CN103740426A - Method of producing substitute natural gas by methanation of synthesis gas - Google Patents
Method of producing substitute natural gas by methanation of synthesis gas Download PDFInfo
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Abstract
The invention relates to a method of producing substitute natural gas by methanation of synthesis gas, mainly solving problems, namely large using amount of recycle gas, high energy consumption of compressors, and excess of the H2 component or the CO2 component in substitute natural gas products, of high-temperature methanation reactions in the prior art. According to the technical scheme adopted by the method, the method comprises: a) a step of providing a high-temperature methanation reaction zone including n-stage series-connected reactors; b) a step of dividing the synthesis gas raw materials into n sections and respectively feeding the n sections of the synthesis gas raw materials into inlets of the reactors at all stages in the high-temperature methanation reaction zone, wherein the stream Vn flowing out from the reactor at the final stage is divided into Vn' and Vn'' and the stream Vn' is condensed and circulated to the inlet of the reactor at the first stage; c) a step of providing a low-temperature methanation reaction zone including m-stage series-connected reactors; and d) a step of supplementing a stream I containing CO2 to a reactor at any stage in the low-temperature methanation reaction zone, and a substitute natural gas product is obtained after the reaction. By the technical scheme, the problems are solved well and the method can be used in industrial production of the substitute natural gas from the synthesis gas.
Description
Technical field
The present invention relates to the method for a kind of synthetic gas methanation production instead of natural gas (SNG).
Background technology
Sweet natural gas is a kind of energy of high-efficiency cleaning, can make up to a certain extent the present situation that petroleum resources are day by day in short supply.But the reserves of China's natural gas demand rapid growth, and China's natural gas are in recent years 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 approximately 30,000,000,000 ~ 70,000,000,000 Nm
3.For solving China's natural gas imbalance between supply and demand, must seek other alternative route.
Coal resources in China, compared with horn of plenty, therefore can be alleviated the demand of China to Sweet natural gas by the method for the synthetic gas methanation instead of natural gas processed (SNG) from gasification effectively.
More external companies started coal to SNG to study from the seventies in last century, the current industrialized coal to SNG factory that only has big plain in u.s.a company in 1984 to build up, Germany Lurgi company carries out technological design for this device, the G1-85 type catalyzer of its methanator original adoption BASF AG, the CRG catalyzer of the Britain Davy company of converting afterwards.The CRG catalyzer of the coal to SNG process using of Britain Davy company oneself, this catalyzer has special high-temperature stability and to unstripped gas H
2the requirement of/CO ratio is not strict, so this coal to SNG technique Raw gas can directly enter methanation unit after purifying.The TREMP of Denmark Topsoe company
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 stricter, and catalyzer still has catalytic activity at 700 ℃.Germany Lurgi company coal to SNG technique is the SNG technique coal-based processed of current unique industrialization operation, so this technique has abundanter technical scale service experience.For the exploitation of efficient methanation catalyst and methanation process, remain at present the emphasis of coal-based SNG research processed.
The chief component of synthetic gas is CO, CO
2and H
2, by methanation reaction, producing a large amount of methane, the reaction occurring 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
2in excessive situation, mainly react (1) and (2), the water that reaction generates can react with CO again (3).Reaction (1) and (2) is all strong exothermal reactions, in the methane building-up reactions of purified synthesis gas the synthetic thermal insulation warming of every 1% CO methane up to 73 ℃, every 1% CO
2approximately 60 ℃ of the synthetic thermal insulation warmings of methane.
Initial methane content is also depended in methanation reaction temperature rise, it is 400 ~ 600 ℃ that single-stage methanation reaction can cause thermal insulation warming △ T, 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 producing in reaction process is removed, can cause damage to catalyst activity.The main method of controlling the temperature rise of methanation reaction process is adopt the part circulation of methanation reaction product or use cold logistics to remove methanation reaction liberated heat.
Document US4133825A discloses high-temperature methanation and has partly adopted single-stage reactor, and reactor outlet is divided into two portions, and a part is mixed 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, in methanator, there is methanation reaction in synthetic gas, the cooling system that enters methanator after simultaneously having water by a series of preheatings utilizes methanation reaction liberated heat to produce steam, removes reaction heat.But still there is high-temperature methanation reaction cycle gas consumption greatly and the high problem of energy consumption of compressor in above-mentioned technology.
In addition, in actual industrial device, (the H in synthetic gas
2-CO
2)/(CO+CO
2) although mol ratio regulates by water gas shift reactor, inevitable fluctuation in service is difficult to make (H
2-CO
2)/(CO+CO
2) ratio is stabilized in ideal value 3.0, the fluctuation that raw material forms can affect the H in products substitution Sweet natural gas
2, CO and CO
2content, and because methanation device reaction process is long, by the component ratio to material synthesis gas, regulate and be reflected to product and certainly will have longer time lag.
In sum, prior art exists high-temperature methanation reaction cycle gas consumption large, 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 large, 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 method of new synthetic gas methanation production instead of 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 stable, 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: a kind of method of synthetic gas methanation production instead of natural gas, 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 the entrance that n section enters respectively each stage reactor in high-temperature methanation reaction zone; Except last step reactor, the logistics flowing out from reactor outlets at different levels enters respectively next stage reactor inlet; The logistics Vn flowing 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 V flowing out from reactor outlets at different levels
m-1enter respectively next stage reactor inlet;
D) in the arbitrary stage reactor in low temperature methanation unit, add containing CO
2logistics I, after reaction, obtain products substitution Sweet natural gas.
In technique scheme, the contain H of raw material of synthetic gas preferred version for being obtained by coal or other carbonaceous materials
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
1be W with entering the volume ratio preferable range of the synthetic gas Wn of each stage reactor afterwards
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 that enters first step reactor
1volume ratio preferable range be Vn ': W
1=(1 ~ 4): 1; Except first step reactor, upper level reactor outlet logistics Vn-
1with the volume ratio preferable range that enters the synthetic gas Wn of each stage reactor be Vn-
1: Wn=1.5 ~ 3.5.In volume percent, described logistics I comprises 40 ~ 100% CO
2, the H of 0 ~ 60 %
2, the CO of 0 ~ 20 %, preferable range is for comprising 60 ~ 100% CO
2, the H of 0 ~ 40 %
2, the CO of 0 ~ 10 %.Logistics I is >0 ~ 0.5 with the volume ratio preferable range that enters the logistics of this stage reactor of low temperature methanation reaction district, and more preferably scope is >0 ~ 0.2.The temperature in of each stage reactor of high-temperature methanation reaction zone is 250～400 ℃, and preferable range is 300～350 ℃; Pressure is 3.0～5.5MPa, and preferable range is 3.5～5.0MPa; Temperature out is 600～700 ℃, and preferable range is 620～680 ℃.The temperature in of each stage reactor of low temperature methanation reaction district is 200～300 ℃, and preferable range is 240～280 ℃; Pressure is 3.0～5.5MPa,, preferable range is 3.5～5.0MPa; Temperature out is 300～500 ℃, and preferable range is 350～450 ℃.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, 20 ~ 150 ℃ of temperature.N preferable range is that 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 in parts by weight, 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 is all cooling 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 boosts by compressor as circulation gas, as thinner, be back to first step high-temperature methanation reactor, between high-temperature methanation reactors at different levels, establish water cooler, can there is high pressure steam and reclaim heat, controlling under the prerequisite of reactor thermal insulation warming, can reduce circulating flow rate simultaneously, reduce the power of compressor, thereby reduce the energy consumption of whole device.
Methanation reaction is strong exothermal reaction, while adopting adiabatic reactor, reaction temperature rising is very high, and high temperature is unfavorable for the raising of methanation reaction transformation efficiency, for obtaining the instead of 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 transforms remaining CO and CO
2, obtain highly purified instead of 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, industrial common employing is worked off one's feeling vent one's spleen partial reaction device to loop back after compression reactor as thinner, the existence of circulation gas has reduced the content that is reacted into CO in implication, thereby reach the object of controlling thermal insulation warming, but as employing single-stage reactor, larger for controlling the needed circulating flow rate of temperature rise, general recycle ratio (circulating flow rate/material gas quantity) is 1.5 ~ 3, recycle compressor energy consumption is very high.And employing the inventive method, high-temperature methanation reactor adopts multistage series-parallel connection fixed bed pattern, circulation gas enters reactor with series connection form, every stage reactor is added 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, controlling under every stage reactor thermal insulation warming prerequisite, effectively reduces circulating flow rate and recycle compressor energy consumption like this, reached 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 instead of natural gas, must control (the H in synthetic gas
2-CO
2)/(CO+CO
2) ratio, avoid remaining in products substitution Sweet natural gas more H
2or CO
2, so (the H in material synthesis gas
2-CO
2)/(CO+CO
2) mol ratio wishes to be controlled at 3.0 ideal values, this normally regulates 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 that raw material forms can affect the H in products substitution Sweet natural gas
2and CO
2content, and because methanation device reaction process is long, by the component ratio to material synthesis gas, regulate and be reflected to product and certainly will have longer time lag.
The present invention is by adopting raw material of synthetic gas with mol ratio (H
2-CO
2)/(CO+CO
2) 3.0 the ratio of being greater than enters high-temperature methanation reaction member, guarantees H in reaction process
2surplus, adds CO in 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 adding
2by superfluous H
2react away, the size of gas volume is H in controlling products substitution Sweet natural gas
2≤ 1.0%, CO
2≤ 3%(mol ratio) index is determined; Because low temperature methanation reaction unit process flow process is short, the H of the method in can 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 being greater than under 3 prerequisite, by supplementing CO
2the control of gas volume, can guarantee to obtain stable high-quality instead of natural gas, and not have too much H
2and CO
2.
Compared with prior art, adopt the inventive method, reactive system circulating flow rate has reduced by 50～80%, recycle compressor Energy Intensity Reduction 30～70%, and the CO transformation efficiency of high-temperature methanation reaction zone has improved 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%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the process flow diagram (the two-stage high-temperature methanation of take reaction and two-stage low temperature methanation reaction are example) of synthetic gas of the present invention instead of natural gas processed (SNG).
Fig. 2 is the process flow diagram of existing synthetic gas instead of natural gas processed (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, 5 is one-level high-temperature methanation reactor discharging gas V
1, 6 is secondary high-temperature methanation reactor feed gas mixture, 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 methanation reactions occur, and obtain one-level high-temperature methanation reactor discharging gas 5.One-level high-temperature methanation reactor discharging gas 5, after one-level high-temperature methanation reactor outlet water cooler 105 is cooling, 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 secondary high-temperature methanation reactor outlet water cooler 106 is cooling, be divided into 2 strands: one material 8 is cooling through recycle gas cooler 107, after recycle compressor 110 compression, as circulation gas material, mix with one section of synthetic gas 2; 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 and mix by 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 minute flow container 111 except anhydrating after 14.Adding gas 13 is >0 ~ 0.5 with 10 the volume ratio of working off one's feeling vent one's spleen.
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 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 one-level high-temperature methanation reactor outlet water cooler 105 is cooling, be divided into 2 strands: one material 8 is cooling through recycle gas cooler 107, after recycle compressor 110 compression, as circulation gas material, mix with material synthesis gas 1; 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 10 enters secondary low temperature methanator after two grade low-temp methanator entrance interchanger 109 heat exchange, obtains the finished product gas 11 after reaction.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Certain 1,200,000,000 Nm
3/ year synthetic gas instead of natural gas device processed (year operation hours 8000 hours), adopts the Technology of Fig. 1, and high-temperature methanation and low temperature methanation reaction district are two-stage, and the catalyzer wherein loading is Ni series catalysts (Al wherein
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 methanation reactions occur at 300 ℃ of temperature, the volume ratio of circulation gas 8 and one section of synthetic gas 2 is 2.4:1, 650 ℃ of reaction outlet logistics 5 temperature, after one-level high-temperature methanation reactor outlet water cooler 105 is cooling, at 300 ℃, enter secondary high-temperature methanation reactor 102 with two sections of mixed materials 6 of synthetic gas 3, reaction outlet logistics 7 temperature are 650 ℃, pressure 3.3 MPa, after secondary high-temperature methanation reactor outlet water cooler 106 is cooling, be divided into 2 strands: one material 8 is cooling through recycle gas cooler 107, recycle compressor 110 is compressed to after 3.5 MPa, as circulation gas material, mix with one section of synthetic gas 2, recycle compressor adopts radial compressor.Another strand of material 9 enters one-level low temperature methanator 103 after grade low-temp methanator entrance interchanger 108 heat exchange to 280 ℃, and 450 ℃ of 10 temperature of working off one's feeling vent one's spleen and are added CO
2gas mixes, and adds CO
2gas volume is 9000Nm
3/ h, through two grade low-temp methanator entrance interchanger 109 heat exchange to 280 ℃, enters two grade low-temp methanators 104,400 ℃ of 11 temperature of working off one's feeling vent one's spleen, and pressure 3.0MPa, divides after anhydrating and obtains products substitution Sweet natural gas through a minute flow container.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 instead of natural gas device processed (year operation hours 8000 hours), the Technology of employing 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 methanation reactions occur under 320 ℃ of temperature, pressure 4.5MPa, the volume ratio of circulation gas 8 and one section of synthetic gas 2 is 2:1,700 ℃ of reaction outlet logistics 5 temperature, 320 ℃ of secondary high-temperature methanation reactor 102 temperature ins, 700 ℃ of temperature outs, pressure 4.2 MPa, add CO
2gas volume is 12000Nm
3/ h, material 7 is 1.53 with the volume ratio of material 8, material 5 is 1.65 with the volume ratio of material 3, the volume ratio 0.055 of material 13 and material 10, 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 instead of natural gas device processed (year operation hours 8000 hours), the Technology of employing 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 methanation reactions occur at 290 ℃ of temperature, 640 ℃ of reaction outlet logistics 5 temperature, after one-level high-temperature methanation reactor outlet water cooler 105 is cooling, at 300 ℃, enter secondary high-temperature methanation reactor 102 with two sections of mixed materials 6 of synthetic gas 3, reaction outlet logistics 7 temperature are 650 ℃, pressure 4.8 MPa, after secondary high-temperature methanation reactor outlet water cooler 106 is cooling, be divided into 2 strands: one material 8 is cooling through recycle gas cooler 107, recycle compressor 110 is compressed to after 5.0 MPa, as circulation gas material 8, mix with one section of synthetic gas 2, recycle compressor adopts reciprocation compressor, another strand of material 9 with add CO
2gas mixes, and adds CO
2gas volume is 10000Nm
3/ h, after grade low-temp methanator entrance interchanger 108 heat exchange to 300 ℃, enter one-level low temperature methanator 103,460 ℃ of 10 temperature of working off one's feeling vent one's spleen, after two grade low-temp methanator entrance interchanger 109 heat exchange to 300 ℃, enter secondary low temperature methanator 104,400 ℃ of 11 temperature of working off one's feeling vent one's spleen, 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 instead of natural gas device processed (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 temperatures at different levels are 300 ℃, 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 ℃, third stage high-temperature methanation reactor outlet gas is divided into 2 strands: one material is cooling, after compression, as circulation gas material, mix with one section of synthetic gas, 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 instead of natural gas device processed (year operation hours 8000 hours), the Technology of employing 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: 80% gas mixture, add position at first step low temperature methanator entrance, adding gas volume is 4000Nm
3/ h, adding gas volume is that 0.015 all the other conditions are with [embodiment 1] with the volume ratio from high temperature reaction zone material.
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 instead of natural gas device processed, the Technology of employing 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 ℃, pressure 3.5 MPa, 650 ℃ of reaction outlet stream temperature, after high-temperature methanation reactor outlet water cooler is cooling, be divided into 2 strands, logistics 5 is 1.5 with the volume ratio of logistics 8, logistics 8 is through cooling, be compressed to after 3.5 MPa, as circulation gas material and material synthesis gas, be mixed into high-temperature methanation reactor, material 9 enters one-level low temperature methanator after heat exchange to 300 ℃, 450 ℃ of 10 temperature of working off one's feeling vent one's spleen, after two grade low-temp methanator entrance interchanger heat exchange to 300 ℃, enter secondary low temperature methanator, 400 ℃ of the temperature of working off one's feeling vent one's spleen, 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 (10)
1. a method for synthetic gas methanation production instead of natural gas, 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 the entrance that n section enters respectively each stage reactor in high-temperature methanation reaction zone; Except last step reactor, the logistics flowing out from reactor outlets at different levels enters respectively next stage reactor inlet; The logistics Vn flowing 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 flowing out from reactor outlets at different levels enters respectively next stage reactor inlet;
D) in the arbitrary stage reactor in low temperature methanation unit, add containing CO
2logistics I, after reaction, obtain products substitution Sweet natural gas.
2. the method for synthetic gas methanation production instead of natural gas according to claim 1, it is characterized in that raw material of synthetic gas be by coal or other carbonaceous materials, obtained 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 3.0.
3. the method for synthetic gas methanation production instead of natural gas according to claim 2, is characterized in that (H in raw material of synthetic gas
2-CO
2)/(CO+CO
2) mol ratio is 3.05 ~ 3.3.
4. the method for synthetic gas methanation production instead of natural gas according to claim 1, is characterized in that entering the synthetic gas W of high-temperature methanation reaction zone first step reactor
1be W with entering the volume ratio of the synthetic gas Wn of each stage reactor afterwards
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 that enters first step reactor
1volume ratio be Vn ': W
1=1 ~ 4; Except first step reactor, upper level reactor outlet logistics Vn-
1with the volume ratio that enters the synthetic gas Wn of each stage reactor be Vn-
1: Wn=1.5 ~ 3.5;
In volume percent, described logistics I comprises 40 ~ 100% CO
2, 0 ~ 60% H
2, the CO of 0 ~ 20 %; Logistics I is >0 ~ 0.5 with the volume ratio that enters the logistics of this stage reactor of low temperature methanation reaction district.
5. the method for synthetic gas methanation production instead of natural gas according to claim 4, is characterized in that in volume percent, and described logistics I comprises 60 ~ 100% CO
2, 0 ~ 40% H
2, 0 ~ 10% CO; Logistics I is >0 ~ 0.2 with the volume ratio that enters the logistics of this stage reactor of low temperature methanation reaction district.
6. the method for synthetic gas methanation production instead of natural gas according to claim 1, is characterized in that the temperature in of each stage reactor of high-temperature methanation reaction zone is 250～400 ℃, and pressure is 3.0～5.5MPa; Temperature out is 600～700 ℃;
The temperature in of each stage reactor of low temperature methanation reaction district is 200～300 ℃, and pressure is 3.0～5.5MPa, and temperature out is 300～500 ℃.
7. the method for synthetic gas methanation production instead of natural gas according to claim 6, is characterized in that the temperature in of each stage reactor of high-temperature methanation reaction zone is 300～350 ℃, and pressure is 3.5～5.0MPa; Temperature out is 620～680 ℃;
The temperature in of each stage reactor of low temperature methanation reaction district is 240～280 ℃, and pressure is 3.5～5.0MPa, and temperature out is 350～450 ℃.
8. the method for synthetic gas methanation production instead of natural gas according to claim 1, is characterized in that each stage reactor in high-temperature methanation reaction zone and low temperature methanation reaction district is insulation fix bed reactor.
9. the method for synthetic gas methanation production instead of natural gas according to claim 1, is characterized in that logistics Vn ' boosts to 3.5 ~ 5.5MPa by compressor, 20 ~ 150 ℃ of temperature.
10. the method for synthetic gas methanation production instead of natural gas according to claim 1, is characterized in that n=2 ~ 6, m=2 ~ 6.
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