CN104073308B - A kind of synthetic gas system substitutes the methanation in presence of sulfur technique of Sweet natural gas - Google Patents
A kind of synthetic gas system substitutes the methanation in presence of sulfur technique of Sweet natural gas Download PDFInfo
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Abstract
To be synthetic gas enter paste state bed reactor carry out methanation through mending hydrogen evolution unstripped gas the methanation in presence of sulfur technique that a kind of synthetic gas system substitutes Sweet natural gas bottom slurry bed system, thick gas product is discharged from paste state bed reactor top and is entered gas-liquid-solid separator, be separated the liquid-solid phase obtained and together enter liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system, the solid phase that liquid-solid separator is separated is discharged from the bottom of liquid-solid separator, enters catalyst regeneration device and carries out catalyst regeneration; The liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, turns back to paste state bed reactor through pump, is separated the thick gas product that obtains through purifying to obtain Sweet natural gas through gas-liquid-solid separator.It is high that the present invention has energy utilization rate, facility investment and working cost low, easy-operating advantage.
Description
Technical field
The invention belongs to a kind of synthetic natural gas technique, be specifically related to the technique that a kind of producing synthesis gas from coal carries out methanation in presence of sulfur synthetic natural gas.
Background technology
Coal, oil and natural gas are three large pillars of world energy sources structure.Sweet natural gas is a kind of clean, efficient Energy resources.In current world energy sources consumption structure, Sweet natural gas accounts for 24%, and China's natural gas proportion is less than 5%, far below world average level.Be badly in need of the consumption improving Sweet natural gas.On the other hand, the rich coal resources of China, but mainly concentrate on remote districts, Midwest, and energy expenditure mainly concentrates on Middle Eastern, Coal Transport ability and economy are the factors that restriction coal directly utilizes.Therefore coal high-efficiency be converted into environmental protection more and easily through the Sweet natural gas of pipeline transportation, there is important economic implications.
To be coal produce synthetic gas through gasification to coal preparing natural gas, synthetic gas by after carbon monodixe conversion and purifying treatment, through methanation synthetic natural gas.The key problem in technology of coal preparing natural gas is methanation catalyst, and current industrial methanation catalyst mainly nickel-base catalyst, this catalyzer has higher methanation ability, but very responsive to the sulphur in raw material, and a small amount of sulphur will cause poisoning of catalyst inactivation.As TREPM methanation technology and the German Lurgi company methanation technology of Topsoe company of Denmark, its core has to pass through low-temp methanol washing process and the sulphur in synthetic gas is removed to below 0.1ppm before being synthetic gas methanation, make synthetic gas temperature from 200-400 DEG C through low-temperature rectisol to-40 DEG C, then synthetic gas is warmed up to 300 DEG C and carries out methanation reaction.The wide variation of this temperature, cause a large amount of energy wastage, running cost is high.Meanwhile, this methanation process also suppresses temperature rise by the transformation efficiency controlling each section of reactor, and the overall temperature control of reaction process is realized by part gas circulation.Large-tonnage product air cooling but Posterior circle makes overall energy consumption huge, and investment cost is high, runs and controls complexity, and process economy reduces.
As patent CN201110058130.7 discloses a kind of device and method adopting gas-solid-gas-solids reactors to carry out synthetic gas full methanation, comprise full methanation, product and inert heat carrier particle separation and inert heat carrier particle reclaims circulation three key steps, but this technical operation flow is complicated, running cost is high, temperature controls not good, there is the problems such as catalyst carbon deposit; Patent CN201010524404.2 discloses a kind of technique of slurry bed system synthesizing natural gas by methanation of coal synthesis gas, this technique introduces the high inert liquid phase medium of thermal capacitance, bed temperature is even, catalyzer reduces in paste state bed reactor, but this technique requires high to the sulphur content of the synthetic gas of methanation reaction, and it is discontinuous that catalyst reduction and methanation reaction two operations exist operation in same reactor, gas switches the problems such as complicated.Patent CN200910093101.7 discloses a kind of synthetic gas fluidized-bed methanation process, it is strong that this technique has exchange capability of heat, bed temperature is even, catalyzer such as can to change online at the advantage, but technical process is complicated, must first carry out highly energy-consuming fine de-sulfur operation before unstripped gas carries out methanation reaction, phenomenon carried secretly by gas backmixing and raw material seriously causes methane conversion low.Above-mentioned main research methanation process and type of reactor, technical process is all waste Sweet natural gas with coal, but methanation reaction all requires harsh to material synthesis gas gas, for avoiding methanation catalyst sulfur poisoning, the fine de-sulfur operation of carrying out highly energy-consuming is needed before methanation reaction, cause technical process complicated, energy dissipation is serious.
Summary of the invention
In order to overcome methanation catalyst in existing coal process for producing natural not resistant to sulfur, meet the shortcoming of the easy poisoning and deactivation of Determination of Trace Sulfur, one is the object of the present invention is to provide to provide a kind of energy utilization rate high, facility investment and working cost low, the easy-operating technique being suitable for producing synthesis gas from coal methanation in presence of sulfur synthetic natural gas.
The present invention to achieve the above object of the invention, by the following technical solutions:
(1) feed coal produces through vapourizing furnace gasification the synthetic gas being used for methanation;
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, enter from the gas distributor bottom slurry bed system the paste state bed reactor that inert liquid phase medium and catalyst for methanation in presence of sulfur are housed and carry out methanation, thick gas product is discharged from paste state bed reactor top, after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator and be separated;
(3) be separated the liquid-solid phase obtained from gas-liquid-solid separator and together enter liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system, the solid phase that liquid-solid separator is separated is discharged from the bottom of liquid-solid separator, enters fixed bed catalyst regeneration device and carries out catalyst regeneration; The liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, turns back to paste state bed reactor through pump, is separated the thick gas product obtained obtains sales-quality gas product through heat exchange, purification through gas-liquid-solid separator;
(4), after the catalyst for methanation in presence of sulfur regenerated enters catalyzer storage tank, add in proportion in the inert liquid phase medium pipeline turning back to paste state bed reactor and enter paste state bed reactor together.
Feed coal as above can be bituminous coal, sub-bituminous coal, hard coal, the coals such as brown coal.
The vapourizing furnace of producing synthesis gas as above can be Lurgi vapourizing furnace, Shell vapourizing furnace, the devices such as GSP vapourizing furnace.
The main ingredient of the synthetic gas produced through vapourizing furnace as above by volume per-cent is:
H
2: 32.30%-38.90%, CO:20.10%-32.50%, CH
4: 7.60%-12.50%, CO
2: 24.50%-30.20%, H
2s:0.03%-0.60% (i.e. 300-6000ppm), N
2: 0.30%-0.90%
Synthetic gas as above obtains the unstripped gas meeting methanation requirement after mending hydrogen.H in unstripped gas
2-CO
2/ CO+CO
2volume ratio between 2.5-4.0, sulphur content is between 300-6000ppm.
Catalyst for methanation in presence of sulfur as above is load type sulfur-tolerant methanation catalyst, and its active ingredient is two or more combinations in Ni, Ce, Fe, Cr, the mass percentage 2-40% of active ingredient; Adjuvant component is the one or more combination in Mo, W, V, Y, Co, La, and the mass percentage of auxiliary agent is 0.5-35%; All the other are carrier, and carrier is Al
2o
3, SiO
2, TiO
2in one or more.Concrete preparation method is shown in: one is applicable to slurry bed system methanation sulfur resistant catalyst and method for making and application, Chinese patent 201310303342.6.
Slurry bed system inert liquid phase medium as above is one or more mixed solutions of paraffinic hydrocarbon, thermal oil, petroleum naphtha, hydrogenated terphenyl.
In slurry bed system methanator as above, the mass percent of sulfur resistant catalyst and inert liquid phase medium is: 1%-35%.
The resistant to sulfur scope of sulfur resistant catalyst as above is 200-8000ppm.
Slurry bed system methanation reaction temperature as above is 260-550 DEG C, and reaction pressure is 1-6MPa, and mixing speed is 300-1000r/min, and methanation unstripped gas air speed is 1000-15000L/hkg.
The reducing gas of fixed bed catalyst regeneration described above is H
2and N
2, H
2the volume ratio accounting for reducing gas is 5%-85%, and reduction temperature is 450-600 DEG C, and air speed is 1000-5000L/hkg.
One in the available low-temperature rectisol of purification as above or hydramine method.
The service temperature of low-temperature rectisol technology as above is between-30 ~-55 DEG C, and working pressure is at 4.0-6.0MPa
Hydramine method as above can adopt MEA, DEA, sulfone amine-II, MDEA.Preferably sulfone amine-II, service temperature between 20-50 DEG C, working pressure 4.0-6.0MPa.
Methyl alcohol also has following various significant advantage with hydramine at desulfurizing and purifying compared with other purification process:
● receptivity is strong, and solution circulated amount is little
● regeneration energy consumption is low
● gas purification degree is high
● solvent thermal stability and chemical stability good, solvent is not degraded, equipment does not corrode
● soltion viscosity is little, is conducive to saving power
● flow process is reasonable, easy and simple to handle.
The present invention compared with prior art, there is obvious technical superiority be: (1) have employed efficient catalyst for methanation in presence of sulfur, this catalyzer resistant to sulfur scope is wide, without the need to adopting synthetic gas fine desulfurizing technology, can directly carry out methanation reaction when the obnoxious flavour such as sulphur need not remove in synthetic gas, shortened process, easy to operate stable easily control, energy consumption is low.(2) traditional methanation process flow process is before methanation,-40 DEG C must be dropped to from 200-400 DEG C and carry out low-temperature rectisol fine de-sulfur by unstripped gas, be warmed up to methanation reaction temperature about 300 DEG C again to carry out in methanation, this process causes heat energy huge waste.The present invention adopts the wide methanation catalyst of resistant to sulfur scope effectively to solve the problem, the high sulfidation resistance of catalyzer can make unstripped gas desulfurization directly need not carry out methanation, thick gas product can after carrying out abundant heat exchange, adopt low-temperature rectisol or hydramine method to carry out desulfurization decarbonization purification again, obtain the sales-quality gas product meeting regulation in GB (GB-17820-2012).Obviously, technical process of the present invention is optimized rationally more, and energy utilization is high.(3) paste state bed reactor beds isothermal is good, inert media has the characteristic that thermal capacitance is large, thermal conductivity is large, reaction heat is shifted rapidly, ensure that whole bed is close to isothermal, the methanation catalyst knot carbon inactivation that there will not be catalyzer local superheating to cause, considerably reduce the energy consumption of producing synthesis gas from coal preparing natural gas by methanation, simplify technical process.(4) the present invention adopts catalyst cyclic regeneration technique, the catalyst for methanation in presence of sulfur of part inactivation is made to be separated, to reduce, to regenerate, recycle, ensures that catalyzer participates in methanation reaction in higher field of activity, makes reaction conversion ratio and the two raising of selectivity.
In a word, it is short that technical scheme provided by the invention has technical process, and energy consumption is low, reactor heat-sinking capability is strong, and reaction bed temperature is even, realizes catalyst cyclic regeneration, there is good Sulfur tolerance, reaction conversion ratio and selectivity high, can the advantages such as scale operation be carried out.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of producing synthesis gas from coal methanation in presence of sulfur synthetic natural gas
As shown in the figure, 1 compressor, 2 slurry bed system methanation in presence of sulfur reactors, 3 gas-liquid-solid separators, 4 liquid-solid separators, 5 catalyst reduction regenerating units, 6 catalyzer storage tanks, 7 inert media hold-up vessels, 8 agitator motors, 9,10 interchanger, 11,12 recycle pumps; B1, b2, b3, b4, b5, b6, b7, b8, b9, b10, b11, b12 and b13 are pipelines; G1, g2 are water of condensation.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to the restriction of following embodiment.
Embodiment 1
Prepared by slurry bed system synthetic gas catalyst for methanation in presence of sulfur:
By 80-100 order, specific surface area 150m
2γ-the Al of/g
2o
3in 400 DEG C of roasting 4h, temperature 25 DEG C, under mixing speed 100r/min condition, by Mo (NO
3)
35H
2o, Ni (NO
3)
26H
2o, γ-Al
2o
3by Mo:Ni:Al mass percent 25%:30%:45% incipient impregnation and stir 8h, after leaving standstill 4h, 60 DEG C are evaporated to sticky, then put into baking oven 80 DEG C of dry 12h, after be ground to 80-100 order and be placed in retort furnace in 450 DEG C of roasting 4h, obtained presoma; 20%H is consisted of at volume
2and 80%N
2flow velocity is in the atmosphere of 100mL/min, adopt two sections of temperature programmings, first be warmed up to 350 DEG C with 4 DEG C/min, then it is for subsequent use to be warming up to 2 DEG C/min the Mo-Ni-Al slurry bed system synthetic gas catalyst for methanation in presence of sulfur that 500 DEG C of constant temperature reduction 6h obtain Mo:Ni:Al mass percent 25%:30%:45%.
(1) brown coal are produced through BGL furnace gasization and are used for the synthetic gas of methanation, and the main ingredient of synthetic gas by volume per-cent is: H
2: 35.35%, CO:26.55%, CH
4: 9.60%, CO
2: 27.82%, H
2s:0.28% (2800ppm), N
2: 0.40%.
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, the paste state bed reactor that thermal oil, petroleum naphtha and Mo-Ni-Al system catalyst for methanation in presence of sulfur are housed in advance is entered bottom slurry bed system, be 500r/min at temperature 280 DEG C, pressure 2.0MPa, mixing speed, air speed 3000L/hkg carries out methanation reaction, wherein H in unstripped gas
2-CO
2/ CO+CO
2volume ratio be 3.1, H
2s is 2000ppm, and catalyzer and thermal oil, petroleum naphtha mass percent are 10%.Thick gas product is discharged from paste state bed reactor top, and after heat reclamation device heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system.
(3) liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, through being pumped into paste state bed reactor;
(4) solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, and entering fixed bed catalyst regeneration device, is 450 DEG C in temperature, air speed 3000L/hkg, 25% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(5) catalyst for methanation in presence of sulfur regenerated is the ratio of 10% in the mass ratio of catalyzer and inert liquid phase medium.Join in inert liquid phase medium pipeline and together enter paste state bed reactor.Thick gas product after gas-liquid-solid separator is separated through heat exchange, through sulfone amine-II temperature 25 DEG C, working pressure purifies under 4.0MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.3, carbonic acid gas volume fraction≤1.15, total sulfur content≤0.06ppm).
Embodiment 2
Prepared by slurry bed system synthetic gas catalyst for methanation in presence of sulfur:
By 60-80 order, specific surface area 150m
2γ-the Al of/g
2o
3in 450 DEG C of roasting 5h, temperature 35 DEG C, under mixing speed 120r/min condition, by Mo (NO
3)
35H
2o, NH
4vO
3, Ni (NO
3)
26H
2o, γ-Al
2o
3by Mo:V:Ni:Al mass percent 25%:10%:30%:35% incipient impregnation and stir 8h, after leaving standstill 4h, 80 DEG C are evaporated to sticky, then put into baking oven 110 DEG C of dry 12h, after be ground to 60-80 order and be placed in retort furnace in 550 DEG C of roasting 6h, obtained presoma; 25%H is consisted of at volume
2and 75%N
2flow velocity is in the atmosphere of 80mL/min, adopt two sections of temperature programmings, first be warmed up to 350 DEG C with 5 DEG C/min, then it is for subsequent use to be warming up to 3 DEG C/min the Mo-V-Ni-Al slurry bed system synthetic gas catalyst for methanation in presence of sulfur that 550 DEG C of constant temperature reduction 6h obtain Mo:V:Ni:Al mass percent 25%:10%:30%:35%.
(1) bituminous coal is produced through the gasification of Lurgi vapourizing furnace and is used for the synthetic gas of methanation, and the main ingredient of synthetic gas by volume per-cent is: H
2: 36.41%, CO:25.45%, CH
4: 9.20%, CO
2: 28.03%, H
2s:0.51% (5100ppm), N
2: 0.40%.
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, the paste state bed reactor that paraffinic hydrocarbon, petroleum naphtha and Mo-V-Ni-Al system catalyst for methanation in presence of sulfur are housed in advance is entered bottom slurry bed system, be 800r/min at temperature 350 DEG C, pressure 4.0MPa, mixing speed, air speed 8000L/hkg carries out methanation reaction, wherein H in unstripped gas
2-CO
2/ CO+CO
2volume ratio be 3.6, H
2s is 4600ppm, and catalyzer and paraffinic hydrocarbon, petroleum naphtha mass percent are 20%.Thick gas product is discharged from paste state bed reactor top, and after heat reclamation device heat exchange, enter gas-liquid-solid separator, liquid-solid phase has separator bottom to discharge, and together enters liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system.
(3) liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, through being pumped into paste state bed reactor;
(4) solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, and entering fixed bed catalyst regeneration device, is 500 DEG C in temperature, air speed 4000L/hkg, 15% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(5) catalyst for methanation in presence of sulfur regenerated is the ratio of 5% in the mass ratio of catalyzer and inert liquid phase medium.Join in inert liquid phase medium pipeline and together enter paste state bed reactor.Thick gas product after gas-liquid-solid separator is separated through heat exchange, through low-temperature rectisol temperature-40 DEG C, working pressure purifies under 4.3MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.6, carbonic acid gas volume fraction≤1.05, total sulfur content≤0.06ppm).
Embodiment 3
Prepared by slurry bed system synthetic gas catalyst for methanation in presence of sulfur:
By 160-200 order, specific surface area 280m
2the SiO of/g
2in 550 DEG C of roasting 7h, temperature 30 DEG C, under mixing speed 180r/min condition, by Mo (NO
3)
35H
2o, Co (NO
3)
26H
2o, SiO
2by Mo:Co:Si mass percent 30%:25%:45% incipient impregnation and stir 18h, after leaving standstill 10h, 60 DEG C are evaporated to sticky, then put into baking oven 100 DEG C of dry 24h, after be ground to 160-200 order and be placed in retort furnace in 500 DEG C of roasting 8h, obtained presoma; 15%H is consisted of at volume
2and 85%N
2flow velocity is in the atmosphere of 120mL/min, adopt two sections of temperature programmings, first be warmed up to 350 DEG C with 5 DEG C/min, then it is for subsequent use to be warming up to 2 DEG C/min the Mo-Co-Si slurry bed system synthetic gas catalyst for methanation in presence of sulfur that 600 DEG C of constant temperature reduction 12h obtain the mass percent 30%:25%:45% of Mo:Co:Si.
(1) brown coal are produced through the gasification of Shell vapourizing furnace and are used for the synthetic gas of methanation, and the main ingredient of synthetic gas by volume per-cent is: H
2: 34.60%, CO:26.43%, CH
4: 11.28%, CO
2: 26.67%, H
2s:0.35% (3500ppm), N
2: 0.67%.
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, the paste state bed reactor that thermal oil and Mo-Co-Si system catalyst for methanation in presence of sulfur are housed in advance is entered bottom slurry bed system, be 650r/min at temperature 450 DEG C, pressure 1.5MPa, mixing speed, air speed 2000L/hkg carries out methanation reaction, wherein H in unstripped gas
2-CO
2/ CO+CO
2volume ratio be 3.9, H
2s is 3000ppm, and catalyzer and thermal oil mass percent are 13%.Thick gas product is discharged from paste state bed reactor top, and after heat reclamation device heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system.
(3) liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, through being pumped into paste state bed reactor;
(4) solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, and entering fixed bed catalyst regeneration device, is 550 DEG C in temperature, air speed 2000L/hkg, 60% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(5) catalyst for methanation in presence of sulfur regenerated is the ratio of 15% in the mass ratio of catalyzer and inert liquid phase medium.Join in inert liquid phase medium pipeline and together enter paste state bed reactor.Thick gas product after gas-liquid-solid separator is separated through heat exchange, through sulfone amine-II at temperature 45 C, working pressure purifies under 5.5MPa condition, obtained sales-quality gas product.(methane volumetric mark >=99.0, carbonic acid gas volume fraction≤0.95, total sulfur content≤0.06ppm).
Embodiment 4
Prepared by slurry bed system synthetic gas catalyst for methanation in presence of sulfur:
By 120-140 order, specific surface area 240m
2γ-the Al of/g
2o
3in 500 DEG C of roasting 6h, at temperature 50 C, under mixing speed 240r/min condition, by Mo (NO
3)
35H
2o, La (NO
3)
36H
2o, Ni (NO
3)
26H
2o, γ-Al
2o
3by Mo:La:Ni:Al mass percent 25%:10%:25%:40% incipient impregnation and stir 12h, after leaving standstill 8h, 90 DEG C are evaporated to sticky, then put into baking oven 110 DEG C of dry 24h, after be ground to 120-140 order and be placed in retort furnace in 600 DEG C of roasting 5h, obtained presoma; 10%H is consisted of at volume
2and 90%N
2flow velocity is in the atmosphere of 180mL/min, adopt two sections of temperature programmings, first be warmed up to 350 DEG C with 6 DEG C/min, then it is for subsequent use to be warming up to 3 DEG C/min the Mo-La-Ni-Al slurry bed system synthetic gas catalyst for methanation in presence of sulfur that 600 DEG C of constant temperature reduction 10h obtain the mass percent 25%:10%:25%:40% of Mo:La:Ni:Al.
(1) gasification of sub-bituminous coal GSP vapourizing furnace is produced and is used for the synthetic gas of methanation, and the main ingredient of synthetic gas by volume per-cent is: H
2: 36.62%, CO:21.36%, CH
4: 12.10%, CO
2: 28.97%, H
2s:0.44% (4400ppm), N
2: 0.51%.
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, the paste state bed reactor that thermal oil, paraffinic hydrocarbon and Mo-La-Ni-Al system catalyst for methanation in presence of sulfur are housed in advance is entered bottom slurry bed system, be 900r/min at temperature 320 DEG C, pressure 5.0MPa, mixing speed, air speed 10000L/hkg carries out methanation reaction, wherein H in unstripped gas
2-CO
2/ CO+CO
2volume ratio be 2.9, H
2s is 4000ppm, and catalyzer and thermal oil, paraffinic hydrocarbon mass percent are 15%.Thick gas product is discharged from paste state bed reactor top, and after heat reclamation device heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system.
(3) liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, through being pumped into paste state bed reactor;
(4) solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, and entering fixed bed catalyst regeneration device, is 600 DEG C in temperature, air speed 4500L/hkg, 20% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(5) catalyst for methanation in presence of sulfur regenerated is the ratio of 20% in the mass ratio of catalyzer and inert liquid phase medium.Join in inert liquid phase medium pipeline and together enter paste state bed reactor.Thick gas product after gas-liquid-solid separator is separated through heat exchange, through low-temperature rectisol temperature-35 DEG C, working pressure purifies under 5.0MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.6, carbonic acid gas volume fraction≤1.05, total sulfur content≤0.06ppm).
Embodiment 5
Prepared by slurry bed system synthetic gas catalyst for methanation in presence of sulfur:
By 100-120 order, specific surface area 160m
2the TiO of/g
2in 500 DEG C of roasting 6h, at temperature 50 C, under mixing speed 240r/min condition, by Co (NO
3)
26H
2o, Fe (NO
3)
39H
2o, Ni (NO
3)
26H
2o, TiO
2by Co:Fe:Ni:Ti mass percent 15%:10%:20%:55% incipient impregnation and stir 12h, after leaving standstill 6h, 80 DEG C are evaporated to sticky, then put into baking oven 110 DEG C of dry 12h, after be ground to 100-120 order and be placed in retort furnace in 600 DEG C of roasting 6h, obtained presoma; 20%H is consisted of at volume
2and 80%N
2flow velocity is in the atmosphere of 180mL/min, adopt two sections of temperature programmings, first be warmed up to 350 DEG C with 5 DEG C/min, then it is for subsequent use to be warming up to 3 DEG C/min the Co-Fe-Ni-Ti slurry bed system synthetic gas catalyst for methanation in presence of sulfur that 650 DEG C of constant temperature reduction 8h obtain the mass percent 15%:10%:20%:55% of Co:Fe:Ni:Ti.
(1) hard coal is produced through the gasification of GSP vapourizing furnace and is used for the synthetic gas of methanation, and the main ingredient of synthetic gas by volume per-cent is: H
2: 35.37%, CO:26.43%, CH
4: 10.55%, CO
2: 26.58%, H
2s:0.49% (4900ppm), N
2: 0.58%.
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, the paste state bed reactor that thermal oil, paraffinic hydrocarbon and Co-Fe-Ni-Ti system catalyst for methanation in presence of sulfur are housed in advance is entered bottom slurry bed system, be 450r/min at temperature 280 DEG C, pressure 2.0MPa, mixing speed, air speed 11000L/hkg carries out methanation reaction, wherein H in unstripped gas
2-CO
2/ CO+CO
2volume ratio be 3.5, H
2s is 4300ppm, and catalyzer and thermal oil, paraffinic hydrocarbon mass percent are 18%.Thick gas product is discharged from paste state bed reactor top, and after heat reclamation device heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system.
(3) liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, through being pumped into paste state bed reactor;
(4) solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, and entering fixed bed catalyst regeneration device, is 580 DEG C in temperature, air speed 4100L/hkg, 35% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(5) catalyst for methanation in presence of sulfur regenerated is the ratio of 13% in the mass ratio of catalyzer and inert liquid phase medium.Join in inert liquid phase medium pipeline and together enter paste state bed reactor.Thick gas product after gas-liquid-solid separator is separated through heat exchange, through low-temperature rectisol temperature-50 DEG C, working pressure purifies under 5.5MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.7, carbonic acid gas volume fraction≤1.00, total sulfur content≤0.06ppm).
Embodiment 6
Prepared by slurry bed system synthetic gas catalyst for methanation in presence of sulfur:
By 120-140 order, specific surface area 240m
2the SiO of/g
2in 400 DEG C of roasting 6h, temperature 35 DEG C, under mixing speed 200r/min condition, by Mo (NO
3)
35H
2o, NH
4vO
3, Ni (NO
3)
26H
2o, SiO
2by Mo:V:Ni:Si mass percent 15%:10%:35%:40% incipient impregnation and stir 18h, after leaving standstill 12h, 90 DEG C are evaporated to sticky, then put into baking oven 100 DEG C of dry 24h, after be ground to 120-140 order and be placed in retort furnace in 550 DEG C of roasting 6h, obtained presoma; 25%H is consisted of at volume
2and 75%N
2flow velocity is in the atmosphere of 150mL/min, adopt two sections of temperature programmings, first be warmed up to 350 DEG C with 10 DEG C/min, then it is for subsequent use to be warming up to 2 DEG C/min the Mo-V-Ni-Si slurry bed system synthetic gas catalyst for methanation in presence of sulfur that 550 DEG C of constant temperature reduction 12h obtain the mass percent 15%:10%:35%:40% of Mo:V:Ni:Si.
(1) brown coal are produced through the gasification of Lurgi vapourizing furnace and are used for the synthetic gas of methanation, and the main ingredient of synthetic gas by volume per-cent is: H
2: 37.41%, CO:25.28%, CH
4: 11.69%, CO
2: 24.74%, H
2s:0.31% (3100ppm), N
2: 0.57%.
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, the paste state bed reactor that petroleum naphtha, paraffinic hydrocarbon and Mo-V-Ni-Si system catalyst for methanation in presence of sulfur are housed in advance is entered bottom slurry bed system, be 750r/min at temperature 380 DEG C, pressure 4.0MPa, mixing speed, air speed 8500L/hkg carries out methanation reaction, wherein H in unstripped gas
2-CO
2/ CO+CO
2volume ratio be 3.2, H
2s is 2600ppm, and catalyzer and petroleum naphtha, paraffinic hydrocarbon mass percent are 5%.Thick gas product is discharged from paste state bed reactor top, and after heat reclamation device heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system.
(3) liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, through being pumped into paste state bed reactor;
(4) solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, and entering fixed bed catalyst regeneration device, is 500 DEG C in temperature, air speed 3700L/hkg, 45% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(5) catalyst for methanation in presence of sulfur regenerated is the ratio of 16% in the mass ratio of catalyzer and inert liquid phase medium.Join in inert liquid phase medium pipeline and together enter paste state bed reactor.Thick gas product after gas-liquid-solid separator is separated through heat exchange, through sulfone amine-II temperature 40 DEG C, working pressure purifies under 5.52MPa condition, obtained sales-quality gas product.(methane volumetric mark >=99.1, carbonic acid gas volume fraction≤0.86, total sulfur content≤0.06ppm).
Claims (15)
1. synthetic gas system substitutes a methanation in presence of sulfur technique for Sweet natural gas, it is characterized in that comprising the following steps:
(1) feed coal produces through vapourizing furnace gasification the synthetic gas being used for methanation;
(2) synthetic gas is through mending the compression of hydrogen evolution unstripped gas, after heat exchange, enter from the gas distributor bottom slurry bed system the paste state bed reactor that inert liquid phase medium and catalyst for methanation in presence of sulfur are housed and carry out methanation, thick gas product is discharged from paste state bed reactor top, after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator and be separated;
(3) be separated the liquid-solid phase obtained from gas-liquid-solid separator and together enter liquid-solid separator with the inert media out containing catalyzer bottom slurry bed system, the solid phase that liquid-solid separator is separated is discharged from the bottom of liquid-solid separator, enters fixed bed catalyst regeneration device and carries out catalyst regeneration; The liquid phase that liquid-solid separator is separated is discharged from the middle and upper part of liquid-solid separator, enters inert media hold-up vessel, turns back to paste state bed reactor through pump, is separated the thick gas product obtained obtains sales-quality gas product through heat exchange, purification through gas-liquid-solid separator;
(4), after the catalyst for methanation in presence of sulfur regenerated enters catalyzer storage tank, add in proportion in the inert liquid phase medium pipeline turning back to paste state bed reactor and enter paste state bed reactor together.
2. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described feed coal is bituminous coal, sub-bituminous coal, hard coal or brown coal.
3. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that the vapourizing furnace of described producing synthesis gas is Lurgi vapourizing furnace, Shell vapourizing furnace or GSP vapourizing furnace.
4. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described through vapourizing furnace produce synthetic gas main ingredient by volume per-cent be: H
2: 32.30%-38.90%, CO:20.10%-32.50%, CH
4: 7.60%-12.50%, CO
2: 24.50%-30.20%, H
2s:0.03%-0.60%, N
2: 0.30%-0.90%.
5. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that H in described unstripped gas
2-CO
2/ CO+CO
2volume ratio between 2.5-4.0, sulphur content is between 300-6000ppm.
6. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described catalyst for methanation in presence of sulfur be active ingredient is Ni, Ce, Fe, two or more combinations in Cr, the mass percentage 2-40% of active ingredient; Adjuvant component is the one or more combination in Mo, W, V, Y, Co, La, and the mass percentage of auxiliary agent is 0.5-35%; All the other are carrier, and carrier is Al
2o
3, SiO
2, TiO
2in one or more.
7. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described slurry bed system inert liquid phase medium is one or more mixed solutions of paraffinic hydrocarbon, thermal oil, petroleum naphtha, hydrogenated terphenyl.
8. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that the mass percent of catalyst for methanation in presence of sulfur and inert liquid phase medium in described slurry bed system methanator is: 1%-35%.
9. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that the resistant to sulfur scope of described catalyst for methanation in presence of sulfur is 200-8000ppm.
10. a kind of synthetic gas system as claimed in claim 1 substitutes the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described slurry bed system methanation reaction temperature is 260-550 DEG C, reaction pressure is 1-6MPa, and mixing speed is 300-1000r/min, and unstripped gas air speed is 1000-15000L/hkg.
11. a kind of synthetic gas systems as claimed in claim 1 substitute the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that the reducing gas of described fixed bed catalyst regeneration is H
2and N
2, H
2the volume ratio accounting for reducing gas is 5%-85%, and reduction temperature is 450-600 DEG C, and air speed is 1000-5000L/hkg.
12. a kind of synthetic gas systems as claimed in claim 1 substitute the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described purification is the one in low-temperature rectisol or hydramine method.
13. a kind of synthetic gas systems as claimed in claim 12 substitute the methanation in presence of sulfur technique of Sweet natural gas, and it is characterized in that the service temperature of described low-temperature rectisol is between-30 ~-55 DEG C, working pressure is at 4.0-6.0MPa.
14. a kind of synthetic gas systems as claimed in claim 12 substitute the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described hydramine method can adopt MEA, DEA, sulfone amine-II, MDEA, service temperature between 20-50 DEG C, working pressure 4.0-6.0MPa.
15. a kind of synthetic gas systems as claimed in claim 14 substitute the methanation in presence of sulfur technique of Sweet natural gas, it is characterized in that described hydramine method is sulfone amine-II.
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|---|---|---|---|---|
| CN101875863A (en) * | 2009-04-29 | 2010-11-03 | 四川大学 | Waste heat-driven circulative heat-carrying gas methanation technology and device |
| CN101979476A (en) * | 2010-10-26 | 2011-02-23 | 赛鼎工程有限公司 | Process for synthesizing natural gas by methanation of coal synthesis gas |
| CN102690157A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院山西煤炭化学研究所 | Process for synthesizing methane through synthesis gas |
| CN103357418A (en) * | 2013-07-17 | 2013-10-23 | 赛鼎工程有限公司 | Sulfur tolerant catalyst suitable for slurry bed methanation, its preparation method and application |
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|---|---|---|---|---|
| CN101875863A (en) * | 2009-04-29 | 2010-11-03 | 四川大学 | Waste heat-driven circulative heat-carrying gas methanation technology and device |
| CN101979476A (en) * | 2010-10-26 | 2011-02-23 | 赛鼎工程有限公司 | Process for synthesizing natural gas by methanation of coal synthesis gas |
| CN102690157A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院山西煤炭化学研究所 | Process for synthesizing methane through synthesis gas |
| CN103357418A (en) * | 2013-07-17 | 2013-10-23 | 赛鼎工程有限公司 | Sulfur tolerant catalyst suitable for slurry bed methanation, its preparation method and application |
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