CN104073307B - A kind of coke-oven gas system substitutes the technique of the methanation in presence of sulfur of Sweet natural gas - Google Patents
A kind of coke-oven gas system substitutes the technique of the methanation in presence of sulfur of Sweet natural gas Download PDFInfo
- Publication number
- CN104073307B CN104073307B CN201410319973.1A CN201410319973A CN104073307B CN 104073307 B CN104073307 B CN 104073307B CN 201410319973 A CN201410319973 A CN 201410319973A CN 104073307 B CN104073307 B CN 104073307B
- Authority
- CN
- China
- Prior art keywords
- gas
- methanation
- sulfur
- coke
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The technique that a kind of coke-oven gas system substitutes the methanation in presence of sulfur of Sweet natural gas coke-oven gas is mended unstripped gas that carbon formed to enter bottom slurry bed system and carry out methanation reaction, thick gas product is discharged from reactor head and is entered gas-liquid-solid separator, the liquid-solid phase be separated together enters liquid-solid separator with the inert media containing catalyzer from slurry bed system bottom cycle, and the solid phase that liquid-solid separator is separated is discharged and carried out catalyst regeneration bottom liquid-solid separator; 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; Catalyst for methanation in presence of sulfur after regeneration enters inert media storage tank, sends into paste state bed reactor after mixing by recycle pump; Thick gas product after gas-liquid-solid separator is separated is through purifying obtained Sweet natural gas.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 coke-oven gas carries out methanation in presence of sulfur synthetic natural gas.Belong to technical field of new energy utilization.
Background technology
China is first coke production state in the world, produces the coke a large amount of coke-oven gas of by-product simultaneously.These coke-oven gas parts are used for methyl alcohol processed, synthetic ammonia and factory's combustion gas, and remote districts are then emitted in vain.The capacity usage ratio of coke-oven gas present stage is about about 55%, and the feature of " the many carbon of hydrogen is few " is formed according to coke-oven gas, utilize gas employing methanation of coke oven synthesis of artificial Sweet natural gas and by-product hydrogen to have very strong economic competitiveness, the object improving coke-oven gas capacity usage ratio can be reached.Current coke-oven gas nearly 300 billion cubic meter coke(oven)gas more than needed every year except production synthetic ammonia and methyl alcohol, cause huge energy dissipation and environmental pollution, utilize coke-oven gas to carry out preparing natural gas by methanation and not only produce obvious economic benefit and environmental benefit, also significant to Energy restructuring.
The main component of coke-oven gas is probably (volume ratio): H
2content 50-60%, CH
4content 20-28%, CO+CO
2content 10-15%.In addition, the H of trace is also had
2s, COS, HCN, NH
3etc. objectionable constituent.
In gas employing methanation of coke oven synthetic natural gas technological process, methanation is an important step.Effective constituent H in coke-oven gas
2, CO, CO
2carry out methanation reaction and produce Artificial Natural Gas, its chemical equation is as follows:
CO+3H
2＝CH
4+H
2O+206KJ/mol
CO
2+4H
2＝CH
4+2H
2O+165KJ/mol
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 content will cause poisoning of catalyst inactivation.Sulphur in raw material must be removed to below 0.1ppm by such catalyzer before methanation reaction.The typical sulfur removal technology of this process is low-temp methanol washing process, and make unstripped gas temperature through the wide variation of 200-400 DEG C to-40 DEG C, need a large amount of energy expenditure, running cost is high.
As patent 5CN201110394228 discloses a kind of technique of coke-oven gas methane, this technique comprise coke-oven gas unstripped gas fine de-sulfur, unstripped gas compression, enter heat exchanger package heat-shift and vapor mixing after enter multistage methanator; Through multistage methanation reaction, intersegmentally carry out heat recuperation, produce superheated vapour; Through obtained gas product of purifying.
Patent CN200910018047 discloses a kind of technique of gas employing methanation of coke oven synthetic natural gas, and the coke-oven gas of this technique obtains sales-quality gas through preliminary cleaning, desulfurization, one section of methanation, two sections of methanations, Sweet natural gas separation values.
Patent CN11280235A discloses a kind of method that a coke-oven gas is raw material production natural gas liquids, the method is that unstripped gas is first through pre-treatment with coke-oven gas, the impurity such as the tar contained by it, naphthalene, benzene are made to obtain deep purifying, carry out methanation reaction after compressed and desulfurization again, obtaining through low temperature separation process containing CH
4the liquefied natural gas product of volume percent more than more than 85%.This technique is multistage methanation (more than three sections and three sections methanations) technically exploitation, and because multistage methanation reaction equipment investment amount is large, energy consumption is high, causes the cost of synthetic natural gas to increase.
Patent CN201210159464.8 discloses a kind of technique of coke-oven gas methane, this technique is the unstripped gas obtained after purification, conversion and decarburization by coke-oven gas, carries out with the Carbon Materials obtained by brown coal or long-flame coal destructive distillation the technique that Sweet natural gas is produced in methanation.
Patent CN200910256481.1 discloses a kind of method utilizing coke-oven gas to prepare substitute natural gas.The method is by after coke oven gas desulfurization, and carry out pressure-variable adsorption, then unstripped gas is compressed, uses catalyst for methanation in presence of sulfur, under 1.2MPa and 500 DEG C condition, carries out methanation reaction.But the method does not illustrate the resistant to sulfur scope of catalyst for methanation in presence of sulfur, and coke-oven gas also needs desulfurization before carrying out methanation.
Summary of the invention
In order to overcome existing coke-oven gas system substitute methanation catalyst in natural gas process not resistant to sulfur, meet the shortcoming of the easy poisoning and deactivation of Determination of Trace Sulfur, the object of the present invention is to provide a kind of energy utilization rate high, facility investment and working cost low, the easy-operating technique being suitable for coke-oven gas 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) coke-oven gas is mended carbon and form unstripped gas, after compressed, 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 reaction, 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;
(2) liquid-solid phase that gas-liquid-solid separator is separated together enters liquid-solid separator with the inert media containing catalyzer from slurry bed system bottom cycle, the solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, enters fixed bed catalyst regeneration device and carries out catalyst regeneration;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in sulfur resistant catalyst and inert liquid phase medium ratio, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, the obtained sales-quality gas product of purification.
Coke-oven gas main ingredient as above by volume per-cent is: H
2: 40.15%-65.10%, CO:5.80%-16.05%, CH
4: 18.80%-31.50%, CO
2: 1.05%-10.60%, H
2s:0.03%-0.65% (i.e. 300-6500ppm), N
2: 1.50%-6.50%.
Coke-oven gas as above obtains the unstripped gas meeting methanation requirement after mending carbon.H in unstripped gas
2-CO
2/ CO+CO
2volume ratio between 2.5-4.0, CO/CO
2volumetric concentration is at 1.5-7.0.
Enter paste state bed reactor as above and to carry out in the unstripped gas of methanation sulphur content between 300-6500ppm.
Coke-oven gas 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%; 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%-30%.
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 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, and 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, has obvious technical superiority as follows:
(1) have employed efficient catalyst for methanation in presence of sulfur, this catalyzer resistant to sulfur scope is wide, without the need to adopting coke-oven gas fine desulfurizing technology, directly methanation reaction can be carried out when the obnoxious flavoures such as sulphur in coke oven gas need not remove, 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 gas employing methanation of coke oven preparing natural gas, 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, improves transformation efficiency and the selectivity of reaction.
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 slurry bed system methanation in presence of sulfur reactor, 2 agitator motors, 3 gas-liquid-solid separators, 4 liquid-solid separators, 5 catalyst reduction regenerating units, 6 catalyzer storage tanks, 7 inert media hold-up vessels, 8,9 interchanger, 10,11,12 recycle pumps, 13 compressors; 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 present invention is not by the restriction of subordinate's embodiment.
Embodiment 1
Prepared by slurry bed system coke-oven 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, 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, 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-Ni-Al slurry bed system coke-oven gas catalyst for methanation in presence of sulfur that 550 DEG C of constant temperature reduction 6h obtain the mass percent 25%:30%:45% of Mo:Ni:Al.
(1) by main ingredient by volume per-cent be: H
2: 56.49%, CO:14.67%, CH
4: 21.41%, CO
2: 4.70%, H
2s:0.27% (2700ppm), N
2: the coke-oven gas of 2.46% is mended carbon and is formed unstripped gas, after compressed, 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 from the gas distributor bottom slurry bed system, be 600r/min at temperature 280 DEG C, pressure 2.0MPa, mixing speed, air speed 3000L/hkg carries out methanation reaction, wherein H in unstripped gas
2s is 2100ppm, CO/CO
2volumetric concentration ratio is 3.1, H
2-CO
2/ CO+CO
2volume ratio be 3.2, catalyzer and thermal oil, petroleum naphtha mass percent are 25%.Thick gas product is discharged from paste state bed reactor top, and after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator and be separated, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media from slurry bed system bottom cycle;
(2) 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 in temperature is 450 DEG C, air speed 3000L/hkg, 25% (volume) H
2h
2and N
2catalyst regeneration is carried out under condition;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in the ratio that the mass ratio of catalyzer and inert liquid phase medium is 25%, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, employing sulfone amine-II temperature 20 DEG C, and working pressure purifies under 6.0MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.5, carbonic acid gas volume fraction≤1.05, total sulfur content≤0.06ppm).
Embodiment 2
Prepared by slurry bed system coke-oven gas catalyst for methanation in presence of sulfur:
By 160-200 order, γ-the Al2O3 of specific surface area 280m2/g is in 550 DEG C of roasting 7h, temperature 30 DEG C, under mixing speed 200r/min condition, by Mo (NO3) 35H2O, Co (NO3) 26H2O, Ni (NO3) 26H2O, γ-Al2O3 by Mo:Co:Ni:Al mass percent 20%:10%:35%:35% incipient impregnation and stir 24h, after leaving standstill 10h, 70 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%H2 and 85%N2 is consisted of at volume, flow 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-Ni-Al slurry bed system coke-oven gas catalyst for methanation in presence of sulfur that 600 DEG C of constant temperature reduction 12h obtain the mass percent 20%:10%:35%:35% of Mo:Co:Ni:Al.
(1) by main ingredient by volume per-cent be: H2:54.37%, CO:11.41%, CH4:28.84%, CO2:2.53%, H2S:0.36% (3600ppm), the coke-oven gas of N2:2.49% is mended carbon and is formed unstripped gas, compressed, after heat exchange, enter from the gas distributor bottom slurry bed system and in advance paraffinic hydrocarbon is housed, the paste state bed reactor of petroleum naphtha and Mo-Co-Ni-Al system catalyst for methanation in presence of sulfur, temperature 350 DEG C, pressure 4.0MPa, mixing speed is 750r/min, air speed 8000L/hkg carries out methanation reaction, wherein in unstripped gas, H2S is 3300ppm, CO/CO2 volumetric concentration ratio is 4.5, the volume ratio of H2-CO2/CO+CO2 is 3.8, catalyzer and paraffinic hydrocarbon, petroleum naphtha mass percent is 18%.Thick gas product is discharged from paste state bed reactor top, and after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator and be separated, liquid-solid phase has separator bottom to discharge, and together enters liquid-solid separator with the inert media from slurry bed system bottom cycle;
(2) 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, carries out catalyst regeneration under H2 and the N2 condition of 15% (volume) H2;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in the ratio that the mass ratio of catalyzer and inert liquid phase medium is 18%, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, employing sulfone amine-II temperature 40 DEG C, and working pressure purifies under 5.0MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.4, carbonic acid gas volume fraction≤1.00, total sulfur content≤0.06ppm).
Embodiment 3
Prepared by slurry bed system coke-oven gas catalyst for methanation in presence of sulfur:
By 80-100 order, the SiO2 of specific surface area 180m2/g is in 450 DEG C of roasting 4h, temperature 25 DEG C, under mixing speed 120r/min condition, by Ni (NO3) 26H2O, Co (NO3) 26H2O, SiO2 by Ni:Co:Si mass percent 30%:20%:50% incipient impregnation and stir 8h, to leave standstill after 4h 80 DEG C and be evaporated to sticky, then put into baking oven 110 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%H2 and 80%N2 is consisted of at volume, flow 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 Ni-Co-Si slurry bed system coke-oven gas catalyst for methanation in presence of sulfur that 550 DEG C of constant temperature reduction 6h obtain the mass percent 30%:20%:50% of Ni:Co:Si.
(1) by main ingredient by volume per-cent be: H2:60.41%, CO:14.37%, CH4:20.46%, CO2:2.13%, H2S:0.47% (4700ppm), the coke-oven gas of N2:2.16% is mended carbon and is formed unstripped gas, compressed, after heat exchange, the paste state bed reactor that thermal oil and Ni-Co-Si system catalyst for methanation in presence of sulfur are housed in advance is entered from the gas distributor bottom slurry bed system, temperature 450 DEG C, pressure 1.5MPa, mixing speed is 900r/min, air speed 2000L/hkg carries out methanation reaction, wherein in unstripped gas, H2S is 3800ppm, CO/CO2 volumetric concentration ratio is 6.7, the volume ratio of H2-CO2/CO+CO2 is 2.8, catalyzer and thermal oil mass percent are 13%.Thick gas product is discharged from paste state bed reactor top, and after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media from slurry bed system bottom cycle;
(2) 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, carries out catalyst regeneration under H2 and the N2 condition of 60% (volume) H2;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in the ratio that the mass ratio of catalyzer and inert liquid phase medium is 13%, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, employing low-temperature rectisol temperature-35 DEG C, and working pressure purifies under 5.5MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.7, carbonic acid gas volume fraction≤0.95, total sulfur content≤0.06ppm).
Embodiment 4
Prepared by slurry bed system coke-oven gas catalyst for methanation in presence of sulfur:
By 120-140 order, the SiO2 of specific surface area 240m2/g is in 500 DEG C of roasting 6h, at temperature 50 C, under mixing speed 240r/min condition, by Mo (NO3) 35H2O, NH4VO3, Ni (NO3) 26H2O, SiO2 by Mo:V:Ni:Si mass percent 30%:5%: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%H2 and 90%N2 is consisted of at volume, flow 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-V-Ni-Si slurry bed system coke-oven gas catalyst for methanation in presence of sulfur that 600 DEG C of constant temperature reduction 10h obtain the mass percent 30%:5%:25%:40% of Mo:V:Ni:Si.
(1) by main ingredient by volume per-cent be: H2:50.61%, CO:12.88%, CH4:29.66%, CO2:3.13%, H2S:0.55% (5500ppm), the coke-oven gas of N2:3.17% is mended carbon and is formed unstripped gas, compressed, after heat exchange, enter from the gas distributor bottom slurry bed system and in advance thermal oil is housed, the paste state bed reactor of paraffinic hydrocarbon and Mo-V-Ni-Si system catalyst for methanation in presence of sulfur, temperature 320 DEG C, pressure 5.0MPa, mixing speed is 500r/min, air speed 10000L/hkg carries out methanation reaction, wherein in unstripped gas, H2S is 4600ppm, CO/CO2 volumetric concentration ratio is 4.1, the volume ratio of H2-CO2/CO+CO2 is 3.6, catalyzer and thermal oil, paraffinic hydrocarbon mass percent is 10%.Thick gas product is discharged from paste state bed reactor top, after heat reclamation device heat exchange, after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media from slurry bed system bottom cycle;
(2) liquid-solid phase that gas-liquid-solid separator is separated together enters liquid-solid separator with the inert media containing catalyzer from slurry bed system bottom cycle, the solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, enter fixed bed catalyst regeneration device, it is 600 DEG C in temperature, air speed 4500L/hkg, carries out catalyst regeneration under H2 and the N2 condition of 20% (volume) H2;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in the ratio that the mass ratio of catalyzer and inert liquid phase medium is 10%, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, employing low-temperature rectisol temperature-45 DEG C, and working pressure purifies under 4.5MPa condition, obtained sales-quality gas product.(methane volumetric mark >=99.0, carbonic acid gas volume fraction≤0.90, total sulfur content≤0.06ppm).
Embodiment 5
Prepared by slurry bed system coke-oven gas catalyst for methanation in presence of sulfur:
By 160-200 order, the TiO2 of specific surface area 280m2/g is in 600 DEG C of roasting 7h, temperature 30 DEG C, under mixing speed 200r/min condition, by Co (NO3) 26H2O, FeCl34H2O, Ni (NO3) 26H2O, TiO2 by Co:Fe:Ni:Ti mass percent 25%:10%:30%:35% incipient impregnation and stir 18h, after leaving standstill 12h, 80 DEG C are evaporated to sticky, then put into baking oven 110 DEG C of dry 30h, after be ground to 160-200 order and be placed in retort furnace in 550 DEG C of roasting 8h, obtained presoma; 10%H2 and 90%N2 is consisted of at volume, flow 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 Co-Fe-Ni-Ti slurry bed system coke-oven gas catalyst for methanation in presence of sulfur that 600 DEG C of constant temperature reduction 15h obtain the mass percent 25%:10%:30%:35% of Co:Fe:Ni:Ti.
(1) by main ingredient by volume per-cent be: H2:48.82%, CO:13.91%, CH4:28.94%, CO2:3.44%, H2S:0.42% (4200ppm), the coke-oven gas of N2:4.47% is mended carbon and is formed unstripped gas, compressed, after heat exchange, enter from the gas distributor bottom slurry bed system and in advance petroleum naphtha is housed, the paste state bed reactor of paraffinic hydrocarbon and Co-Fe-Ni-Ti system catalyst for methanation in presence of sulfur, temperature 340 DEG C, pressure 3.0MPa, mixing speed is 800r/min, air speed 8000L/hkg carries out methanation reaction, wherein in unstripped gas, H2S is 3600ppm, CO/CO2 volumetric concentration ratio is 4.0, the volume ratio of H2-CO2/CO+CO2 is 3.1, catalyzer and petroleum naphtha, paraffinic hydrocarbon mass percent is 5%.Thick gas product is discharged from paste state bed reactor top, and after interchanger and unstripped gas heat exchange, enter gas-liquid-solid separator, liquid-solid phase is discharged by separator bottom, together enters liquid-solid separator with the inert media from slurry bed system bottom cycle;
(2) liquid-solid phase that gas-liquid-solid separator is separated together enters liquid-solid separator with the inert media containing catalyzer from slurry bed system bottom cycle, the solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, enter fixed bed catalyst regeneration device, it is 580 DEG C in temperature, air speed 4300L/hkg, carries out catalyst regeneration under H2 and the N2 condition of 45% (volume) H2;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in the ratio that the mass ratio of catalyzer and inert liquid phase medium is 5%, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, employing low-temperature rectisol temperature-40 DEG C, and working pressure purifies under 6.0MPa condition, obtained sales-quality gas product.(methane volumetric mark >=98.8, carbonic acid gas volume fraction≤0.95, total sulfur content≤0.06ppm).
Claims (13)
1. coke-oven gas system substitutes a technique for the methanation in presence of sulfur of Sweet natural gas, it is characterized in that comprising the steps:
(1) coke-oven gas is mended carbon and form unstripped gas, after compressed, 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 reaction, 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;
(2) liquid-solid phase that gas-liquid-solid separator is separated together enters liquid-solid separator with the inert media containing catalyzer from slurry bed system bottom cycle, the solid phase that liquid-solid separator is separated is got rid of from the bottom of liquid-solid separator, enters fixed bed catalyst regeneration device and carries out catalyst regeneration;
(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, and by recycle pump, the sparger of inert media through top is sent into paste state bed reactor;
(4) catalyst for methanation in presence of sulfur after regeneration enters into regenerated catalyst storage tanks, and joins with in inert media in sulfur resistant catalyst and inert liquid phase medium ratio, enters paste state bed reactor with inert media;
(5) the thick gas product after gas-liquid-solid separator is separated is through heat exchange, the obtained sales-quality gas product of purification.
2. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur of Sweet natural gas, it is characterized in that described coke-oven gas main ingredient by volume per-cent be: H
2: 40.15%-65.10%, CO:5.80%-16.05%, CH
4: 18.80%-31.50%, CO
2: 1.05%-10.60%, H
2s:0.03%-0.65%, N
2: 1.50%-6.50%.
3. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur of Sweet natural gas, it is characterized in that described coke-oven gas obtains H in full unstripped gas after mending carbon
2-CO
2/ CO+CO
2volume ratio between 2.5-4.0, CO/CO
2volumetric concentration is at 1.5-7.0.
4. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur of Sweet natural gas, it is characterized in that described catalyst for methanation in presence of sulfur for its active ingredient be 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%; Carrier is Al
2o
3, SiO
2, TiO
2in one or more.
5. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur 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.
6. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur 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%-30%.
7. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur 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.
8. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur 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 methanation unstripped gas air speed is 1000-15000L/hkg.
9. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur 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.
10. a kind of coke-oven gas system as claimed in claim 1 substitutes the technique of the methanation in presence of sulfur of Sweet natural gas, it is characterized in that described purification is the one in low-temperature rectisol or hydramine method.
11. a kind of coke-oven gas systems as claimed in claim 10 substitute the technique of the methanation in presence of sulfur 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.
12. a kind of coke-oven gas systems as claimed in claim 10 substitute the technique of the methanation in presence of sulfur of Sweet natural gas, it is characterized in that described hydramine method adopts MEA, DEA, sulfone amine-II or MDEA, service temperature between 20-50 DEG C, working pressure 4.0-6.0MPa.
13. a kind of coke-oven gas systems as claimed in claim 12 substitute the technique of the methanation in presence of sulfur of Sweet natural gas, it is characterized in that described hydramine method is sulfone amine-II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410319973.1A CN104073307B (en) | 2014-07-08 | 2014-07-08 | A kind of coke-oven gas system substitutes the technique of the methanation in presence of sulfur of Sweet natural gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410319973.1A CN104073307B (en) | 2014-07-08 | 2014-07-08 | A kind of coke-oven gas system substitutes the technique of the methanation in presence of sulfur of Sweet natural gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104073307A CN104073307A (en) | 2014-10-01 |
| CN104073307B true CN104073307B (en) | 2016-03-02 |
Family
ID=51594919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410319973.1A Expired - Fee Related CN104073307B (en) | 2014-07-08 | 2014-07-08 | A kind of coke-oven gas system substitutes the technique of the methanation in presence of sulfur of Sweet natural gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104073307B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268574A (en) * | 2015-06-04 | 2017-01-04 | 北京化工大学 | A kind of method, device and application being realized selective catalysis reaction by regulation and control liquid film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875863B (en) * | 2009-04-29 | 2013-08-07 | 四川大学 | Waste heat-driven circulative heat-carrying gas methanation technology and device |
| CN101979476B (en) * | 2010-10-26 | 2013-05-29 | 赛鼎工程有限公司 | Process for synthesizing natural gas by methanation of coal synthesis gas |
| CN102690157B (en) * | 2012-06-05 | 2014-04-16 | 中国科学院山西煤炭化学研究所 | Process for synthesizing methane through synthesis gas |
| CN103357418B (en) * | 2013-07-17 | 2015-09-02 | 赛鼎工程有限公司 | One is applicable to slurry bed system methanation sulfur resistant catalyst and method for making and application |
-
2014
- 2014-07-08 CN CN201410319973.1A patent/CN104073307B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104073307A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103275777B (en) | Method for preparing hydrogen and liquefied natural gas through using gas retort raw gas | |
| JP6956665B2 (en) | Method of methaneization of carbon dioxide in combustion exhaust gas and methane production equipment | |
| CN104119975B (en) | Coke-oven plant's combined production of methanol and the method for liquefied natural gas | |
| CN101434879B (en) | Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal | |
| CN101649232B (en) | Synthesis process of natural gas employing methanation of coke oven gas | |
| CN107758617B (en) | Method for producing hydrogen by using biogas biomass | |
| CN102134519B (en) | Combined process for natural gas desulfurization with high resource utilization ratio and good environmental protection effect | |
| CN104232195A (en) | Method for jointly producing methanol and synthetic natural gas by utilizing coke oven gas | |
| CN110963464A (en) | Method for producing hydrogen by coupling natural gas direct cracking and steam reforming | |
| CN104046398B (en) | A kind of methanation in presence of sulfur technique of synthetic gas preparing natural gas | |
| CN204211707U (en) | Utilize the device of coke-oven gas and blast furnace gas combination producing Sweet natural gas and liquefied ammonia | |
| CN104762116B (en) | Production technology of natural gas or liquefied natural gas | |
| CN101921641A (en) | Process for preparing synthetic natural gas from coke oven gas | |
| US11707725B2 (en) | Acid gas absorbent in biogas and biogas purification system using the same | |
| CN203513271U (en) | High-yield and high-purity device for producing hydrogen through reforming and converting refinery dry gas | |
| CN105111045A (en) | Method for synthesizing lower alcohol by coke oven gas and secondarily producing natural gas and liquid ammonia | |
| CN204848257U (en) | Device of methane catalytic cracking production hydrogen | |
| CN104073307B (en) | A kind of coke-oven gas system substitutes the technique of the methanation in presence of sulfur of Sweet natural gas | |
| CN104098437A (en) | Method for co-production of methanol, liquefied natural gas and hydrogen by employing coke oven gas | |
| CN104194851B (en) | A kind of coke-stove gas is through the technique of methanation in presence of sulfur synthetic natural gas | |
| CN104046399B (en) | Sulfur-tolerant methanation process for preparing natural gases from coke oven gases | |
| CN103343025A (en) | Process for synthesizing natural gas employing methanation of calcium carbide furnace gas | |
| CN102876828B (en) | Reducing gas purification process and system matched with gas-based shaft furnace | |
| CN102659102B (en) | Technology and device for preparing industrial carbon monoxide with water gas | |
| CN104073308B (en) | A kind of synthetic gas system substitutes the methanation in presence of sulfur technique of Sweet natural gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160302 Termination date: 20170708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |