CN104774662B - It is a kind of that crude synthesis gas is converted into the technique rich in methane gas - Google Patents
It is a kind of that crude synthesis gas is converted into the technique rich in methane gas Download PDFInfo
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- CN104774662B CN104774662B CN201510154335.3A CN201510154335A CN104774662B CN 104774662 B CN104774662 B CN 104774662B CN 201510154335 A CN201510154335 A CN 201510154335A CN 104774662 B CN104774662 B CN 104774662B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 61
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 239000000047 product Substances 0.000 claims abstract description 64
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000009413 insulation Methods 0.000 claims abstract description 15
- 239000013589 supplement Substances 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 58
- 229910052717 sulfur Inorganic materials 0.000 claims description 57
- 239000011593 sulfur Substances 0.000 claims description 57
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000003034 coal gas Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 204
- 239000003345 natural gas Substances 0.000 abstract description 30
- 230000008569 process Effects 0.000 abstract description 23
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 24
- 239000003245 coal Substances 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 13
- 239000002918 waste heat Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000002309 gasification Methods 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 201000004792 malaria Diseases 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- -1 compound Chemical compound 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 208000013403 hyperactivity Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Industrial Gases (AREA)
Abstract
Crude synthesis gas is converted into the methanation process rich in methane gas the invention discloses a kind of, the system includes at least two insulation fix bed reactor, at least one constant temperature fixed bed reactors and at least one acid gas removal unit being sequentially connected in series, wherein, crude synthesis gas or product gas pass through at least three methanation fixed bed reactors after being incorporated a certain amount of vapor, methane and carbon dioxide are converted into more than 99% synthesis gas, product gas removing CO2It can obtain CH afterwards4Replacement natural gas of the content more than 90%, it is not necessary to carry out supplement methanation reaction.The technique have methanator requirement it is few, without circulation of tail gas device and supplement methanator, the significant advantage low to methanation catalyst hydrothermal stability requirement.
Description
Technical field
The present invention relates to rich in CH4The production technology of gas, is converted into rich in CH more particularly to by crude synthesis gas4
The methanation process of gas and it is rich in CH using the technique productions4The method of gas.
Background technology
Natural gas is as a kind of energy of clean and effective, and proportion rises year by year in international energy consumption.China
Resource reserve has the characteristics of " rich coal, oil starvation, few gas ", and natural gas ratio in the consumption of Chinese primary energy less than 6%, is far below
International average level 24%.Rich coal resources in China, development natural gas from coal (SNG) technology can not only meet growing
The market demand, and energy security to China, energy-saving and emission-reduction etc. are significant.
Existing natural gas from coal technology can be divided to two classes, and one kind is the conventional methane using Ni methylmethane catalyst
Micronizing technology, its flow are that feed coal produces synthesis gas by gasification process；Synthesis gas through water-gas shift procedure regulation CO with
H2Ratio；Sour gas is removed by low-temp methanol washing process；Pure synthesis gas is rich in CH through methanator system4Synthesis
Natural gas.Another kind of is the natural gas from coal technology using Mo base catalyst for methanation in presence of sulfur, as US3904386 discloses one kind
Using the natural gas from coal technique of the catalyst of Mo or W bases, its flow is that feed coal produces crude synthesis gas by gasification unit；Slightly
Synthesis gas enters methanation and methanation and water gas shift reaction occurs with Water gas shift/WGS integrated reactor；Then removing is mixed
Close CO in gas2And sulfide；Remaining CO is finally reacted away in methanator is supplemented, production is rich in CH4Gas.
Methanation is strong exothermal reaction, and significant challenge is how to control in the methanation technology for the purpose of producing natural gas
The temperature and the high performance heat-resisting methanation catalyst of exploitation of methanator processed.
Existing methanation process technology is mainly for non-resistant to sulfur Ni methylmethane catalyst.Rope house journal of Top of Denmark
US4298694 is disclosed one kind and is connected using multistage reactor and reach control by circulating second segment reactor outlet gas
The methanation process of first paragraph reactor outlet temperature, it is a kind of modified Ni methylmethanes chemical industry skill.For effectively control first
Section reactor outlet temperature, second segment reactor outlet gas internal circulating load and first stage reactor inlet gas volume in above-mentioned technique
Than it need to be maintained at 0.1-0.9 between, this significantly increases the energy consumption of whole system.US20090264542A1 discloses one kind
The simultaneously parallel methanation process for entering four sections of insulation fix bed reactors is divided into after four strands using unstripped gas, the in the technique
The needs part of working off one's feeling vent one's spleen of first stage reactor is circulated into this section of entrance, and the volume ratio of wherein circulating air and virgin gas is about 2.
At present, still without the methanation fixed bed reactors technique for the exploitation of Mo bases catalyst for methanation in presence of sulfur, and have
It is also relatively fewer to close such document report.US3904386 discloses a kind of natural gas from coal work for Mo base sulfur resistant catalysts
Skill, in the process Water gas shift/WGS are coupling in the circulating fluid bed reactor of a heat exchange with methanation and carried out, due to
The recirculating fluidized bed is needed in the high pressing operation more than 3MPa, so commercial Application is more difficult, and the document is not closed
In the specific descriptions of circulating fluid bed reactor structure.CN102126906B and CN101982448B discloses two kinds by synthesis gas
The fluidized bed reaction system rich in methane gas is prepared, two systems are by methanation reaction and CO2And H2S's is adsorbing coupled same
Carried out in one reactor, two documents are not referred to reaction system using which kind of catalyst.
CN103146447A discloses a kind of coal system that methane gas is rich in using resistant to sulfur Mo methylmethanes Catalyst Production
Natural gas process, in the process will be partially synthetic first by three sections of methanation fixed bed reactors equipped with Mo base catalyst
Gas is converted into methane and CO2, CO is removed by low temperature acid gas removal unit2After sulfurous gas, reuse equipped with Ni base catalyst
Supplement methanation unit remaining synthesis gas is fully converted to methane.It is seen that the technique not only long flow path, and mistake
Need to operate by multiple heating and cooling in journey, significant malaria drawback be present.
The invention provides a kind of fixed bed reactors methanation process suitable for Mo base sulfur resistant catalysts, in the work
In skill, there is the Mo base catalyst for methanation in presence of sulfur of different operating temperature and performance due to having used two classes simultaneously, therefore use
Not only flow is more simple but also avoids malaria drawback present in prior art for the natural gas from coal technology of the technique,
System do not have circulation of tail gas device and supplement methanator so that production substitute natural gas technology become it is simpler and
It is cheap, and then enhance the market competitiveness of natural gas from coal technology.
The content of the invention
According to the first aspect of the invention, there is provided a kind of that crude synthesis gas is converted into the fixed bed rich in methane gas
Methanator system, at least two insulation fix bed reactor, at least one constant temperature that the system includes being sequentially connected in series are consolidated
Fixed bed reactor and at least one acid gas removal unit,
Wherein, last fixed bed reactors is constant temperature fixed bed reactors, to last fixed bed reactors it
Water vapour is passed through at least two outer fixed bed reactors, to be catalyzed in resistant to sulfur Mo methylmethaneizations in these reactors
Methanation reaction and water gas shift reaction are carried out simultaneously in the presence of agent, and in resistant to sulfur in last fixed bed reactors
Methanation reaction is only carried out in the presence of Mo methylmethane catalyst,
Above-mentioned fixed bed reactors are divided into high temperature fixed bed reactor according to fixed bed reactors outlets products temperature degree
With low temperature fixed bed reactors, fixed bed reactors outlets products temperature degree is high temperature fixed bed reactor higher than 550 DEG C, at it
It is middle to be less than using the high temperature resistant to sulfur Mo methylmethane catalyst with high-fire resistance, fixed bed reactors outlets products temperature degree
550 DEG C are low temperature fixed bed reactors, wherein using the low temperature resistant to sulfur Mo methylmethane catalyst of high catalytic activity；
After above-mentioned crude synthesis gas is passed sequentially through the fixed bed reactors of all series connection, then take off into sour gas through cooling down
Except sulfide gas and carbon dioxide therein in unit, is removed, finally it is allowed to be changed into being rich in methane gas, wherein, it is each anti-
Answer device all without circulation of tail gas, whole reaction system is without circulation of tail gas device and supplement methanator.
Preferably, in above-mentioned reactor assembly, the methanation reaction air speed is 2000~10000/ hours, the water
Gas shift reaction air speed is 2000~10000/ hours；The high temperature fixed bed reactor inlet crude synthesis gas or product temperature
Spend for 200-450 DEG C, more preferably 250-350 DEG C；Low temperature fixed bed reactor inlet unstripped gas or product the temperature degree is
200-450 DEG C, more preferably 230-450 DEG C；The high temperature fixed bed reactor outlet product temperature degree is 550 DEG C -680 DEG C,
The low temperature fixed bed reactor outlet product temperature degree is 380 DEG C -550 DEG C.
Preferably, in above-mentioned reactor assembly, high temperature resistant to sulfur Mo methylmethanes catalyst and low temperature the resistant to sulfur Mo bases
Methanation catalyst is all for catalytic activity phase, with Co or Ni sulfide with Mo, W or/and V sulfide or/and oxide
Or/and oxide is coagent, wherein, high temperature resistant to sulfur Mo methylmethanes catalyst is with aluminium, zirconium, lanthanum, yttrium, titanium, cerium and magnesium
Three to four kinds of hopcalites be carrier；Low temperature resistant to sulfur Mo methylmethanes catalyst is with two to three kinds in above-mentioned metal
Hopcalite is carrier.High temperature resistant to sulfur Mo methylmethanes catalyst forms：0-10 parts CoO, 8-25 part MoO3, 10-
30 parts of CeO2, 1-25 part MgO and 40-60 parts Al2O3；.；Low temperature resistant to sulfur Mo methylmethanes catalyst forms：0-10 part NiO,
10-30 parts MoO3, 5-15 parts Y2O3And 50-90 parts ZrO2。
Preferably, in above-mentioned reactor assembly, it is passed through into each high temperature fixed bed reactor and accounts for unstripped gas or product
Gas (butt) 3%-20 volumes % water vapour, it is passed through into low temperature fixed bed reactors and accounts for unstripped gas or product gas (butt)
3%-10% volumes % water vapour.
According to the second aspect of the invention, there is provided one kind uses foregoing fixed bed methanator system by crude synthesis gas
The method rich in methane gas is converted into, is comprised the following steps successively：(1) crude synthesis gas is made to pass sequentially through all series connection
Fixed bed reactors, wherein in the fixed bed reactors of water vapour are passed through while methanation reaction occurs and Water gas shift/WGS is anti-
Should, methanation reaction is only carried out in the fixed bed reactors that last is not passed through water vapour；(2) last is fixed
The product air cooling of bed reactor discharge, then be passed into the acid gas removal unit, remove sulfide gas therein
Body and carbon dioxide, so as to be allowed to be changed into be rich in methane gas.
In the above-mentioned methods, as needed, to also to be fixed after being discharged from a fixed bed reactors into another
The product gas or unstripped gas reacted in bed reactor, before entering in another fixed bed reactors, is carried out cold to it
But cool.
Brief description of the drawings
Fig. 1 is that the present invention is segmented the fixed bed methanator system and its work that water vapour is injected into multiple reactors
The schematic diagram of skill.
Fig. 2 is the fixed bed methanator system and its technique that water vapour is disposably injected into first reactor
Schematic diagram.
Embodiment
By the way that the present invention is further explained in detail below with reference to the description of accompanying drawing, but following description is only used for making institute of the present invention
The principle and marrow of the present invention can be more clearly understood in the those of ordinary skill of category technical field, be not meant to this hair
It is bright to carry out any type of limitation.Equivalent or corresponding part or feature are represented with identical reference numerals in accompanying drawing.
The characteristics of compared with fluidized-bed reactor, fixed bed reactors have simple structure, and easily operation and industry are amplified.
The invention discloses a kind of fixed bed methanator technique suitable for resistant to sulfur Mo methylmethane catalyst, and technique is using extremely
The mode of few three fixed bed reactors series connection, can be achieved crude synthesis gas being converted into rich in CH4Product gas, product gas enters one
Step removing H2S and CO2Afterwards, you can obtain the natural gas for meeting Standard.
Present invention process is only applicable to Mo base catalyst, because the catalyst is provided simultaneously with methanation and Water gas shift/WGS pair
The synthesis gas that the gasification furnace such as heavy activity, therefore lurgi gasifier, Texaco, E-Gas obtains is used equally for this technique.According to unstripped gas
H2/ CO than difference, the steam vapour amount that each methanator entrance need to add is also different, unstripped gas H2/ CO ratios are lower, system
Needed for total steam vapour amount for adding it is also higher.It is that water-gas becomes progress in more preferable promotion reactor in system, vapor needs
It is usually added in excess.
In conventional methane series reactor process, to control front reaction device outlet temperature, it usually needs by part
Rear end reactor tail gas is circulated to dilute the concentration of fresh synthesis gas in leading portion reactor.Therefore, urged in front reaction device
The heat resistant requirements of agent are higher, and catalyst heat resistance is better, and the recycle ratio needed for tail gas is lower.The high temperature that the present invention uses
Resistant to sulfur Mo methylmethane catalyst the upper limit temperature of heat tolerance is higher than 650 DEG C, therefore this technique can avoid circulation of tail gas.In addition, with
The progress of reaction, CO in system2Concentration gradually increases, catalyst methaneization activity is gradually suppressed, at the same time with
The carry out methanation reaction of reaction moves closer to balance, wants further to promote the progress of methanation reaction, reaction must be low
Temperature is lower to be carried out.Therefore to the resistance to CO of catalyst in the second half section of technique or end reaction device2Performance requires more with low temperature active
It is high.The present invention has used the low temperature resistant to sulfur Mo methylmethane catalyst of high catalytic activity in these reactors, and it is with ZrO2Deng
Oxide is carrier, and due to the use of this catalyst, the synthesis gas in reaction system is fully converted into methane, is avoided existing
Have in technology acid gas removing after reuse supplement methanator, so as to produce mass energy waste the drawbacks of.
Preferably, directly prepared rich in CH by crude synthesis gas in the present invention4In the methanation process of gas, into the first
The H of crude synthesis gas in alkylation reactors2/ CO mol ratios are 0.4-1.6, it is preferable that H2/ CO mol ratios are 0.7-1.3.
The present invention is provided a kind of directly prepared using crude synthesis gas and is rich in CH4The methanation in presence of sulfur technique of gas, wherein slightly
Synthesis gas can be by shell, Texaco, and GSP, E-Gas and the Shandong coal gasifier such as very are prepared, and preferably synthesis gas is by moral scholar
Ancient and E-Gas gasification furnaces are prepared.H in the crude synthesis gas be prepared by shell and GSP2/ CO ratios typically smaller than 0.6, far
Required less than 1.0 needed for reaction, to ensure that the middle synthesis gas of system is completely converted, then need additionally to supplement substantial amounts of water steaming
Gas, this not only lowers methanation efficiency and a large amount of vapor need to be consumed.And the synthesis gas that Texaco and E-Gas gasification furnaces obtain
H2/ CO ratios typically larger than 0.65, substantially close to 1.0 needed for reaction, therefore it is more suitable for this technique.For lurgi gasifier, it is closed
Into gas H2/ CO ratios typically larger than 1.5, under this high hydrogen-carbon ratio can vapour gas shift reaction speed against the current in accelerating reactor,
Thus also it is unfavorable for the progress of methanation reaction.
Therefore, prepared in crude synthesis gas provided by the invention and be rich in CH4In the methanation in presence of sulfur technique of gas, required water steams
Gas need to be added parallel by being segmented into multiple reactors.In existing multiple reactor methanation process, vapor is once
Property be added in first reactor, this causes in first reactor water coal vapour transformationreation excessively occurs, whole so as to reduce
The methanation efficiency of methanation unit, cause the synthesis gas in system can not to be only fully converted into by direct methanation process
Methane using low temperature acid gas, it is necessary to remove process by the CO of generation2After removing, reuse supplement methanation process and synthesize residue
Gas is fully converted into methane.
Direct methanation reaction is substantially carried out in methanator, reaction equation is：
But work as porch crude synthesis gas H2When being less than 1.0 with CO mol ratio, CO will occur with entering the vapor in implication
Water coal vapour transformationreation, with the H in replenishment system2Content, reaction equation are：
The high temperature resistant to sulfur Mo methylmethane catalyst of high-temperature heat-resistance, the high-temperature heat-resistance are loaded in high temperature fixed bed reactor
Resistant to sulfur Mo methylmethane catalyst ensure that high temperature of the high temperature fixed bed reactor more than 650 DEG C in system first half
Under can still have to follow in follow-up tail gas for control reactor outlet product temperature degree so as to avoid with stable operation
Ring.
Being loaded in low temperature fixed bed reactors under low temperature has high catalytic activity and resistance to CO2Low temperature resistant to sulfur Mo Ji Jia
Alkanizing catalyst, the catalyst can make system latter half or the low temperature fixed bed reactors of end in high CO2Grasped with low temperature
Make that still there is high methanation catalyst activity under environment, ensure all fully to convert all synthesis gas in system, avoid use
Supplement methanator and the malaria drawback thus brought.
Not only flow becomes shorter natural gas from coal technique including methanation system of the present invention, and also reduces whole
The equipment investment of natural gas from coal technology, further, since methanation process of the present invention is without using the Ni Ji Jia sensitive to sulfur species
Alkanizing catalyst, therefore, the thick synthetic natural gas obtained after methanation only need to take off sulfur species concentration to meeting Standard i.e.
Can (about 4ppm), avoid the deep desulfuration process being in the prior art removed to sulfur species less than 0.1ppm.
As shown in figure 1, in the present invention, contain H2、CO、CO2, vapor and a certain amount of sulfide gas synthesis gas
Into in the fixed bed methanator of multiple series connection, and direct methanation is carried out wherein and reacts anti-with water-gas conversion
Should, by H in synthesis gas2CH is changed into CO4, so as to form the rough gas of the synthesis of natural containing a small amount of impurity；
The above-mentioned rough gas of the synthesis of natural containing a small amount of impurity is removed most CO in thick gas clean unit2And sulphur
The sour gas such as compound, so as to form the refined synthetic natural gas after purification, the refined synthetic natural gas is fully met naturally
Gas national standard (GB17820-2012) technical specification.
In order to ensure by CO and H2It is fully converted to CH4, need to add in fixed bed methanator system of the present invention
A certain amount of vapor, to promote the progress that Water gas shift/WGS (WGS) is reacted.The difference formed according to crude synthesis gas air inlet, water steam
The addition of gas is also different.If all vapor add from first reactor, system front end or first half will be caused
Reactor in Water gas shift/WGS (WGS) hyperactivity so that methanation reaction is suppressed in these reactors, to solve
This problem, the present invention add vapor simultaneously into multiple reactors by stages.In addition, if all vapor pass through
One reactor is added, and steam partial pressure is higher in the reactor, and this is proposed to being loaded into catalyst hydrothermal stability therein
Requirements at the higher level.And if vapor is segmented into multiple reactors while added, it is right in first reactor to mitigate significantly
The strict demand of catalyst hydrothermal stability index.
The advantage of fixed bed methanator system of the present invention includes：(1) Mo methylmethane catalyst is used, can be by slightly
Synthesis gas is converted into the gas rich in methane.(2) methanation uses the fixed bed reactors of at least three series connection, nothing
Circulation of tail gas need to be carried out, it is not required that supplement methanator, therefore, system energy consumption reduces.(3) vapor needed for be segmented to
Added simultaneously in multiple fixed bed reactors, rather than all vapor are disposably added in first reactor, this
Sample can not only ensure that raw material of synthetic gas is more efficiently converted into methane, can also reduce to catalyst hydrothermal stability index
Strict demand.
Typical exemplary process flow of the invention is as shown in figure 1, the technique includes the fixed bed methanation of four series connection
Reactor.Crude synthesis gas from gasification furnace is exchanged heat to 250-350 DEG C, then is incorporated 5%-20 volumes % vapor entrance
In 101 reactors, 101 reactors use insulation fix bed reactor, reactor outlet product temperature degree 560-680 DEG C it
Between.101 reactor outlet product gas are through being exchanged heat to 250-350 DEG C, then are incorporated 4%-18 volumes % vapor to enter 102 anti-
Answer in device, 102 reactors also use insulation fix bed reactor, and reactor outlet product temperature degree is between 540-630 DEG C.
102 reactor outlet product gas through exchange heat to 250-450 DEG C, then be incorporated 0%-10% vapor enter 103 reactors in,
103 reactors use insulation fix bed reactor or constant temperature fixed bed reactors, if the reactor is insulation fix bed reactor,
Reactor outlet product temperature degree is between 400-540 DEG C, if the reactor is isothermal reactor, whole temperature of reactor control
System is between 400-500 DEG C.103 reactor outlet product gas enter 104 reactors after heat exchange is cooled, and 104 reactors are adopted
With constant temperature fixed bed reactors, whole temperature of reactor control is between 350-450 DEG C.104 outlets products gas are sent to acid gas
In removal unit, H therein is removed2S and CO2Afterwards, sulfur species concentration is made to reach below 40ppm, you can to obtain meeting national standard
CH4Replacement natural gas of the content more than 90 volume %.
Fig. 2 gives the schematic diagram of another fixed bed methanator system and its technique, wherein, with Fig. 1 institutes
The technique shown is compared, and water vapour is disposably added in first reactor.
Embodiment
In following examples and comparative example, high temperature resistant to sulfur Mo methylmethanes catalyst composition used is：5CoO/
10MoO3/15CeO2/25MgO/45Al2O3；Low temperature resistant to sulfur Mo methylmethanes catalyst forms：5NiO/15MoO3/10Y2O3/
70ZrO2。
Embodiment 1
Acid methanation reaction, raw gas 98,000Nm are carried out according to technological process shown in Fig. 13/ h, pressure 4.5MPa,
After the impurity such as removing dust, tar, preliminary clearning slightly synthesizes (volume %, butt) composition and is：H2：41.6%, CO:38.7%,
CO2：18.6%, CH4：0.1%, H2S+COS：0.08%, N2+AR：0.9%.
Preliminary clearning synthesis gas adds water vapour, water vapour addition is preliminary clearning synthesis gas volume through exchanging heat to 250 DEG C
15%, afterwards into first adiabatic methanation (high temperature) reactor.Under high temperature resistant to sulfur Mo methylmethane catalyst actions,
Methanation reaction and water gas shift reaction occurs simultaneously in methanator.First paragraph adiabatic reactor outlets products temperature
Spend for 650 DEG C, obtain first paragraph initial action raw gas, its (volume %, butt) composition is：H2：32.2%, CO：31.8%,
CO2：27.5%, CH4：7.5%, N2+AR：1.0%.
After waste heat boiler reclaims heat, first paragraph initial action raw gas temperature declines, afterwards into second methanation
In (high temperature) reactor, second (high temperature) reactor uses insulation fix bed reactor, its import product temperature degree：250 DEG C,
Water vapour is added, water vapour addition is 15 volume % of preliminary clearning synthesis gas, in high temperature resistant to sulfur Mo methylmethane catalyst
Under effect, direct methanation reaction and water gas shift reaction, reactor outlet product temperature degree occurs：586 DEG C, obtain second
Duan Fanying raw gas, its (butt) composition are：H2：26.0%, CO：13.0%, CO2：43.4%, CH4：15.9%, N2+AR：
1.1%.
After waste heat boiler reclaims heat, second segment reaction raw gas temperature declines, (low into the 3rd methanation afterwards
Temperature) in reactor, the 3rd (low temperature) reactor use insulation fix bed reactor, and its import product temperature degree is 260 DEG C,
In the presence of low temperature resistant to sulfur Mo methylmethane catalyst, direct methanation reaction and water gas shift reaction, the reactor occurs
Outlets products temperature degree：547 DEG C, the 3rd section of reaction raw gas is obtained, its (volume %, butt) composition is：H2：8.9%, CO：
2.9%, CO2：58.1%, CH4：28.6%, N2+AR：1.4%.
After waste heat boiler reclaims heat, the 3rd section of reaction raw gas temperature declines, (low into the 4th methanation afterwards
Temperature) in reactor, the 4th (low temperature) reactor be isothermal reactor, and temperature control is 380 DEG C, in low temperature resistant to sulfur Mo methylmethanes
In the presence of changing catalyst, direct methanation reaction occurs, after reactor outlet gas is cooled to normal temperature, obtains the 4th section slightly
Product gas, consisting of：H2:1.2%, CO:0.1%, CO2:62.9%, CH4:34.0%, N2+AR:1.5%；
In acid gas removal unit, the CO in the 4th section of crude product gas is removed2And sulfide, it is made and meets natural gas
The synthetic natural gas of national standard (GB17820-2012) technical specification, it forms (volume %, butt)：H2：3.1%, CO：0.2%,
CO2：0.9%, CH4:91.8%, N2+AR：4.1%, H2S+COS：3ppm.Product gas calorific value is 36.9MJ/NM3, meet and be made full
The one-level synthetic natural gas standard of sufficient natural gas national standard (GB17820-2012) technical specification.
Embodiment 2
Acid methanation reaction, raw gas 98,000Nm are carried out according to technological process shown in Fig. 13/ h, pressure 4.5MPa,
After the impurity such as removing dust, tar, preliminary clearning crude synthesis gas (volume %, butt) composition is：H2：41.6%, CO:
38.7%, CO2：18.6%, CH4：0.11%, H2S+COS：0.08%, N2+AR：0.89%.
Preliminary clearning synthesis gas adds water vapour after exchanging heat to 250 DEG C, and water vapour addition is preliminary clearning synthesis gas volume
15%, afterwards, into first adiabatic methanation (high temperature) reactor.It is mounted with methanation (high temperature) reactor
High temperature resistant to sulfur Mo methylmethane catalyst, so as to methanation reaction should occur simultaneously in (high temperature) reactor and Water gas shift/WGS is anti-
Should.First thermal insulation (high temperature) reactor outlet product temperature degree is 650 DEG C, obtains first paragraph reaction raw gas, its (body
Product %, butt) composition be：H2：32.2%, CO：31.8%, CO2：27.5%, CH4：7.5%, N2+AR：1.0%.
After waste heat boiler reclaims heat, first paragraph reaction raw gas enters in second methanation (high temperature) reactor,
Second (high temperature) reactor is adiabatic reactor, and its import product temperature degree is 250 DEG C, adds water vapour, and water vapour adds
Measure as the 7.5% of preliminary clearning synthesis gas volume, in the presence of high temperature resistant to sulfur Mo methylmethane catalyst, (high temperature) reactor
In simultaneously occur direct methanation reaction and water gas shift reaction, reactor outlet product temperature degree be 620 DEG C, obtain second
Duan Fanying raw gas, its (volume %, butt) composition are：H2：23.7%, CO：16.7%, CO2：42.0%, CH4：16.3%,
N2+AR：1.2%.
After waste heat boiler reclaims heat, second segment reaction raw gas enters in the 3rd methanation (low temperature) reactor,
3rd methanation (low temperature) reactor is isothermal reactor, and reaction temperature is 450 DEG C, and water vapour is mixed into it enters implication,
Water vapour addition is the 7.5% of preliminary clearning synthesis gas volume, should in the presence of low temperature resistant to sulfur Mo methylmethane catalyst
Direct methanation reaction and water gas shift reaction occurs in (low temperature) reactor simultaneously, obtains the 3rd section of reaction raw gas, its
(volume %, butt) forms：H2：9.6%, CO：3.5%, CO2：57.4%, CH4：28.0%, N2+AR：1.4%；
After waste heat boiler reclaims heat, the 3rd section of reaction raw gas enters in the 4th methanation (low temperature) reactor,
4th (low temperature) reactor is isothermal reactor, and reaction temperature is 380 DEG C, in the work of low temperature resistant to sulfur Mo methylmethane catalyst
Under, direct methanation reaction should occur in (low temperature) reactor simultaneously, reactor outlet gas after heat exchange is cooled to normal temperature,
Crude product gas is obtained, its composition (volume %, butt) is：H2:1.3%, CO:0.1%, CO2:63.2%, CH4:33.8%, N2+
AR:1.5%.
In acid gas removal unit, the CO in above-mentioned crude product gas is removed2And sulfide, it is met natural gas state
Mark the synthetic natural gas of (GB17820-2012) technical specification, its (volume %, butt) composition：H2：3.6%, CO：0.2%,
CO2：0.9%, CH4:91.3%, N2+AR：4.1%, H2S+COS：3ppm.Product gas calorific value is 37.6MJ/NM3, meet and be made full
The one-level synthetic natural gas standard of sufficient natural gas national standard (GB17820-2012) technical specification.
Embodiment 3
Acid methanation reaction is carried out according to flow shown in Fig. 1, using Texaco stove raw gas, its flow is 2000Nm3/
H, pressure 4.5MPa, after the impurity such as removing dust, tar, preliminary clearning crude synthesis gas (volume %, butt) composition is：H2：
36.2%, CO:49.6%, CO2：12.9%, CH4：0.4%, H2S+COS：0.08%, N2+AR：0.9%.
Preliminary clearning raw material of synthetic gas adds water vapour, water vapour addition is preliminary clearning synthesis gas after exchanging heat to 240 DEG C
The 7.5% of volume, afterwards into first insulation fix bed methanation (high temperature) reactor.Reacted in the methanation (high temperature)
High temperature resistant to sulfur Mo methylmethane catalyst is mounted with device, so as to methanation reaction and water should occur simultaneously in (high temperature) reactor
Gas shift reaction.First thermal insulation (high temperature) reactor outlet product temperature degree is 678 DEG C, obtains first paragraph reaction rough coal
Gas, its (volume %, butt) composition are：H2：29.2%, CO：39.1%, CO2：23.4%, CH4：7.2%, N2+AR：0.9%.
After waste heat boiler reclaims heat, first paragraph reaction raw gas enters in second methanation (high temperature) reactor,
Second (high temperature) reactor is adiabatic reactor, and its import product temperature degree is 250 DEG C, adds water vapour, and water vapour adds
Measure as the 7.5% of preliminary clearning synthesis gas volume, should be in (high temperature) reactor under high temperature resistant to sulfur Mo methylmethane catalyst actions
Direct methanation reaction and water gas shift reaction occur simultaneously, reactor outlet product temperature degree is 630 DEG C, obtains second segment
Raw gas is reacted, its (volume %, butt) composition is：H2：22.2%, CO：22.9%, CO2：30.8%, CH4：12.3%, N2+
AR：1.0%.
After waste heat boiler reclaims heat, second segment reaction raw gas enters in the 3rd methanation (high temperature) reactor,
3rd (high temperature) reactor is adiabatic reactor, and import product temperature degree is 230 DEG C, adds water vapour, water vapour addition
, should be same in (high temperature) reactor under high temperature resistant to sulfur Mo methylmethane catalyst actions for the 7.5% of preliminary clearning synthesis gas volume
Shi Fasheng direct methanations react and water gas shift reaction, and reactor outlet product temperature degree is 548 DEG C, obtain the 3rd section instead
Raw gas is answered, its (volume %, butt) composition is：H2：11.0%, CO：6.8%, CO2：54.9%, CH4：26.1%, N2+AR：
1.0%.
After waste heat boiler reclaims heat, the 3rd section of reaction raw gas enters in the 4th methanation (low temperature) reactor,
4th (low temperature) reactor is isothermal reactor, and reaction temperature is 380 DEG C, in the work of low temperature resistant to sulfur Mo methylmethane catalyst
Under, direct methanation reaction should occur in (low temperature) reactor, its exit gas is slightly produced after heat exchange is cooled to normal temperature
Product gas, crude product gas (volume %, butt) composition are：H2:2.1%, CO:0.3%, CO2:63.1%, CH4:33.80%, N2+
AR:1.4%.
In acid gas removal unit, the CO in crude product gas is removed2And sulfide, it is met natural gas national standard
(GB17820-2012) synthetic natural gas of technical specification, its (volume %, butt) composition：H2：5.6%, CO：0.9%,
CO2：0.3%, CH4：90.0%, N2+AR：3.8%, H2S+COS：3ppm.Product gas calorific value is 37.7MJ/NM3, meet natural gas
The one-level synthetic natural gas standard of national standard (GB17820-2012) technical specification.
Comparative example 1
Acid methanation reaction is carried out according to technological process shown in Fig. 2, rough coal throughput is 98,000Nm3/ h, pressure are
4.5MPa, after the impurity such as removing dust, tar, preliminary clearning slightly synthesizes (volume %, butt) composition and is：H2：41.6%, CO:
38.7%, CO2：18.6%, CH4：0.1%, N2+AR：0.9%, H2S+COS：0.08%.
Preliminary clearning raw material of synthetic gas adds water vapour, water vapour addition is preliminary clearning synthesis gas after exchanging heat to 250 DEG C
The 30% of volume, afterwards into first adiabatic methanation (high temperature) reactor.Filled in methanation (high temperature) reactor
High temperature resistant to sulfur Mo methylmethane catalyst is loaded with, so as to methanation reaction and water-gas change should occur simultaneously in (high temperature) reactor
Change reaction.First thermal insulation (high temperature) reactor outlet product temperature degree is 640 DEG C, obtains first paragraph reaction raw gas, its (body
Product %, butt) composition be：H2：38.8%, CO：20.3%, CO2：33.7%, CH4：6.2%, N2+AR：0.9%.
After waste heat boiler reclaims heat, first paragraph reaction raw gas enters in second methanation (high temperature) reactor,
Second methanation (high temperature) reactor is insulation fix bed reactor, and its import product temperature degree is 250 DEG C, in high temperature resistant to sulfur
Under Mo methylmethane catalyst actions, it is somebody's turn to do in (high temperature) reactor while direct methanation occurs and react anti-with Water gas shift/WGS
Should, reactor outlet product temperature degree is 580 DEG C, obtains second segment reaction raw gas, and its (volume %, butt) composition is：H2：
24.8%, CO：10.8%, CO2：45.3%, CH4：17.9%, N2+AR：1.1%.
After waste heat boiler reclaims heat, second segment reaction raw gas enters in the 3rd methanation (low temperature) reactor,
3rd (low temperature) reactor is adiabatic reactor, and Reactor inlet product temperature degree is 250 DEG C, in low temperature resistant to sulfur Mo methylmethanes
In the presence of changing catalyst, direct methanation reaction and water gas shift reaction, reaction should occur simultaneously in (low temperature) reactor
Device outlets products temperature degree is 490 DEG C, obtains the 3rd section of reaction raw gas, and its (volume %, butt) composition is：H2：6.1%,
CO：5.9%, CO2：56.9%, CH4：29.7%, N2+AR：1.4%.
After waste heat boiler reclaims heat, the 3rd section of reaction raw gas enters in the 4th methanation (low temperature) reactor,
4th (low temperature) reactor is isothermal reactor, and reaction temperature is 380 DEG C, in the work of low temperature resistant to sulfur Mo methylmethane catalyst
Under, direct methanation reaction and water gas shift reaction should occur simultaneously in (low temperature) reactor, it is thick to obtain the 4th section of reaction
Coal gas, after the 4th section of reaction raw gas is cooled to normal temperature, crude product gas is obtained, crude product gas (volume %, butt) composition is：
H2:0.7%, CO:3.5%, CO2:63.1%, CH4:31.3%, N2+AR:1.5%.
In acid gas removal unit, the CO in crude product gas is removed2And sulfide, it is met natural gas national standard
(GB17820-2012) synthetic natural gas of technical specification, its (volume %, butt) composition are：H2：1.8%, CO：9.4%,
CO2：0.8%, CH4：83.9%, N2+AR：3.9%, H2S+COS：3ppm.Product gas calorific value is 34.8MJ/NM3, meet natural gas
The one-level synthetic natural gas standard of national standard (GB17820-2012) technical specification.
Table 1
a:In national standard GB17820-2012, the standard reference conditions of gas volume are 101.325KPa, 20 DEG C；b:National standard
In GB17820-2012, under transport condition, when the buried temperature of pipeline tube top is 0 DEG C, water dew point should be not higher than -5 DEG C；c:State
Mark in GB17820-2012, into the natural gas of gas pipeline, the pressure of water dew point should be highest discharge pressure.
As shown in table 1,1-3 of the embodiment of the present invention and right is determined according to natural gas national standard (GB17820-2012) technical specification
The synthetic natural gas product obtained than embodiment 1, synthetic natural gas product only meets two class natural gas marks in comparative example 1
It is accurate.And all technical of the synthetic natural gas product in 1-3 of the embodiment of the present invention, all meet a kind of Natural gas standard.
Term and form of presentation used in this specification are merely used as descriptive and nonrestrictive term and statement side
Formula, it is not intended to have represented and any equivalent of the feature described or its part when using these terms and form of presentation
Exclusion.
Although having show and described several embodiments of the invention, the present invention is not limited to described implementation
Mode.On the contrary, those skilled in the art are not it should be recognized that departing from the feelings of principle and spirit of the present invention
These embodiments can be carried out with any flexible and improvement, protection scope of the present invention is by appended claim and its waits under condition
Jljl is determined.
Claims (10)
1. a kind of be converted into the fixed bed methanator system rich in methane gas, the system bag by crude synthesis gas
Include at least two insulation fix bed reactor being sequentially connected in series, at least one constant temperature fixed bed reactors and at least one sour gas
Removal unit,
Wherein, last fixed bed reactors is constant temperature fixed bed reactors, to outside last fixed bed reactors
Water vapour is passed through at least two fixed bed reactors, to cause in these reactors in resistant to sulfur Mo methylmethane catalyst
Effect is lower to carry out methanation reaction and water gas shift reaction simultaneously, and in resistant to sulfur Mo bases in last fixed bed reactors
Methanation reaction is only carried out in the presence of methanation catalyst,
Above-mentioned fixed bed reactors are divided into high temperature fixed bed reactor and low according to fixed bed reactors outlets products temperature degree
Warm fixed bed reactors, fixed bed reactors outlets products temperature degree are high temperature fixed bed reactor higher than 550 DEG C, are made wherein
With the high temperature resistant to sulfur Mo methylmethane catalyst with high-fire resistance, fixed bed reactors outlets products temperature degree is less than 550 DEG C
For low temperature fixed bed reactors, wherein using the low temperature resistant to sulfur Mo methylmethane catalyst of high catalytic activity；
After above-mentioned crude synthesis gas is passed sequentially through the fixed bed reactors of all series connection, then through cooling enter acid gas removal list
In member, sulfide gas and carbon dioxide therein are removed, is eventually become rich in methane gas, wherein, each reactor nothing
Circulation of tail gas is needed, whole reaction system is without circulation of tail gas device and supplement methanator.
2. reactor assembly according to claim 1, the methanation reaction air speed is 2000~10000/ hours, the water coal
Gas transformationreation air speed is 2000~10000/ hours.
3. reactor assembly according to claim 1, high temperature fixed bed reactor inlet crude synthesis gas or product the temperature degree
For 200-450 DEG C；Low temperature fixed bed reactor inlet unstripped gas or product the temperature degree is 200-450 DEG C.
4. reactor assembly according to claim 3, high temperature fixed bed reactor inlet crude synthesis gas or product the temperature degree
It is further 250-350 DEG C；Low temperature fixed bed reactor inlet unstripped gas or product the temperature degree is further 230-450
℃。
5. reactor assembly according to claim 1, the high temperature fixed bed reactor outlet product temperature degree is 550 DEG C -680
℃；The low temperature fixed bed reactor outlet product temperature degree is 380 DEG C -550 DEG C.
6. reactor assembly according to claim 1, high temperature resistant to sulfur Mo methylmethanes catalyst and low temperature resistant to sulfur the Mo Ji Jia
Alkanizing catalyst be all with Mo, W or/and V sulfide or/and oxide for catalytic activity phase, with Co or Ni sulfide or/
It is coagent with oxide, wherein, high temperature resistant to sulfur Mo methylmethanes catalyst is with three in aluminium, zirconium, lanthanum, yttrium, titanium, cerium and magnesium
It is carrier to four kinds of hopcalites；Low temperature resistant to sulfur Mo methylmethanes catalyst is with two to three kinds of oxidations in above-mentioned metal
The mixture of thing is carrier.
7. reactor assembly according to claim 6, wherein, high temperature resistant to sulfur Mo methylmethanes catalyst composition is：0-10 parts
CoO, 8-25 part MoO3, 10-30 parts CeO2, the Al of 1-25 part MgO and 40-60 parts2O3；Low temperature resistant to sulfur Mo methylmethane catalyst
Form and be：0-10 parts NiO, 10-30 part MoO3, 5-15 parts Y2O3And 50-90 parts ZrO2。
8. reactor assembly according to claim 1, wherein, it is passed through into each high temperature fixed bed reactor and accounts for unstripped gas or production
The water vapour of thing gas butt 3%-20% volumes, it is passed through into low temperature fixed bed reactors and accounts for unstripped gas or product gas butt 3%-
The water vapour of 10% volume.
9. a kind of fixed bed methanator system with described in claim 1-8 is one of any directly converts crude synthesis gas
For the method rich in methane gas, comprise the following steps successively：
(1) crude synthesis gas is made to pass sequentially through the fixed bed reactors of all series connection, wherein being passed through the fixed bed reaction of water vapour
Methanation reaction and water gas shift reaction occurs simultaneously in device, in the fixed bed reactors that last is not passed through water vapour
In only carry out methanation reaction；
(2) the product air cooling for discharging last fixed bed reactors, then it is passed into the acid gas removal unit
In, sulfide gas and carbon dioxide therein are removed, so as to be allowed to be changed into be rich in methane gas.
10. method according to claim 9, wherein, as needed, to also to enter after being discharged from a fixed bed reactors
The product gas or unstripped gas reacted in another fixed bed reactors, before entering in another fixed bed reactors,
It is cooled down.
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