining products substitution Sweet natural gas after reaction solves this problem preferably, can be used for synthetic gas system and substitutes in the industrial production of Sweet natural gas.
Description
Technical field
The present invention relates to a kind of synthetic gas methanation and produce the method substituting Sweet natural gas (SNG).
Background technology
Sweet natural gas is a kind of energy of high-efficiency cleaning, can make up petroleum resources present situation day by day in short supply to a certain extent.But China's natural gas demand increases fast in recent years, and China's natural gas reserves are less.It is predicted, the demand of Natural Gas In China in 2015 will reach 1700 ~ 2,100 hundred million Nm
3, and the gas production of the same period can only reach 1,400 hundred million Nm
3, insufficiency of supply-demand about 30,000,000,000 ~ 70,000,000,000 Nm
3.For solving China's natural gas imbalance between supply and demand, other alternative route must be sought.
Coal resources in China is horn of plenty comparatively, and the method therefore the synthetic gas methanation from gasification being substituted Sweet natural gas (SNG) can alleviate the demand of China to Sweet natural gas effectively.
More external companies started to study coal to SNG from the seventies in last century, the at present industrialized coal to SNG factory only having big plain in u.s.a company in 1984 to build up, Lurgi company of Germany carries out technological design for this device, the G1-85 type catalyzer of its methanator original adoption BASF AG, the CRG catalyzer of Davy company of Britain of converting afterwards.The coal to SNG technique of Davy company of Britain adopts oneself CRG catalyzer, this catalyzer to have special high-temperature stability and to unstripped gas H
2the requirement of/CO ratio is not strict, and therefore this coal to SNG technique Raw gas directly can enter methanation unit after purification.The TREMP of Topsoe company of Denmark
tMthe full name of technique is circulating energy-saving methanation process, and the heat recovery rate of this technique is higher, to H
2/ CO ratio requires relatively stricter, and catalyzer still has catalytic activity at 700 DEG C.Lurgi company of Germany coal to SNG technique is the SNG technique coal-based processed that unique industrialization at present runs, and therefore this technique has abundanter technical scale service experience.At present the emphasis that coal-based SNG processed studies is remained for the exploitation of efficient methanation catalyst and methanation process.
The main composition of synthetic gas is CO, CO
2and H
2, produce a large amount of methane by methanation reaction, the reaction occurred in methane building-up process mainly comprises:
CO+3H
2→CH
4+H
2O+206.2KJ/mol(1)
CO
2+4H
2→CH
4+2H
2O+165KJ/mo(2)
CO+H
2O→H
2+CO
2+41KJ/mol(3)
At H
2mainly react when excessive (1) and (2), and the water that reaction generates can react (3) again with CO.Reaction (1) and (2) are all strong exothermal reactions, in the methane building-up reactions of purified synthesis gas every 1% CO methane synthesize thermal insulation warming up to 73 DEG C, the CO of every 1%
2the thermal insulation warming about 60 DEG C of methane synthesis.
Initial methane content is also depended in methanation reaction temperature rise, single-stage methanation reaction can cause thermal insulation warming △ T to be 400 ~ 600 DEG C, low temperature can make reaction carry out to positive dirction, and high temperature can suppress the generation of methane, and if not in time the heat produced in reaction process is removed, can cause damage to catalyst activity.The main method controlling the temperature rise of methanation reaction process adopts the component loops of methanation reaction product or uses cold logistics to remove methanation reaction liberated heat.
Document US4133825A discloses high-temperature methanation part and adopts single-stage reactor, and reactor outlet is divided into two portions, and a part mixes with high-temperature methanation reactor feedstocks as circulation gas, and another part is as the charging of low temperature methanator.Document CN87102871 discloses the methanator that there is cooled catalyst bed cooling system an inside, methanation reaction is there is in synthetic gas in methanator, there is water to utilize methanation reaction liberated heat to produce steam by the cooling system entering methanator after a series of preheating simultaneously, remove reaction heat.But still there is the problem that high-temperature methanation reaction cycle gas consumption is large and energy consumption of compressor is high in above-mentioned technology.
In addition, in actual industrial device, (the H in synthetic gas
2-CO
2)/(CO+CO
2) although mol ratio regulated by water gas shift reactor, in running, inevitably fluctuation is difficult to make (H
2-CO
2)/(CO+CO
2) ratio is stabilized in ideal value 3.0, the fluctuation of raw material composition can affect the H in products substitution Sweet natural gas
2, CO and CO
2content, and due to methanation device reaction process long, longer time lag certainly will be there is by being reflected to product to the component proportion adjustment of material synthesis gas.
In sum, it is large to there is high-temperature methanation reaction cycle gas consumption in prior art, and energy consumption of compressor is high, H in products substitution Sweet natural gas (SNG)
2or CO
2the problem that component exceeds the quata.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists high-temperature methanation reaction cycle gas consumption greatly, and energy consumption of compressor is high, H in products substitution Sweet natural gas
2or CO
2the problem that component exceeds the quata, provides a kind of new synthetic gas methanation and produces the method substituting Sweet natural gas.It is low that the method has circulating flow rate, and recycle compressor energy consumption is low, H in products substitution Sweet natural gas
2or CO
2component content is stablized, H
2≤ 1.0%, CO
2≤ 3%, the advantage that product high-grade-goods rate is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method substituting Sweet natural gas is produced in a kind of synthetic gas methanation, comprises the following steps:
A) provide high-temperature methanation reaction zone, described high-temperature methanation reaction zone comprises the reactor of n level series connection, n >=2;
B) containing H
2, CO, CO
2and H
2the raw material of synthetic gas of O is divided into n section to enter the entrance of each stage reactor in high-temperature methanation reaction zone respectively; Except last step reactor, the logistics flowed out from reactor outlet at different levels enters next stage reactor inlet respectively; The logistics Vn flowed out from last step reactor outlet is divided into Vn ' and Vn ", logistics Vn ' is circulated to first step reactor inlet after compression;
C) provide low temperature methanation reaction district, described low temperature methanation reaction district comprises the reactor of m level series connection, m>=2; Except last step reactor, from the logistics V that reactor outlet at different levels flows out
m-1enter next stage reactor inlet respectively;
D) add containing CO in the arbitrary stage reactor of low temperature methanation unit
2logistics I, obtain products substitution Sweet natural gas after reaction.
In technique scheme, raw material of synthetic gas preferred version be by coal or other carbonaceous materials obtain containing H
2, CO, CO
2and H
2the gas of O.(H in raw material of synthetic gas
2-CO
2)/(CO+CO
2) mol ratio preferable range is for being greater than 3.0, more preferably scope is 3.05 ~ 3.3.Enter the synthetic gas W of high-temperature methanation reaction zone first step reactor
1with enter after the volume ratio preferable range of synthetic gas Wn of each stage reactor be W
1: Wn=1:(1 ~ 2); The volume ratio preferable range of Vn and Vn ' is Vn:Vn '=1.1 ~ 2.0; Vn ' and the synthetic gas W entering first step reactor
1volume ratio preferable range be Vn ': W
1=(1 ~ 4): 1; Except first step reactor, upper level reactor outlet logistics Vn-
1be Vn-with the volume ratio preferable range of the synthetic gas Wn entering each stage reactor
1: Wn=1.5 ~ 3.5.With volume percentage, described logistics I comprises the CO of 40 ~ 100%
2, the H of 0 ~ 60%
2, the CO of 0 ~ 20%, the CO of preferable range for comprising 60 ~ 100%
2, the H of 0 ~ 40%
2, the CO of 0 ~ 10%.Logistics I is >0 ~ 0.5 with the volume ratio preferable range of the logistics entering this stage reactor of low temperature methanation reaction district, and more preferably scope is >0 ~ 0.2.The temperature in of each stage reactor in high-temperature methanation reaction zone is 250 ~ 400 DEG C, and preferable range is 300 ~ 350 DEG C; Pressure is 3.0 ~ 5.5MPa, and preferable range is 3.5 ~ 5.0MPa; Temperature out is 600 ~ 700 DEG C, and preferable range is 620 ~ 680 DEG C.The temperature in of each stage reactor in low temperature methanation reaction district is 200 ~ 300 DEG C, and preferable range is 240 ~ 280 DEG C; Pressure is 3.0 ~ 5.5MPa, preferable range is 3.5 ~ 5.0MPa; Temperature out is 300 ~ 500 DEG C, and preferable range is 350 ~ 450 DEG C.Each stage reactor preferred version in high-temperature methanation reaction zone and low temperature methanation reaction district is for being insulation fix bed reactor.Logistics Vn ' boosts to 3.5 ~ 5.5MPa by compressor, temperature 20 ~ 150 DEG C.N preferable range is 2 ~ 6, m preferable range is 2 ~ 6.
In the inventive method, the catalyzer of the reactor bed fillings at different levels in high-temperature methanation reaction zone and low temperature methanation reaction district is Ni series catalysts known in the art, forms with weight parts, comprises the Al of 40 ~ 80 parts
2o
3carrier and load and the nickel of 20 ~ 60 parts on it.Logistics after reactor reactions at different levels in high-temperature methanation reaction zone and low temperature methanation reaction district all cools through heat exchange.Compressor can be radial compressor, reciprocation compressor or spiral-lobe compressor.
The present invention is by adopting the high-temperature methanation reactor of at least 2 grades of series connection, after the partial reaction product of last step high-temperature methanation reactor is boosted by compressor as circulation gas, first step high-temperature methanation reactor is back to as thinner, water cooler is established between high-temperature methanation reactor at different levels, high pressure steam can be there is and reclaim heat, simultaneously under the prerequisite controlling reactor thermal insulation warming, can circulating flow rate be reduced, reduce the power of compressor, thus reduce the energy consumption of whole device.
Methanation reaction is strong exothermal reaction, during employing adiabatic reactor, reaction temperature rising is very high, and high temperature is unfavorable for the raising of methanation reaction transformation efficiency, for obtaining the alternative Sweet natural gas of higher degree, methanation reaction is divided into high-temperature methanation reaction zone and low temperature methanation reaction district, and high-temperature methanation reaction zone transforms most CO and CO
2, low temperature methanator then transforms remaining CO and CO
2, obtain highly purified alternative Sweet natural gas.In high-temperature methanation reaction zone, because reaction thermal insulation warming is very high, from guard catalyst, reactor apparatus and raising transformation efficiency several respects are considered, the temperature rise of high-temperature methanation reactor must be controlled, partial reaction device is worked off one's feeling vent one's spleen as thinner and is looped back reactor after compression by industrial usual employing, the existence of circulation gas reduces the content being reacted into CO in implication, thus reach the object controlling thermal insulation warming, but as adopted single-stage reactor, for the circulating flow rate controlled required for temperature rise is larger, general recycle ratio (circulating flow rate/material gas quantity) is 1.5 ~ 3, recycle compressor energy consumption is very high.And adopt the inventive method, high-temperature methanation reactor adopts multistage series-parallel connection fixed bed pattern, circulation gas enters reactor with cascade, every stage reactor adds material synthesis gas, every stage reactor is worked off one's feeling vent one's spleen after heat-obtaining and is entered next stage reactor again, like this under the every stage reactor thermal insulation warming prerequisite of control, effectively reduces circulating flow rate and recycle compressor energy consumption, reach energy-conservation effect, total conversion rate is high simultaneously.
In addition, in methanation reaction, 1 mole of CO consumes 3 moles of H in theory
2, 1 mole of CO
2consume 4 moles of H
2, for obtaining highly purified alternative Sweet natural gas, (the H in synthetic gas must be controlled
2-CO
2)/(CO+CO
2) ratio, avoid remaining more H in products substitution Sweet natural gas
2or CO
2, (the H therefore in material synthesis gas
2-CO
2)/(CO+CO
2) mol ratio wishes to control in 3.0 ideal values, this is normally regulated by water gas shift reactor, but in actual motion inevitably operation fluctuation be difficult to make (H
2-CO
2)/(CO+CO
2) ratio is stabilized in ideal value, the fluctuation of raw material composition can affect the H in products substitution Sweet natural gas
2and CO
2content, and due to methanation device reaction process long, longer time lag certainly will be there is by being reflected to product to the component proportion adjustment of material synthesis gas.
The present invention is by adopting raw material of synthetic gas with mol ratio (H
2-CO
2)/(CO+CO
2) ratio that is greater than 3.0 enters high-temperature methanation reaction member, ensures H in reaction process
2surplus, adds CO at any one-level low temperature methanation unit
2gas or be rich in CO
2gas and a small amount of H
2, CO gas mixture, by the CO added
2by the H of surplus
2react away, the size of gas volume is by controlling H in products substitution Sweet natural gas
2≤ 1.0%, CO
2≤ 3%(mol ratio) index determines; Because low temperature methanation reaction unit process flow process is short, the method can H in sensitive control products substitution Sweet natural gas
2and CO
2content, no matter material synthesis gas (H
2-CO
2)/(CO+CO
2) how to fluctuate under the prerequisite being greater than 3, by supplementary CO
2the control of gas volume, can ensure to obtain stable high-quality alternative Sweet natural gas, and not have too much H
2and CO
2.
Compared with prior art, adopt the inventive method, reactive system circulating flow rate reduces 50 ~ 80%, and recycle compressor energy consumption reduces by 30 ~ 70%, and the CO transformation efficiency of high-temperature methanation reaction zone improves 5 ~ 15%, the H in products substitution Sweet natural gas
2≤ 1.0%, CO
2≤ 3%, product high-grade-goods rate improves more than 10%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the process flow diagram (for the reaction of two-stage high-temperature methanation and two-stage low temperature methanation reaction) that synthetic gas system of the present invention substitutes Sweet natural gas (SNG).
Fig. 2 is the process flow diagram that existing synthetic gas system substitutes Sweet natural gas (SNG).
In Fig. 1 and Fig. 2,1 is raw material of synthetic gas, and 2 is one-level high-temperature methanation reactor feed synthetic gas W
1, 3 is secondary high-temperature methanation reactor feed synthetic gas W
2, 4 is one-level high-temperature methanation reactor feed gas mixture, and 5 is one-level high-temperature methanation reactor discharging gas V
1, 6 is secondary high-temperature methanation reactor feed gas mixture, and 7 is secondary high-temperature methanation reactor discharging gas V
2, 8 for removing the circulation gas V of recycle compressor
2', 9 is that a grade low-temp methanator enters implication V
2", 10 is that a grade low-temp methanator is worked off one's feeling vent one's spleen, 11 is that two grade low-temp methanators are worked off one's feeling vent one's spleen, 13 for adding gas (logistics I), 101 is one-level high-temperature methanation reactor, 102 is secondary high-temperature methanation reactor, 103 is a grade low-temp methanator, 104 is two grade low-temp methanators, 105 is one-level high-temperature methanation reactor outlet water cooler, 106 is secondary high-temperature methanation reactor outlet water cooler, 107 is recycle gas cooler, 108 is a grade low-temp methanator entrance interchanger, 109 is two grade low-temp methanator entrance interchanger, 110 is recycle gas compressor, 111 divide flow container for product.
In Fig. 1, material synthesis gas 1 is divided into two portions, and one section of synthetic gas 2 and the mixed logistics 4 of circulation gas 8 enter one-level high-temperature methanation reactor 101 and methanation reaction occurs, and obtains one-level high-temperature methanation reactor discharging gas 5.One-level high-temperature methanation reactor discharging gas 5, after the cooling of one-level high-temperature methanation reactor outlet water cooler 105, enters secondary high-temperature methanation reactor 102 with two sections of mixed materials 6 of synthetic gas 3, obtains secondary high-temperature methanation reactor discharging gas 7.Secondary high-temperature methanation reactor discharging gas 7 is after the cooling of secondary high-temperature methanation reactor outlet water cooler 106, be divided into 2 strands: one material 8 cools through recycle gas cooler 107, recycle compressor 110 compress after, mix with one section of synthetic gas 2 as circulation gas material; Another strand of material 9 enters one-level low temperature methanator 103 after a grade low-temp methanator entrance interchanger heat exchange, work off one's feeling vent one's spleen 10 with add gas 13 mix after through two grade low-temp methanator entrance interchanger 109 heat exchange, enter two grade low-temp methanators 104, working off one's feeling vent one's spleen 11 obtains products substitution Sweet natural gas 15 through point flow container 111 except anhydrating after 14.Add gas 13 with work off one's feeling vent one's spleen 10 volume ratio be >0 ~ 0.5.
In Fig. 2, material synthesis gas 1 all mixes with circulation gas 8, and mixed logistics 4 enters one-level high-temperature methanation reactor 101 and methanation reaction occurs, and obtains one-level high-temperature methanation reactor discharging gas 5.One-level high-temperature methanation reactor discharging gas 5 is after the cooling of one-level high-temperature methanation reactor outlet water cooler 105, be divided into 2 strands: one material 8 cools through recycle gas cooler 107, recycle compressor 110 compress after, mix with material synthesis gas 1 as circulation gas material; Another strand of material 9 enters one-level low temperature methanator 103 after grade low-temp methanator entrance interchanger 108 heat exchange, work off one's feeling vent one's spleen and 10 after two grade low-temp methanator entrance interchanger 109 heat exchange, enter secondary low temperature methanator, after reaction, obtain the finished product gas 11.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Certain 1,200,000,000 Nm
3/ year, synthetic gas system substituted gas plant (year operation hours 8000 hours), and adopt the Technology of Fig. 1, high-temperature methanation and low temperature methanation reaction district are two-stage, and the catalyzer wherein loaded is Ni series catalysts (wherein Al
2o
3carrier 60%, nickel 35%).Material synthesis gas 1 consists of: (H
2-CO
2)/(CO+CO
2)=3.1, pressure 3.5MPa, inlet amount is 600,000 Nm
3/ h, be divided into two portions, the ratio of one section of synthetic gas 2 and two sections of synthetic gas 3 is 1:1.5, one section of synthetic gas 2 and the mixed logistics 4 of circulation gas 8 enter one-level high-temperature methanation reactor 101 and methanation reaction occur at temperature 300 DEG C, the volume ratio of circulation gas 8 and one section of synthetic gas 2 is 2.4:1, reaction outlet streams 5 temperature 650 DEG C, after the cooling of one-level high-temperature methanation reactor outlet water cooler 105, at 300 DEG C, secondary high-temperature methanation reactor 102 is entered with two sections of mixed materials 6 of synthetic gas 3, reaction outlet streams 7 temperature is 650 DEG C, pressure 3.3MPa, after the cooling of secondary high-temperature methanation reactor outlet water cooler 106, be divided into 2 strands: one material 8 cools through recycle gas cooler 107, after recycle compressor 110 is compressed to 3.5MPa, mix with one section of synthetic gas 2 as circulation gas material, recycle compressor adopts radial compressor.Another strand of material 9 enters one-level low temperature methanator 103,10 temperature 450 DEG C of working off one's feeling vent one's spleen after grade low-temp methanator entrance interchanger 108 heat exchange to 280 DEG C, and adds CO
2gas and vapor permeation, adds CO
2gas volume is 9000Nm
3/ h, through two grade low-temp methanator entrance interchanger 109 heat exchange to 280 DEG C, enters two grade low-temp methanators 104,11 temperature 400 DEG C of working off one's feeling vent one's spleen, pressure 3.0MPa, after dividing a flow container to divide and anhydrating, obtain products substitution Sweet natural gas.Material 7 is 1.38 with the volume ratio of material 8, and material 5 is 2.0 with the volume ratio of material 3, and material 13 is 0.04 with the volume ratio of material 10.
This device product Various Components In Natural Gas volume content is: CH
496%, H
20.5%, CO
21.8%, N
21.7%, high-temperature methanation reaction CO transformation efficiency 76%, energy consumption of compressor 2400KW, product high-grade-goods rate 98%.
[embodiment 2]
Certain 1,200,000,000 Nm
3/ year, synthetic gas system substituted gas plant (year operation hours 8000 hours), and adopt the Technology of Fig. 1, material synthesis gas consists of: (H
2-CO
2)/(CO+CO
2)=3.2, one section of synthetic gas 2 and the mixed logistics 4 of circulation gas 8 enter one-level high-temperature methanation reactor 101 and methanation reaction occur under temperature 320 DEG C, pressure 4.5MPa, the volume ratio of circulation gas 8 and one section of synthetic gas 2 is 2:1, reaction outlet streams 5 temperature 700 DEG C, secondary high-temperature methanation reactor 102 temperature in 320 DEG C, temperature out 700 DEG C, pressure 4.2MPa, adds CO
2gas volume is 12000Nm
3/ h, material 7 is 1.53 with the volume ratio of material 8, and material 5 is 1.65 with the volume ratio of material 3, the volume ratio 0.055 of material 13 and material 10, and all the other conditions are with [embodiment 1].
This device product Various Components In Natural Gas volume content is: CH
495%, H
20.8%, CO
22.5%, N
21.7%, high-temperature methanation reaction CO transformation efficiency 74%, energy consumption of compressor 1700KW, product high-grade-goods rate 97%.
[embodiment 3]
Certain 1,200,000,000 Nm
3/ year, synthetic gas system substituted gas plant (year operation hours 8000 hours), and adopt the Technology of Fig. 1, material synthesis gas 1 consists of: (H
2-CO
2)/(CO+CO
2)=3.1, pressure 5.0MPa, be divided into two portions, the ratio of one section of synthetic gas 2 and two sections of synthetic gas 3 is 1:1, the volume ratio of circulation gas 8 and one section of synthetic gas 2 is 2:1, one section of synthetic gas 2 and the mixed logistics 4 of circulation gas 8 enter one-level high-temperature methanation reactor 101 and methanation reaction occur at temperature 290 DEG C, reaction outlet streams 5 temperature 640 DEG C, after the cooling of one-level high-temperature methanation reactor outlet water cooler 105, at 300 DEG C, secondary high-temperature methanation reactor 102 is entered with two sections of mixed materials 6 of synthetic gas 3, reaction outlet streams 7 temperature is 650 DEG C, pressure 4.8MPa, after the cooling of secondary high-temperature methanation reactor outlet water cooler 106, be divided into 2 strands: one material 8 cools through recycle gas cooler 107, after recycle compressor 110 is compressed to 5.0MPa, mix with one section of synthetic gas 2 as circulation gas material 8, recycle compressor adopts reciprocation compressor, another strand of material 9 with add CO
2gas and vapor permeation, adds CO
2gas volume is 10000Nm
3/ h, one-level low temperature methanator 103 is entered after grade low-temp methanator entrance interchanger 108 heat exchange to 300 DEG C, to work off one's feeling vent one's spleen 10 temperature 460 DEG C, secondary low temperature methanator 104 is entered after two grade low-temp methanator entrance interchanger 109 heat exchange to 300 DEG C, to work off one's feeling vent one's spleen 11 temperature 400 DEG C, pressure 4.5MPa.Material 7 is 1.4 with the volume ratio of material 8, and material 5 is 2.9 with the volume ratio of material 3, and material 13 is 0.035 with the volume ratio of material 10.All the other conditions are with [embodiment 1].
This device product Various Components In Natural Gas volume content is: CH
495.5%, H
20.8%, CO
22.2%, N
21.5%, high-temperature methanation reaction CO transformation efficiency 75.5%, energy consumption of compressor 2100KW, product high-grade-goods rate 96%.
[embodiment 4]
Certain 1,200,000,000 Nm
3/ year, synthetic gas system substituted gas plant (year operation hours 8000 hours), adopt the Technology of Fig. 1, high-temperature methanation adopts three reactor, material synthesis gas 1 is divided into three parts, three sections of synthetic gas ratios are 1:1.2:1.2, high-temperature methanation reactor inlet temperature at different levels is 300 DEG C, the volume ratio of circulation gas and one section of synthetic gas is 2.4:1, three sections of high-temperature methanation reactor outlet stream temperature are 650 DEG C, third stage high-temperature methanation reactor outlet gas is divided into 2 strands: one material cools, after compression, mix with one section of synthetic gas as circulation gas material, another strand of material enters low temperature methanation reaction district, all the other conditions are with [embodiment 1].
This device product Various Components In Natural Gas volume content is: CH
496%, H
20.4%, CO
21.8%, N
21.8%, high-temperature methanation reaction CO transformation efficiency 78%, energy consumption of compressor 1400KW, product high-grade-goods rate 97.5%.
[embodiment 5]
Certain 1,200,000,000 Nm
3/ year, synthetic gas system substituted gas plant (year operation hours 8000 hours), and adopt the Technology of Fig. 1, material synthesis gas 1 consists of: (H
2-CO
2)/(CO+CO
2)=3.05, low temperature methanation reaction unit is added and is consisted of H
2: 17%, CO:3%, CO
2: the gas mixture of 80%, add position at first step low temperature methanator entrance, adding gas volume is 4000Nm
3/ h, adding gas volume with the volume ratio from high temperature reaction zone material is that 0.015 all the other conditions are with [embodiment 1].
This device product Various Components In Natural Gas volume content is: CH
496%, H
20.4%, CO
21.8%, N
21.8%, high-temperature methanation reaction CO transformation efficiency 78%, energy consumption of compressor 1400KW, product high-grade-goods rate 97.5%.
[comparative example 1]
Certain 1,000,000,000 Nm
3/ year, synthetic gas methanation substituted gas plant, and adopt the Technology of Fig. 2, material synthesis gas 1 consists of: (H
2-CO
2)/(CO+CO
2)=2.85, high-temperature methanation adopts first order reaction, low temperature methanation reaction adopts two-stage reaction, high-temperature methanation reactor feed temperature is 300 DEG C, pressure 3.5MPa, reaction outlet stream temperature 650 DEG C, after the cooling of high-temperature methanation reactor outlet water cooler, be divided into 2 strands, logistics 5 is 1.5 with the volume ratio of logistics 8, logistics 8 is through cooling, after being compressed to 3.5MPa, high-temperature methanation reactor is mixed into as circulation gas material and material synthesis gas, material 9 enters one-level low temperature methanator after heat exchange to 300 DEG C, to work off one's feeling vent one's spleen 10 temperature 450 DEG C, secondary low temperature methanator is entered after two grade low-temp methanator entrance interchanger heat exchange to 300 DEG C, temperature of working off one's feeling vent one's spleen 400 DEG C, pressure 3.0MPa.
This device product Various Components In Natural Gas volume content is: CH
493%, H
21.2%, CO
22.0%, N
21.8%, high-temperature methanation reaction CO transformation efficiency 73%, energy consumption of compressor 5000KW, product high-grade-goods rate 88%.
Claims (7)
1. the method substituting Sweet natural gas is produced in synthetic gas methanation, comprises the following steps:
A) provide high-temperature methanation reaction zone, described high-temperature methanation reaction zone comprises the reactor of n level series connection, n >=2;
B) containing H
2, CO, CO
2and H
2the raw material of synthetic gas of O is divided into n section to enter the entrance of each stage reactor in high-temperature methanation reaction zone respectively; Except last step reactor, the logistics flowed out from reactor outlet at different levels enters next stage reactor inlet respectively; The logistics Vn flowed out from last step reactor outlet is divided into Vn ' and Vn ", logistics Vn ' is circulated to first step reactor inlet after compression;
C) provide low temperature methanation reaction district, described low temperature methanation reaction district comprises the reactor of m level series connection, m >=2; Except last step reactor, the logistics flowed out from reactor outlet at different levels enters next stage reactor inlet respectively;
D) add containing CO in the arbitrary stage reactor of low temperature methanation unit
2logistics I, obtain products substitution Sweet natural gas after reaction;
Raw material of synthetic gas be by coal or other carbonaceous materials obtain containing H
2, CO, CO
2and H
2the gas of O, (H in raw material of synthetic gas
2-CO
2)/(CO+CO
2) mol ratio is greater than 3.05 ~ 3.3; H in products substitution Sweet natural gas
2≤ 1.0%, CO
2≤ 3%;
Wherein, the temperature in of each stage reactor in high-temperature methanation reaction zone is 250 ~ 400 DEG C, and pressure is 3.0 ~ 5.5MPa; Temperature out is 600 ~ 700 DEG C;
The temperature in of each stage reactor in low temperature methanation reaction district is 200 ~ 300 DEG C, and pressure is 3.0 ~ 5.5MPa, and temperature out is 300 ~ 500 DEG C.
2. the method substituting Sweet natural gas is produced in synthetic gas methanation according to claim 1, it is characterized in that the synthetic gas W entering high-temperature methanation reaction zone first step reactor
1with enter after the volume ratio of synthetic gas Wn of each stage reactor be W
1: Wn=1:(1 ~ 2); The volume ratio of Vn and Vn ' is Vn:Vn '=1.1 ~ 2.0; Vn ' and the synthetic gas W entering first step reactor
1volume ratio be Vn ': W
1=1 ~ 4; Except first step reactor, upper level reactor outlet logistics Vn-
1be Vn-with the volume ratio of the synthetic gas Wn entering each stage reactor
1: Wn=1.5 ~ 3.5;
With volume percentage, described logistics I comprises the CO of 40 ~ 100%
2, the H of 0 ~ 60%
2, the CO of 0 ~ 20%; Logistics I is >0 ~ 0.5 with the volume ratio of the logistics entering this stage reactor of low temperature methanation reaction district.
3. the method substituting Sweet natural gas is produced in synthetic gas methanation according to claim 1, and it is characterized in that with volume percentage, described logistics I comprises the CO of 60 ~ 100%
2, the H of 0 ~ 40%
2, the CO of 0 ~ 10%; Logistics I is >0 ~ 0.2 with the volume ratio of the logistics entering this stage reactor of low temperature methanation reaction district.
4. the method substituting Sweet natural gas is produced in synthetic gas methanation according to claim 1, and it is characterized in that the temperature in of each stage reactor in high-temperature methanation reaction zone is 300 ~ 350 DEG C, pressure is 3.5 ~ 5.0MPa; Temperature out is 620 ~ 680 DEG C;
The temperature in of each stage reactor in low temperature methanation reaction district is 240 ~ 280 DEG C, and pressure is 3.5 ~ 5.0MPa, and temperature out is 350 ~ 450 DEG C.
5. the method substituting Sweet natural gas is produced in synthetic gas methanation according to claim 1, it is characterized in that each stage reactor in high-temperature methanation reaction zone and low temperature methanation reaction district is insulation fix bed reactor.
6. the method substituting Sweet natural gas is produced in synthetic gas methanation according to claim 1, it is characterized in that logistics Vn ' boosts to 3.5 ~ 5.5MPa by compressor, temperature 20 ~ 150 DEG C.
7. the method substituting Sweet natural gas is produced in synthetic gas methanation according to claim 1, it is characterized in that n=2 ~ 6, m=2 ~ 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210392935.XA CN103740426B (en) | 2012-10-17 | 2012-10-17 | The method substituting Sweet natural gas is produced in synthetic gas methanation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210392935.XA CN103740426B (en) | 2012-10-17 | 2012-10-17 | The method substituting Sweet natural gas is produced in synthetic gas methanation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103740426A CN103740426A (en) | 2014-04-23 |
| CN103740426B true CN103740426B (en) | 2015-12-09 |
Family
ID=50497495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210392935.XA Active CN103740426B (en) | 2012-10-17 | 2012-10-17 | The method substituting Sweet natural gas is produced in synthetic gas methanation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103740426B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152201B (en) * | 2014-08-21 | 2017-02-15 | 中海石油气电集团有限责任公司 | Coal syngas circulation gas free methanation technology |
| CN105733716A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Process for preparing synthetic natural gas through coke-oven gas methanation |
| CN104830391A (en) * | 2015-05-15 | 2015-08-12 | 西南化工研究设计院有限公司 | Methanation device and process for synthesizing high-quality natural gas produced by coal |
| CN105296034A (en) * | 2015-11-03 | 2016-02-03 | 中海石油气电集团有限责任公司 | Method for preparing LNG from coke oven gas by supplementing carbon dioxide to improve device security and yield |
| CN108102751B (en) * | 2016-11-25 | 2020-11-06 | 惠生工程（中国）有限公司 | Energy-saving device and process for preparing natural gas by single pass of synthesis gas |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133825A (en) * | 1976-05-21 | 1979-01-09 | British Gas Corporation | Production of substitute natural gas |
| GB2060686A (en) * | 1979-10-22 | 1981-05-07 | Conoco Inc | Concurrent shift-methanation process |
| US20090264542A1 (en) * | 2008-04-16 | 2009-10-22 | Methanol Casale S.A. | Process and Plant for Substitute Natural Gas |
| CN101880558A (en) * | 2009-05-07 | 2010-11-10 | 赫多特普索化工设备公司 | Process for the production of substitute natural gas |
| CN102329671A (en) * | 2011-09-13 | 2012-01-25 | 西南化工研究设计院 | Methanation process of synthetic natural gas prepared from coal |
-
2012
- 2012-10-17 CN CN201210392935.XA patent/CN103740426B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133825A (en) * | 1976-05-21 | 1979-01-09 | British Gas Corporation | Production of substitute natural gas |
| GB2060686A (en) * | 1979-10-22 | 1981-05-07 | Conoco Inc | Concurrent shift-methanation process |
| US20090264542A1 (en) * | 2008-04-16 | 2009-10-22 | Methanol Casale S.A. | Process and Plant for Substitute Natural Gas |
| CN101880558A (en) * | 2009-05-07 | 2010-11-10 | 赫多特普索化工设备公司 | Process for the production of substitute natural gas |
| CN102329671A (en) * | 2011-09-13 | 2012-01-25 | 西南化工研究设计院 | Methanation process of synthetic natural gas prepared from coal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103740426A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103740426B (en) | The method substituting Sweet natural gas is produced in synthetic gas methanation | |
| KR20140012992A (en) | Method for producing methanol or hydrocarbons from a carbon material, including a reforming step, the operating conditions of which are selectively adjusted | |
| CN103695058B (en) | Novel methanation reaction process for preparing synthetic natural gas | |
| CN101812339A (en) | Method and device for producing synthetic natural gas, and natural gas product thereof | |
| CN104152201B (en) | Coal syngas circulation gas free methanation technology | |
| CN100503790C (en) | Method of producing chemical product by double fuel reforming chemical system | |
| CN103409187B (en) | Methanation technology for preparing non-recycling gas of SNG or LNG from coke-oven gas | |
| CN102899112B (en) | Method and device for producing synthetic natural gas | |
| CN103666611B (en) | System and method for preparing alternative natural gas | |
| CN103740428B (en) | Synthesis gas methanation substitutes the method for natural gas | |
| CN102596808A (en) | Ammonia production process | |
| CN102041019B (en) | Method for coproducing substitute natural gas through coal liquefaction | |
| CN102876411B (en) | Method and device for producing synthetic natural gas | |
| CN104229831A (en) | Process for preparing synthesis ammonia from synthesis gas and co-producing ethylene glycol | |
| CN104709876A (en) | Process method for preparing synthesis gas by using zero carbon or negative carbon emission system | |
| CN103740425B (en) | Synthesis gas produces the method substituting natural gas | |
| CN103421561B (en) | Synthesis gas methanation reaction method | |
| CN104830391A (en) | Methanation device and process for synthesizing high-quality natural gas produced by coal | |
| CN101985574B (en) | A kind of processing method utilizing synthetic gas to prepare Sweet natural gas | |
| CN103773526A (en) | Method for producing substitute natural gas | |
| CN103540376B (en) | Synthetic gas methanation substitutes the method for Sweet natural gas | |
| CN101659879B (en) | Chemical-electric poly-generation method and equipment | |
| CN103740424A (en) | Method of producing substitute natural gas from synthesis gas | |
| CN101381616B (en) | Technique for producing oil products by fischer-tropsch synthesis | |
| CN103740427B (en) | Method of producing substitute natural gas from synthesis gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |