CN104178236B - A kind of producing synthesis gas from coal carries out the technique of methanation in presence of sulfur synthetic natural gas - Google Patents
A kind of producing synthesis gas from coal carries out the technique of methanation in presence of sulfur synthetic natural gas Download PDFInfo
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- CN104178236B CN104178236B CN201410407752.XA CN201410407752A CN104178236B CN 104178236 B CN104178236 B CN 104178236B CN 201410407752 A CN201410407752 A CN 201410407752A CN 104178236 B CN104178236 B CN 104178236B
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Abstract
The technique that a kind of producing synthesis gas from coal carries out methanation in presence of sulfur synthetic natural gas be by producing synthesis gas from coal after washing, first on sulfur-resisting transformation and methanation in presence of sulfur loading type molybdenum base dual-function catalyst, carry out the reaction of secondary methanation in presence of sulfur, reacted gas removes after sour gas through low-temperature rectisol, to carry out after one-level methanation reaction obtaining gas product through Ni methylmethane catalyzer.The present invention has the advantage that technical process is simple, facility investment is few, comprehensive energy consumption is low and gas product is excellent.
Description
Technical field
The invention belongs to a kind of coal process for producing natural, particularly relate to the technique that a kind of producing synthesis gas from coal carries out methanation in presence of sulfur synthetic natural gas.
Background technology
China has the Energy Situation of rich coal, oil-poor and weak breath, therefore the comprehensive optimal control of coal resources is extremely urgent.In recent years, along with increasing sharply of China's natural gas demand, domestic natural gas insufficiency of supply-demand increases gradually, and then limits the stable and rapid development of Chinese national economy.Coal preparing natural gas take coal as the Technology of raw material production Sweet natural gas, can by the clean fuel CH of coal conversion for ease of long-distance sand transport
4, be the important channel alleviated Sweet natural gas imbalance between supply and demand and realize coal high-efficiency clean conversion.
Methanation is the core technology of coal preparing natural gas, is specially CO, CO in synthetic gas
2and H
2cH is synthesized under certain temperature, pressure and catalyst action
4, specifically see reaction formula (1) and (2).At present, industrial methanation technology primarily of external Lurgi,
grasp with the fewer companies such as Davy, above-mentioned technology all adopts Ni catalyst based.Nickel-base catalyst shows higher hydrogenation activity and methane selectively in methanation reaction, but this catalyzer anti-carbon deposition ability difference and not resistant to sulfur, therefore must through water-gas shift and acid gas removal (H before carrying out methanation
2s < 0.1 × 10
-6) two processes.The cost of water-gas shift and acid gas removal very high, especially the low-temperature rectisol that industry is conventional removes sour gas technology, make unstripped gas temperature through 300 ~ 400 DEG C to-40 DEG C changes on a large scale, considerably increase facility investment, energy expenditure and running cost.Therefore, developing a kind of resistant to sulfur novel methanation technology is overcome the in-problem key of existing methanation technology, becomes the research emphasis of numerous scientific research institution.
CO+3H
2→CH
4+H
2O△H＝-206KJ/mol(1)
CO
2+4H
2→CH
4+2H
2O△H＝-165KJ/mol(2)
Patent CN103480362A discloses a kind of preparation method of load type sulfur-tolerant methanation catalyst, and this invention is with Mo, W and V for active ingredient, and Co, Ni, La and K are auxiliary agent, with Al
2o
3or ZrO
2for carrier, prepared catalyst for methanation in presence of sulfur by the precipitator method, this catalyzer has the advantage that preparation process is simple and sulfur tolerance is good.Patent CN103495421A has prepared a kind of cobalt molybdenum catalyst for methanation in presence of sulfur of magnesium-aluminium spinel load by kneading method or pickling process, and this catalyzer can use in the pressure range of 0 ~ 6MPa, catalyst strength and having good stability.Patent CN10343326A discloses a kind of ZrO
2the high stability catalyst for methanation in presence of sulfur of load, by step impregnation method successively by Y
2o
3and Mo
2o
3be carried on ZrO
2on carrier, wherein Y
2o
3part can by MgO, CaO and/or Cr
2o
3substitute, this catalyzer shows higher methanation reaction activity and high stability in high hydrogen sulfide atmosphere.
Above-mentioned patent shows, catalyst for methanation in presence of sulfur is active ingredient mainly with Mo, and Co, Ni, W, Ru, to calumniate be add as auxiliary agent with elements such as actinium series, and carrier is Al
2o
3, ZrO
2, SiO
2and CeO
2deng.Mo
2o
3first cure as MoS before methanation reaction
2active centre, this catalyzer is to the sulphur content no maximum requirement in unstripped gas, and synthetic gas can carry out methanation without the need to desulfurization, and then synthetic natural gas.Because the active ingredient of this catalyzer is similar to sulfur-resistant transformation catalyst, therefore this catalyzer has conversion and methanation dual-use function simultaneously.Consider that in synthetic gas, CO content is higher, the volume that crushed coal pressure gasifying as strange in Shandong generates gas consists of: H
237 ~ 39%, CO17% ~ 18%, CO
232%, CH
48% ~ 10%, the volume that texaco coal gasification technology generates gas consists of: H
235 ~ 36%, CO44% ~ 51%, CO
213% ~ 18%, CH
40.1%, needed to carry out water-gas shift adjustment hydrogen-carbon ratio to unstripped gas before carrying out methanation.For above-mentioned situation, if by synthetic gas under the condition of molybdenum base dual-function catalyst, directly carry out converting and methanation reaction, then removing of sour gas is carried out, not only can save water-gas shift operation, reduce facility investment greatly and running cost, and after first carrying out methanation, gas volume be reduced, reduce the gas volume of acid gas removal, also reduce the facility investment and energy consumption that remove sour gas.
But should be noted, above-mentioned catalyst for methanation in presence of sulfur has the dual-use function of water-gas shift and methanation, therefore in methanation, inevitably have the generation of water-gas shift, methanation and reverse water-gas-shift reaction, from aerodynamic point, while CO hydrogenation synthesis methane, carry out CO water-gas shift simultaneously and generate CO
2and hydrogen, and then cause CO in tail gas
2content increases greatly, considers the reversibility of CO water-gas shift, a large amount of CO
2can cause the generation of transformationreation against the current, therefore be subject to the restriction of thermodynamic(al)equilibrium, the CO in synthetic gas is difficult to transform completely, removes after sour gas through low-temperature rectisol, still has a large amount of CO and H in product except methane
2gas, have impact on the quality of Sweet natural gas, limits its industrial applications.
Summary of the invention
The object of this invention is to provide the technique that a kind of technical process is simple, facility investment is few, comprehensive energy consumption is low and gas product is excellent producing synthesis gas from coal carries out methanation in presence of sulfur synthetic natural gas.
The present invention is that synthetic gas is after washing, first on sulfur-resisting transformation and methanation in presence of sulfur loading type molybdenum base dual-function catalyst, carry out the reaction of secondary methanation in presence of sulfur, reacted gas removes after sour gas through low-temperature rectisol, to carry out after one-level methanation reaction obtaining gas product through Ni methylmethane catalyzer.
For reaching above-mentioned purpose, inventor herein is by catalyst preparing many times, activity rating, Theoretical Calculation and software simulation, grasp the reaction rule of synthetic gas sulfur-resisting transformation and methanation in presence of sulfur on loading type molybdenum base dual-function catalyst, obtain a large amount of basic datas of gaseous fraction with reaction conditions, and the coal preparing natural gas Engineering Design experience combined for many years, first the synthetic gas proposing gasification generation carries out the reaction of two-stage methanation in presence of sulfur, and by selecting suitable reaction conditions as temperature, pressure, air speed and water-gas ratio etc., product methane content wherein is not only made greatly to improve, and by H
2/ CO is adjusted between 3.0 ~ 3.3, the gas product of methanation in presence of sulfur removes sour gas (CO through low-temperature rectisol
2+ H
2s) after, under the effect of nickel-base catalyst, carry out peace and quiet methanation reaction, after cooling and gas-liquid separation, obtain more than methane volumetric content>=96.5% gas product.Compared with existing industrial methanation process, the methanation in presence of sulfur technique that the present invention proposes is without the need to independently converter unit, flow process is simpler, reduce facility investment and the energy consumption of conversion, and reduce reaction because methane turns to volume, therefore the facility investment of low-temperature rectisol and energy consumption are also reduced greatly, there are great industrial value and potentiality.
The invention discloses the technique that a kind of producing synthesis gas from coal carries out methanation in presence of sulfur synthetic natural gas, its concrete technology route is:
(1) synthetic gas is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, loading type molybdenum base dual-function catalyst carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, again after input and output material interchanger I and synthetic gas heat exchange, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of loading type Mo base dual-function catalyst, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and synthetic gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter in rectisol system and remove CO
2and H
2after S, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is worked off one's feeling vent one's spleen after heat exchange through input and output material interchanger III and methanator, methanator is entered from top, under the effect of Ni-based methanation catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, work off one's feeling vent one's spleen and first reclaim heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, and separating tank top expellant gas is gas product, sends into gas distributing system after drying and compression.
Synthetic gas as above obtains through crushed coal pressure gasifying technology, and its synthetic gas consists of H
237 ~ 40%, CO17% ~ 20%, CO
228 ~ 33%, CH
48% ~ 12%, N
20.3 ~ 0.7%.
Loading type molybdenum base dual-function catalyst quality group as above becomes: active ingredient Mo
2o
310 ~ 35wt%, auxiliary agent oxide compound 2 ~ 20wt%, carrier 50 ~ 85wt%; Wherein auxiliary agent is one or more in Co, La, Ce, Zr, Fe, Ni and K, and preferably Co, La, Ce or Zr; Carrier is γ-Al
2o
3, SiO
2, magnesium-aluminium spinel, ZrO
2, CeO
2-Al
2o
3complex carrier or Al
2o
3-ZrO
2complex carrier, and preferably magnesium aluminate, CeO
2-Al
2o
3complex carrier or Al
2o
3-ZrO
2complex carrier; Active ingredient is carried on carrier by pickling process, coprecipitation method or sol-gel method, and pickling process refers to patent 102463118A or CN103495421A, and coprecipitation method refers to patent CN103480362A, and sol-gel method refers to patent CN101733115A.
Methanation in presence of sulfur reactor I described above and methanation in presence of sulfur reactor II is fixed bed isothermal reactor.Temperature of reaction is 450 ~ 600 DEG C, and reaction pressure is 2 ~ 7MPa, and reaction velocity is 2000 ~ 8000h
-1.
In methanation in presence of sulfur reactor I inlet gas as above, the mol ratio of water vapour and synthetic gas is 0.1 ~ 0.3, and methanation in presence of sulfur reactor II import is without the need to passing into water vapour, and the inlet gas temperature of two reactors is 270 ~ 300 DEG C.
Low-temperature rectisol as above is made up of thionizer and decarbonizing tower, and service temperature is-20 ~-60 DEG C, working pressure 2.0 ~ 7.0MPa, and the sulphur after low-temperature rectisol in gas takes off to 0.01 ~ 0.1ppm, CO
2volume content takes off to 0.3 ~ 0.8V%.
One in a kind of wide temperature range type methanation catalyst that the catalyst based MCR-2X methanation catalyst for Top's rope of the Ni used in methanator I and II as above, Davy company CEG-LH methanation catalyst or Dalian Physical and Chemical Inst. develop, the catalyzer of wherein Dalian Physical and Chemical Inst. exploitation becomes with the quality group of oxide basis: active ingredient NiO10 ~ 75%, auxiliary agent La
2o
30.1 ~ 15% and carrier A l
2o
3-ZrO
2surplus, auxiliary agent is the composition of lanthanum trioxide or lanthanum trioxide and nickel lanthanum compound, and carrier is the composition that aluminum oxide and nickel aluminide and zirconium white are formed, and its preparation process and condition refer to patent CN102029162.
Methanator I described above and II first are insulation fix bed reactor, and its inlet gas temperature is 250 ~ 270 DEG C, and reaction pressure is 2 ~ 7MPa, and reaction velocity is 2000 ~ 8000h
-1, temperature of working off one's feeling vent one's spleen is 300 ~ 450 DEG C.
The volume of the synthetic gas of synthetic gas as above after above-mentioned technology and condition consists of: CH
493 ~ 96%, CO
20.5 ~ 1.0, H
20.5 ~ 2%, N
22 ~ 3%, C
2~
61 ~ 2%.
Compared with prior art, the present invention has substantive distinguishing features and marked improvement is in the present invention:
(1) sulfur-resisting transformation and methanation in presence of sulfur merge by the producing synthesis gas from coal methanation in presence of sulfur technique of the present invention's exploitation, compared with existing industrial coal process for producing natural, decrease independent sulfur-resisting transformation unit, save investment and the running cost of conversion equipment.
(2) traditional coal process for producing natural is that synthetic gas is through sulfur-resisting transformation, low-temperature rectisol and methanation finally obtained Sweet natural gas, and the present invention first carries out low-temperature rectisol and removes sour gas after sulfur-resisting transformation and methanation in presence of sulfur, because methane turns to the reaction of deduction, gas volume after methanation in presence of sulfur and sulfur-resisting transformation reduces about 20%, greatly reduces equipment size and the process cost of low-temperature rectisol.
(3) the present invention sets up the methanator that is filled with nickel-base catalyst after low-temperature rectisol, makes due to CO
2unreacted CO and H of part that excessive and inverse water-gas shift causes
2transform completely, the methane content in gas product, up to more than 93%, while taking full advantage of sulfur-resisting transformation and methanation dual-function catalyst advantage, compensate for the shortcoming of this catalyzer.
(4) the present invention just carries out removing of sour gas after methanation in presence of sulfur, contains a large amount of CO when carrying out methanation in presence of sulfur in gas
2rare gas element, thus in methanation without the need to gas circulation to shift out reaction heat, decrease input and the circulating consumption of recycle compressor.
(5) resistant to sulfur change and methanation in presence of sulfur merge by the present invention, due to the strong exothermal reaction of methanation, sulfur-resisting transformation temperature is increased, avoids in independent sulfur-resisting transformation process and cause because temperature is too low realizing the conversion of organosulfur to inorganic sulfur, and then affect the problem of sulfur recovery.
Accompanying drawing explanation
Accompanying drawing 1 carries out the technique of methanation in presence of sulfur synthetic natural gas for producing synthesis gas from coal
As shown in Figure 1,1 is methanation in presence of sulfur reactor I, and 2 is methanation in presence of sulfur reactor II, 3 is methanator I, and 4 is water wash systems, and 5 is rectisol systems, 6 is knockout drum I, 7 knockout drum II, and 8 is air-cooler I, 9 is air-cooler II, and 10 is waste heat boiler I, and 11 is waste heat boiler II, 12 is waste heat boiler III, and 13 is water coolers, and 14 is input and output material interchanger I, 15 is input and output material interchanger II, and 16 is input and output material interchanger III, 17 deep freezers.
Embodiment
The proposition of present invention process and condition is all propose on the basis to numerous Mo base sulfur resistant catalyst and Ni methylmethane chemical industry catalyst screening, if originally for commercial catalysts the present invention can provide catalyzer model in implementation process, if from the catalyzer of other inventions, the present invention can provide its composition or source.
Below by specific embodiment, the specific embodiment of the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to above-described embodiment.
Embodiment 1
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer used in methanation in presence of sulfur reactor II, and its oxide mass consists of MoO
310wt%-Co
2o
35wt%/Al
2o
3-ZrO
2the catalyzer of 85wt%, active ingredient MoO
3with auxiliary agent Co
2o
3carrier A l is carried on by the mode of co-precipitation
2o
3-ZrO
2on, concrete preparation method and technique are shown in CN101733115A embodiment 3; Nickel-base catalyst in methanator adopts the MCR-2X catalyzer of Top's rope.Adopt above-mentioned catalyzer, its specific embodiment and condition as follows:
(1) volume consists of H
237%, CO17.3%, CO
233%, CH
412% and N
2the synthetic gas of 0.7 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 300 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.3, in 450 DEG C, 7MPa and 8000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
310wt%-Co
2o
35wt%/Al
2o
3-ZrO
2on carry out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 300 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 450 DEG C, 7MPa and 8000h
-1condition under, at loading type Mo base dual-function catalyst MoO
310wt%-Co
2o
35wt%/Al
2o
3-ZrO
2effect under carry out second stage methanation in presence of sulfur and sulfur-tolerant water gas shift, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and synthetic gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-20 DEG C and 7.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.01ppm, and CO
2be removed to volume content 0.3V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 250 DEG C, and entering methanator from top, is 8000h in pressure 7MPa and reaction velocity
-1condition under, under the effect of MCR-2X nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 450 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas group of the present embodiment and gas product composition for details see attached table 1.
Embodiment 2
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer used in methanation in presence of sulfur reactor II, and its oxide mass consists of MoO
315wt%-Co
2o
3+ La
2o
3the catalyzer of 10wt%/magnesium-aluminium spinel 75wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ La
2o
3carrier A l is carried on by the mode of collosol and gel
2o
3-ZrO
2on, concrete preparation method and technique are shown in CN101733115A embodiment 6; Nickel-base catalyst in methanator adopts the MCR-2X catalyzer of Top's rope.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
238%, CO18%, CO
232%, CH
411.5% and N
2the synthetic gas of 0.5 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 295 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.25, in 600 DEG C, 6MPa and 7500h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
315wt%-Co
2o
3+ La
2o
310wt%/Al
2o
3-ZrO
275wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 300 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 600 DEG C, 6MPa and 7500h
-1condition under, at loading type Mo base dual-function catalyst MoO
315wt%-Co
2o
3+ La
2o
310wt%/Al
2o
3-ZrO
2second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 75wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-20 DEG C and 6.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.02ppm, and CO
2be removed to volume content 0.35V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 255 DEG C, and entering methanator from top, is 7500h in pressure 6MPa and reaction velocity
-1condition under, under the effect of MCR-2X nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 432 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 3
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer used in methanation in presence of sulfur reactor II, and its oxide mass consists of MoO
320wt%-Co
2o
3+ Ce
2o
312wt%/γ-Al
2o
3the catalyzer of 68wt%, active ingredient Mo
2o
3with auxiliary agent Co
2o
3+ Ce
2o
3carrier γ-Al is carried on by the mode of collosol and gel
2o
3on, concrete preparation method and technique are shown in CN101733115A embodiment 4; Nickel-base catalyst in methanator adopts the MCR-2X catalyzer of Top's rope.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
238%, CO18%, CO
232%, CH
411.5% and N
2the synthetic gas of 0.5 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 295 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.20, in 550 DEG C, 5MPa and 7000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
320wt%-Co
2o
3+ Ce
2o
312wt%/γ-Al
2o
368wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 295 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 550 DEG C, 5MPa and 7000h
-1condition under, at loading type Mo base dual-function catalyst MoO
320wt%-Co
2o
3+ Ce
2o
312wt%/γ-Al
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 68wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-60 DEG C and 5.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.03ppm, and CO
2be removed to volume content 0.40V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 260 DEG C, and entering methanator from top, is 7000h in pressure 5MPa and reaction velocity
-1condition under, under the effect of MCR-2X nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 421 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 4
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer used in methanation in presence of sulfur reactor II, and its oxide mass consists of MoO
325wt%-Co
2o
3+ ZrO
215wt%/CeO
2-Al
2o
3the catalyzer of 60wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ ZrO
2support C eO is carried on by the mode of dipping
2-Al
2o
3on, concrete preparation method and technique are shown in CN102463118A embodiment 5; Nickel-base catalyst in methanator adopts the MCR-2X catalyzer of Top's rope.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
239%, CO19.5%, CO
233%, CH
48.0% and N
2the synthetic gas of 0.5 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 290 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.15, in 550 DEG C, 4.5MPa and 6500h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
325wt%-Co
2o
3+ ZrO
215wt%/CeO
2-Al
2o
360wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 290 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 550 DEG C, 4.5MPa and 6500h
-1condition under, at loading type Mo base dual-function catalyst MoO
325wt%-Co
2o
3+ ZrO
215wt%/CeO
2-Al
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 60wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-50 DEG C and 4.5MPa condition, remove CO
2and H
2s, H
2s is removed to 0.04ppm, and CO
2be removed to volume content 0.45V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 265 DEG C, and entering methanator from top, is 6500h in pressure 4.5MPa and reaction velocity
-1condition under, under the effect of MCR-2X nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 410 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 5
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer used in methanation in presence of sulfur reactor II, and its oxide mass consists of MoO
330wt%-Co
2o
3+ Fe
2o
3+ NiO20wt%/CeO
2-Al
2o
3the catalyzer of 50wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ Fe
2o
3+ NiO is carried on support C eO by the mode of dipping
2-Al
2o
3on, concrete preparation method and technique are shown in CN102463118A embodiment 5; Nickel-base catalyst in methanator adopts the MCR-2X catalyzer of Top's rope.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
239%, CO19.5%, CO
231.5%, CH
49.5% and N
2the synthetic gas of 0.5 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 285 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.10, in 500 DEG C, 4.0MPa and 6000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
330wt%-Co
2o
3+ Fe
2o
3+ NiO20wt%/CeO
2-Al
2o
350wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 285 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 500 DEG C, 4.0MPa and 6000h
-1condition under, at loading type Mo base dual-function catalyst MoO
330wt%-Co
2o
3+ Fe
2o
3+ NiO20wt%/CeO
2-Al
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 50wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-40 DEG C and 4.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.05ppm, and CO
2be removed to volume content 0.50V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 270 DEG C, and entering methanator from top, is 6000h in pressure 4.0MPa and reaction velocity
-1condition under, under the effect of MCR-2X nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 397 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 6
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO
335wt%-Co
2o
3+ KO
22wt%/ZrO
2the catalyzer of 63wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ KO
2carrier ZrO is carried on by the mode of dipping
2on, concrete preparation method and technique are shown in CN103495421A embodiment 14; Nickel-base catalyst in methanator adopts the CEG-LH catalyzer of Davy.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
240%, CO20%, CO
230%, CH
49.5% and N
2the synthetic gas of 0.5 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 280 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.20, in 500 DEG C, 3.5MPa and 5500h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
335wt%-Co
2o
3+ KO
22wt%/ZrO
263wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 280 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 500 DEG C, 3.5MPa and 5500h
-1condition under, at loading type Mo base dual-function catalyst MoO
335wt%-Co
2o
3+ KO
22wt%/ZrO
2second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 63wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-35 DEG C and 3.5MPa condition, remove CO
2and H
2s, H
2s is removed to 0.06ppm, and CO
2be removed to volume content 0.55V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 260 DEG C, and entering methanator from top, is 5500h in pressure 3.5MPa and reaction velocity
-1condition under, under the effect of CEG-LH nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 372 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 7
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO
327wt%-Co
2o
3+ La
2o
3the catalyzer of 8wt%/magnesium-aluminium spinel 65wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ La
2o
3be carried on carrier magnesium-aluminium spinel by the mode of dipping, concrete preparation method and technique are shown in CN103495421A embodiment 14; Nickel-base catalyst in methanator adopts the CEG-LH catalyzer of Davy.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
240%, CO20%, CO
228%, CH
411.3% and N
2the synthetic gas of 0.7 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 275 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.20, in 500 DEG C, 3.0MPa and 5000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
327wt%-Co
2o
3+ La
2o
38wt%/magnesium-aluminium spinel 65wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 275 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 500 DEG C, 3.0MPa and 5000h
-1condition under, at loading type Mo base dual-function catalyst MoO
327wt%-Co
2o
3+ La
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 8wt%/magnesium-aluminium spinel 65wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-30 DEG C and 3.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.07ppm, and CO
2be removed to volume content 0.55V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 260 DEG C, and entering methanator from top, is 5000h in pressure 3.0MPa and reaction velocity
-1condition under, under the effect of CEG-LH nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 351 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 8
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO
323wt%-Co
2o
3+ ZrO
2+ CeO
27wt%/γ-Al
2o
3the catalyzer of 70wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ ZrO
2+ CeO
2carrier γ-Al is carried on by the mode of co-precipitation
2o
3on, concrete preparation method and technique are shown in CN103480362A embodiment 2; Nickel-base catalyst in methanator adopts the CEG-LH catalyzer of Davy.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
240%, CO19.3%, CO
228%, CH
412% and N
2the synthetic gas of 0.7 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 270 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.20, in 450 DEG C, 2.5MPa and 4000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
323wt%-Co
2o
3+ ZrO
2+ CeO
27wt%/γ-Al
2o
370wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 270 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 450 DEG C, 2.5MPa and 4000h
-1condition under, at loading type Mo base dual-function catalyst MoO
323wt%-Co
2o
3+ ZrO
2+ CeO
27wt%/γ-Al
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 70wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-25 DEG C and 2.5MPa condition, remove CO
2and H
2s, H
2s is removed to 0.08ppm, and CO
2be removed to volume content 0.6V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 260 DEG C, and entering methanator from top, is 4000h in pressure 2.5MPa and reaction velocity
-1condition under, under the effect of CEG-LH nickel-base catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 334 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 9
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO
313wt%-Co
2o
3+ CeO
214.5wt%/γ-Al
2o
3the catalyzer of 72.5wt%, active ingredient MoO
3with auxiliary agent Co
2o
3+ ZrO
2+ CeO
2carrier γ-Al is carried on by the mode of co-precipitation
2o
3on, concrete preparation method and technique are shown in CN103480362A embodiment 5; Nickel-base catalyst quality group in methanator becomes NiO40wt%-La
2o
37wt%-Al
2o
343wt%-ZrO
27wt%, concrete preparation method and step are shown in CN102029162A embodiment 5.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
237%, CO20%, CO
230%, CH
412% and N
2the synthetic gas of 1.0 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 280 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.20, in 450 DEG C, 2.0MPa and 3000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
313wt%-Co
2o
3+ CeO
214.5wt%/γ-Al
2o
372.5wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and unstripped gas heat exchange to 280 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 450 DEG C, 2.0MPa and 3000h
-1condition under, at loading type Mo base dual-function catalyst MoO
313wt%-Co
2o
3+ CeO
214.5wt%/γ-Al
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 72.5wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-20 DEG C and 2.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.09ppm, and CO
2be removed to volume content 0.7V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 270 DEG C, and entering methanator from top, is 3000h in pressure 2.0MPa and reaction velocity
-1condition under, at NiO40wt%-La
2o
37wt%-Al
2o
343wt%-ZrO
2carry out methanation reaction under the effect of 7wt% nickel-base catalyst, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 314 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Embodiment 10
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO
313wt%-ZrO
214.5wt%/γ-Al
2o
3the catalyzer of 72.5wt%, active ingredient MoO
3with auxiliary agent ZrO
2γ-Al is carried on by the mode of co-precipitation
2o
3on, concrete preparation method and technique are shown in CN103480362A embodiment 7; Nickel-base catalyst quality group in methanator becomes NiO75wt%-La
2o
37wt%-Al
2o
315wt%-ZrO
23wt%, concrete preparation method and step are shown in CN102029162A embodiment 4.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) volume consists of H
237%, CO20%, CO
230%, CH
412% and N
2the synthetic gas of 1.0 is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange to 280 DEG C through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, the mol ratio of water vapour and synthetic gas is 0.20, in 450 DEG C, 4.0MPa and 2000h
-1reaction conditions under, at loading type Mo base dual-function catalyst MoO
313wt%-ZrO
214.5wt%/γ-Al
2o
372.5wt% carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, works off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, then after input and output material interchanger I and synthetic gas heat exchange to 280 DEG C, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, in 450 DEG C, 4.0MPa and 2000h
-1condition under, at loading type Mo base dual-function catalyst MoO
313wt%-ZrO
214.5wt%/γ-Al
2o
3second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of 72.5wt%, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and unstripped gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter rectisol system, under-20 DEG C and 4.0MPa condition, remove CO
2and H
2s, H
2s is removed to 0.1ppm, and CO
2be removed to volume content 0.8V%, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is after input and output material interchanger III and methanator work off one's feeling vent one's spleen heat exchange to 270 DEG C, and entering methanator from top, is 2000h in pressure 4.0MPa and reaction velocity
-1condition under, at NiO75wt%-La
2o
37wt%-Al
2o
315wt%-ZrO
2carry out methanation reaction under the effect of 3wt% nickel-base catalyst, the CO so far in synthetic gas is all converted into CH
4gas, temperature is that 300 DEG C work off one's feeling vent one's spleen first reclaims heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, separating tank top expellant gas and gas product, sends into gas distributing system after drying and compression.
The unstripped gas of the present embodiment and gas product composition for details see attached table 1.
Subordinate list 1
Claims (11)
1. producing synthesis gas from coal carries out a technique for methanation in presence of sulfur synthetic natural gas, it is characterized in that comprising the steps:
(1) synthetic gas is through water wash system dedusting with except after wet goods impurity, first to be worked off one's feeling vent one's spleen heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, to work off one's feeling vent one's spleen heat exchange through input and output material interchanger I and methanation in presence of sulfur I again, and enter methanation in presence of sulfur reactor I from top after mixing with water vapour, loading type molybdenum base dual-function catalyst carries out first step methanation in presence of sulfur and sulfur-tolerant water gas shift, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers I, again after input and output material interchanger I and synthetic gas heat exchange, enter methanation in presence of sulfur reactor II;
(2) from the reaction gas of methanation in presence of sulfur reactor I after top enters methanation in presence of sulfur reactor II, second stage methanation in presence of sulfur and sulfur-tolerant water gas shift is carried out under the effect of loading type Mo base dual-function catalyst, work off one's feeling vent one's spleen and first reclaim heat by high-pressure waste-heat boilers II, again through input and output material interchanger II and synthetic gas heat exchange, and enter in knockout drum I after being cooled further by air-cooler I, phlegma self-separation pot bottom is discharged, and after the discharge of gas phase self-separation tank top, after being cooled by deep cooler, enter in rectisol system and remove CO
2and H
2after S, send into and the catalyst based methanator of Ni is housed;
(3) gas after low-temperature rectisol is worked off one's feeling vent one's spleen after heat exchange through input and output material interchanger III and methanator, methanator I is entered from top, under the effect of Ni-based methanation catalyst, carry out methanation reaction, the CO so far in synthetic gas is all converted into CH
4gas, work off one's feeling vent one's spleen and first reclaim heat by waste heat boiler III, through input and output material interchanger III with from the gas converting heat of low-temperature rectisol, and after air-cooler II and water cooler cool further, enter in knockout drum II and carry out gas-liquid separation, phlegma self-separation pot bottom is discharged, and separating tank top expellant gas is gas product, sends into gas distributing system after drying and compression;
The temperature of reaction of described methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II is 450 ~ 600 DEG C, and reaction pressure is 2 ~ 7MPa, and reaction velocity is 2000 ~ 8000h
-1;
In described methanation in presence of sulfur reactor I inlet gas, the mol ratio of water vapour and synthetic gas is 0.1 ~ 0.3;
The inlet gas temperature of described methanation in presence of sulfur reactor I or methanation in presence of sulfur reactor II is 270 ~ 300 DEG C;
The inlet gas temperature of described methanator I is 250 ~ 270 DEG C, and reaction pressure is 2 ~ 7MPa, and reaction velocity is 2000 ~ 8000h
-1, temperature of working off one's feeling vent one's spleen is 300 ~ 450 DEG C.
2. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, and it is characterized in that described synthetic gas obtains through crushed coal pressure gasifying technology, its synthetic gas consists of H
237 ~ 40%, CO17% ~ 20%, CO
228 ~ 33%, CH
48% ~ 12%, N
20.3 ~ 0.7%.
3. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described loading type molybdenum base dual-function catalyst quality group becomes: active ingredient Mo
2o
310 ~ 35wt%, auxiliary agent oxide compound 2 ~ 20wt%, carrier 50 ~ 85wt%; Wherein auxiliary agent is one or more in Co, La, Ce, Zr, Fe, Ni and K, and carrier is γ-Al
2o
3, SiO
2, magnesium-aluminium spinel, ZrO
2, CeO
2-Al
2o
3complex carrier or Al
2o
3-ZrO
2complex carrier.
4. a kind of producing synthesis gas from coal as claimed in claim 3 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described auxiliary agent is Co, La, Ce or Zr.
5. a kind of producing synthesis gas from coal as claimed in claim 3 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described carrier is magnesium-aluminium spinel, CeO
2-Al
2o
3complex carrier or Al
2o
3-ZrO
2complex carrier.
6. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II is fixed bed isothermal reactor.
7. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described low-temperature rectisol is made up of thionizer and decarbonizing tower, and service temperature is-20 ~-60 DEG C, working pressure 2.0 ~ 7.0MPa.
8. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that the sulphur after low-temperature rectisol in gas takes off to 0.01 ~ 0.1ppm, CO
2volume content takes off to 0.3 ~ 0.8V%.
9. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that the catalyst based MCR-2X methanation catalyst for Top's rope of Ni, Davy company CEG-LH methanation catalyst or the catalyzer that use in described methanator I or methanator II become with the quality group of oxide basis: active ingredient NiO10 ~ 75%, auxiliary agent La
2o
30.1 ~ 15% and carrier A l
2o
3-ZrO
2surplus, auxiliary agent is the composition of lanthanum trioxide or lanthanum trioxide and nickel lanthanum compound, and carrier is the composition that aluminum oxide and nickel aluminide and zirconium white are formed.
10. a kind of producing synthesis gas from coal as claimed in claim 1 carries out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described methanator I or methanator II first are insulation fix bed reactor.
11. a kind of producing synthesis gas from coal as described in any one of claim 1-10 carry out the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that the volume of the synthetic gas of described synthetic gas after above-mentioned technology and condition consists of: CH
493 ~ 96%, CO
20.5 ~ 1.0, H
20.5 ~ 2%, N
22 ~ 3%, C
2 ~ 61 ~ 2%.
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| CN104774662B (en) * | 2014-12-18 | 2017-11-10 | 神华集团有限责任公司 | It is a kind of that crude synthesis gas is converted into the technique rich in methane gas |
| CN105925328B (en) * | 2016-05-06 | 2019-01-04 | 青岛联信催化材料有限公司 | The production technology of natural gas is produced in a kind of high CO content unstripped gas sulphur-resistant conversion-methanation |
| CN108219879B (en) * | 2016-12-14 | 2020-08-04 | 中国石化工程建设有限公司 | Non-circulation sulfur-tolerant methanation process for coal-based substitute natural gas |
| WO2019240586A1 (en) * | 2018-06-15 | 2019-12-19 | Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center | Catalyst for catalytic oxidative cracking of hydrogen sulphide with concurrent hydrogen production |
| CN112916051B (en) * | 2021-01-25 | 2023-08-18 | 内蒙古中煤远兴能源化工有限公司 | Protective agent of sulfur-tolerant shift catalyst and preparation method thereof |
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| 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 |
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