CN104164263B - A kind of coke(oven)gas methanation in presence of sulfur prepares the method for natural gas liquids - Google Patents

A kind of coke(oven)gas methanation in presence of sulfur prepares the method for natural gas liquids Download PDF

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CN104164263B
CN104164263B CN201410407692.1A CN201410407692A CN104164263B CN 104164263 B CN104164263 B CN 104164263B CN 201410407692 A CN201410407692 A CN 201410407692A CN 104164263 B CN104164263 B CN 104164263B
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gas
methanation
sulfur
coke
oven
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CN201410407692.1A
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CN104164263A (en
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张庆庚
范辉
崔晓曦
李晓
李德宝
贾丽涛
孙德魁
史郭晓
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赛鼎工程有限公司
中国科学院山西煤炭化学研究所
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Abstract

A kind of method that coke(oven)gas methanation in presence of sulfur prepares natural gas liquids be by coke-oven gas after oil removing, the de-impurity such as naphthalene and de-benzene, loading type molybdenum base catalyst for methanation in presence of sulfur directly carries out three sections of methanation reactions, then once removes sulphur, CO through low-temperature rectisol 2and C 2-4the impurity such as hydro carbons, isolate N finally by a cryogenic liquefying 2and H 2deng after methane content up to more than 97% natural gas liquids.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

A kind of coke(oven)gas methanation in presence of sulfur prepares the method for natural gas liquids
Technical field
The invention belongs to a kind of method preparing natural gas liquids, be specifically related to a kind of method that coke(oven)gas methanation in presence of sulfur prepares natural gas liquids.
Background technology
China is maximum in the world coke production, consumption and export State.2012, China's coke output reached 4.43 hundred million t, if produce 430m by production one ton of coke 3coke-oven gas calculate, only the coke-oven gas of this year just reaches 1,905 hundred million m 3, wherein the coke-oven gas of about 70% is used for coke oven heating and domestic gas, and remaining nearly 57,000,000,000 m 3coke-oven gas is not utilized, and causes the serious wasting of resources and environmental pollution.Sweet natural gas is a kind of high-quality, efficient and safe clean energy.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.Synthesizing natural gas from coke oven gas, especially the new way that LNG Technology opens coke-oven gas efficiency utilization is synthesized, not only can alleviate the situation of domestic natural gas shortage, and solve coke-oven gas and discharge the environmental pollution and problem of resource waste that cause, the recycle and economic Sustainable development realizing china natural resources is had great importance.
At present, the technology of coke-oven gas synthesis natural gas liquids mainly comprises Physical and chemical method two kinds, and wherein the operational path of Physical is: coke-oven gas → purification → low temperature separation process → natural gas liquids; And chemical method adds methanation in Physical, be specially: coke-oven gas → purification → methanation → low temperature separation process → natural gas liquids, although the operational path that chemical method prepares natural gas liquids is more complicated than Physical, it is by most in coke(oven)gas CO, CO 2and H 2transform in order to CH 4gas, make the yield of methane be increased to about 35% by 25%, energy utilization rate is higher, becomes the optimization technique of current coke-oven gas synthesis natural gas liquids project.But because the composition of coke-oven gas is very complicated, except CH in gas 4, CO, CO 2and H 2deng outside available gas composition, also containing the etching apparatuses such as tar, naphthalene, benzene, ammonia and sulphur and the impurity affecting Ni methylmethane catalyzer, in the gas after methanation simultaneously, still there is a large amount of N 2, H 2and C 2-4hydro carbons hydro carbons etc. affects the component of natural gas liquids quality.Due to prior art adopt Ni methylmethane catalyzer poison resistance, especially resistant to sulfur ability is poor, require that the sulphur content in methanation gas must lower than 0.1ppm, but containing the organosulfur being difficult in a large number remove in coke(oven)gas, need multistage hydrogenation to be the H easily removed by organic sulfur conversion 2s, and sulphur content just can be made to reach above-mentioned requirements by the complicated technology of Multistage desulfuration; Simultaneously in order to isolate the N after methanation in gas 2, H 2and C 2-4the components such as hydro carbons hydro carbons, the technique of multistage cooling and multistage liquefaction need be adopted could to obtain the liquefied natural gas product meeting national requirements, and then cause the low temperature separation process operation after the cleaning section before methanation and methanation extremely complicated, its operation length accounts for more than 3/4 (idiographic flow is shown in upper figure) of whole flow process, considerably increases facility investment and the energy consumption of coke-oven gas synthesis natural gas liquids.Therefore, how to optimize coke-oven gas liquefaction prepare Sweet natural gas technical process, reduce the study hotspot that energy consumption and facility investment become numerous mechanism.
Patent CN101597527A discloses a kind of method utilizing coke-oven gas to produce Sweet natural gas, by filling into carbon source in coke(oven)gas, makes synthetic gas meet (H 2-3CO)/CO 2the stoichiometric ratio of ≈ 4, has then obtained Sweet natural gas by fine de-sulfur and methanation, although this invention further increases the productive rate of Sweet natural gas, and itself and the purification process before unreduced methanation and the gas separating technology after methanation.Patent CN101649232A discloses a kind of technique of gas employing methanation of coke oven synthetic natural gas, be specially after coke-oven gas is compressed, through preliminary cleaning, desulfurization, the Sweet natural gas of Sweet natural gas GB (GB17820-1999) must be met after two sections of methanation reactions and pressure-variable adsorption or membrane sepn, membrane sepn is introduced in pressure-variable adsorption the effect that improve to a certain extent and be separated, but compared with prior art, the cost of membrane sepn is higher, be not suitable for large-scale industrial application, and pressure-variable adsorption is in energy consumption, facility investment and operation easier do not have obvious advantage, and the purification process of coke(oven)gas is not shortened in this invention.Patent CN101391935A discloses a kind of method utilizing coke-oven gas synthesizing methane, by purifying and dedusting, compress heat exchange, add water vapour, the step such as three sections of methane and PSA separation of methane, obtain the gas product of methane concentration more than 90%, but this invention also adopts the complicated technology of multistage hydrogenation and Multistage desulfuration, do not provide the effective ways simplifying sulfur removal technology.Although above-mentioned patent improves natural gas yield and separating effect to a certain extent by Optimization Technology, but it does not fundamentally solve synthesizing natural gas from coke oven gas, especially complicated, the energy consumption of the technical process of natural gas liquids and the large problem of facility investment.
Catalyst for methanation in presence of sulfur take mainly Mo as active metal, adds Co, La, Zr, Ce and Fe etc. as auxiliary agent simultaneously, and said components is carried on Al with the method for dipping, kneading or collosol and gel by active ingredient and auxiliary agent 2o 3, ZrO 2and SiO 2deng on carrier.Because the catalyst for methanation in presence of sulfur after sulfuration is with MoS 2for active centre, it is to the sulphur content no maximum requirement in synthetic gas, therefore without the need to just can methanation reaction be carried out to synthetic gas desulfurization, for methanation synthetic natural gas technology provides new thinking.The present inventor is found by a large amount of experiments, and above-mentioned catalyzer not only has good catalytic production of methane performance, also has catalysis organosulfur hydrogenation or hydrolysis generation H simultaneously 2the performance of S, and this catalyzer is owing to having and sulfur-resisting transformation similar catalyst component, also shows the catalytic performance of extremely strong carbon monoxide water-gas shift.Consider Problems existing in gas employing methanation of coke oven synthetic natural gas technique, if the coke(oven)gas before desulfurization is first carried out methanation reaction under the effect of above-mentioned sulfur resistant catalyst, and then carry out desulfurization, just avoid the multistage hydrogenation problem of the organosulfur existed in existing technique, enormously simplify the purification process of coke-oven gas, reduce investment and the energy consumption of synthesizing natural gas from coke oven gas, there is larger industrialization potential quality.
Summary of the invention
The object of the invention is to develop the method that a kind of technical process is simple, facility investment is few, comprehensive energy consumption is low and gas product is excellent coke(oven)gas methanation in presence of sulfur prepares natural gas liquids.
The present invention be by coke-oven gas after oil removing, the de-impurity such as naphthalene and de-benzene, loading type molybdenum base catalyst for methanation in presence of sulfur directly carries out three sections of methanation reactions, then once removes sulphur, CO through low-temperature rectisol 2and C 2-4the impurity such as hydro carbons, isolate N finally by a cryogenic liquefying 2and H 2deng after methane content up to more than 97% natural gas liquids.
For reaching above-mentioned purpose, inventor herein is by catalyst preparing many times, activity rating, Theoretical Calculation and software simulation, grasp the methanation in presence of sulfur of coke-oven gas on loading type molybdenum base catalyst for methanation in presence of sulfur, the reaction rule of organosulfur hydrogenation and water-gas shift, composition and the preparation method of the loading type molybdenum base catalyst for methanation in presence of sulfur being suitable for gas employing methanation of coke oven synthetic natural gas are filtered out, and the coal preparing natural gas Engineering Design experience combined for many years, propose through oil removing, coke-oven gas after the de-impurity such as naphthalene and de-benzene directly carries out three grades of methanation in presence of sulfur reactions, methane content is not only made greatly to improve, and be H by more than 99% organic sulfur conversion 2s gas, after cooling de-watering, gas is once removed H by low-temperature rectisol 2s (≤0.1ppm), CO 2and C 4above heavy hydrocarbon, isolates N finally by cryogenic liquefying is disposable 2and H 2deng after noncondensable gas methane content up to more than 97% liquefied natural gas product.The coke-oven gas methanation in presence of sulfur that the present invention proposes prepares the technique of natural gas liquids, while methanation in presence of sulfur, make the organic sulfur conversion of in gas 99% be H by hydrogenation and hydrolysis 2s, is then removed to below 0.1ppm through low-temperature rectisol by sulphur, avoids in prior art the complicated technology needing multistage hydrogenation and Multistage desulfuration; And due to desulfurization, de-CO 2and C 2-4the hydro carbons of hydro carbons all in low-temperature rectisol a step complete, just liquefied natural gas product is obtained by a cryogenic liquefying, avoid the Complicated Flow needing multistep deep cooling in existing technique, enormously simplify the technical process of coke-oven gas methanation in presence of sulfur synthetic natural gas, reduce facility investment and energy consumption, there is larger industrial prospect.
The invention discloses a kind of method that coke(oven)gas methanation in presence of sulfur prepares natural gas liquids, its step is as follows:
(1) coke-oven gas after oil removing, deamination, de-benzene and de-naphthalene is first worked off one's feeling vent one's spleen by input and output material interchanger II and methanation in presence of sulfur reactor II and is carried out heat exchange, again after input and output material interchanger I and methanator I works off one's feeling vent one's spleen heat exchange, methanation in presence of sulfur reactor I is entered from top, coke-oven gas carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction on loading type molybdenum base catalyst for methanation in presence of sulfur, work off one's feeling vent one's spleen and first reclaim heat through waste heat boiler I, again after inlet outlet heat exchanger I and coke-oven gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) reaction gas from methanation in presence of sulfur reactor I is after heat recuperation, methanation in presence of sulfur reactor II is entered from top, loading type molybdenum base sulfur resistant catalyst carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, reaction gas first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter in knockout drum I after air cooler I cools and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top discharge and after input and output material interchanger III and methanation in presence of sulfur reactor III works off one's feeling vent one's spleen heat exchange, methanation in presence of sulfur reactor III is entered from top,
(3) inlet gas carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur on loading type molybdenum base sulfur resistant catalyst, reacted gas reclaims heat by waste heat boiler III, and through inlet outlet heat exchanger III and inlet gas heat exchange, then after air-cooler II and water cooler cooling, knockout drum II is entered respectively, discharge bottom water of condensation self-separation tank II, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device and from the expellant gas heat exchange of knockout drum III top, and after deep cooler I cools, enter rectisol system and remove sulphur, carbonic acid gas, C 2-4the impurity such as hydro carbons, through the gas phase of low-temperature rectisol after deep cooler II cools further, enter knockout drum III, gas phase is discharged from top, and liquid phase is liquefied natural gas product.
Coke-oven gas as above through de-oiling, deamination, de-benzene and de-naphthalene consists of H 250 ~ 60%, CO5% ~ 8%, CO 21.5 ~ 4%, CH 423% ~ 27%, N 23 ~ 7%, C 2-4hydro carbons 2 ~ 4%.
The loading type molybdenum base catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor I and II as above uses becomes: active ingredient MoO 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 or K, and preferably Co, La, Ce or Fe; 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 and auxiliary agent are 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;
The quality group of the loading type molybdenum base catalyst for methanation in presence of sulfur that methanation in presence of sulfur reactor III as above uses becomes: active ingredient MoO 310 ~ 30wt%, auxiliary agent oxide compound 5 ~ 30wt%, carrier 50 ~ 85wt%; Auxiliary agent be La, Zr or Ce one or more; Carrier is γ-Al 2o 3, Al 2o 3-ZrO 2complex carrier, ZrO 2or CeO 2-Al 2o 3complex carrier, and by pickling process, active ingredient and auxiliary agent are carried on carrier, preparation condition and step are shown in patent 102463118A or CN103495421A.
Methanation in presence of sulfur reactor I as above, methanation in presence of sulfur reactor II and methanation in presence of sulfur reactor III, is characterized by three reactor devices and be insulation fix bed reactor.
The inlet gas temperature of methanation in presence of sulfur reactor I as above is 270 ~ 300 DEG C, and temperature out is 500 ~ 650 DEG C, and reaction pressure is 2 ~ 6MPa, and reaction velocity is 2000 ~ 8000h -1.
The inlet gas temperature of methanation in presence of sulfur reactor II as above is 270 ~ 300 DEG C, and temperature out is 350 ~ 550 DEG C, and reaction pressure is 2 ~ 6MPa, and reaction velocity is 2000 ~ 8000h -1.
The inlet gas temperature of methanation in presence of sulfur reactor III as above is 250 ~ 270 DEG C, and temperature out is 290 ~ 320 DEG C, and reaction pressure is 2 ~ 6MPa, and reaction velocity is 2000 ~ 8000h -1.
As above from methanation in presence of sulfur reactor III out and reclaim after heat and water cooler cooling through waste heat boiler III, gas temperature is down to 25-45 DEG C, is 2.0 ~ 4.5MPa, isolates process condensate water in knockout drum II at pressure; The isolated gas phase of knockout drum II, after precool heat exchanger device and deep cooler I are cooled to-30 ~-60 DEG C, enters rectisol system, and under the condition of-30 ~-60 DEG C and 2.0 ~ 4.5MPa, disposablely removes H 2s, CO 2and C 2-4hydro carbons and remaining naphthalene, benzene and tar, wherein H 2s is removed to 0.01 ~ 0.1ppm, and CO 2be removed to 20 ~ 50ppm; And gas phase is cooled to-150 ~-165 DEG C further by deep cooler II, in knockout drum III, carry out gas-liquid separation in 0.5 ~ 1.2MPa, tower top is H 2, N 2with trace amounts of CO gas, at the bottom of tower, obtain liquefied natural gas product.
Coke-oven gas as above consists of through above-mentioned technique and reacted natural gas liquids: CH 497 ~ 99%, N 20.3 ~ 1.0%, C 2-3hydro carbons 0.5 ~ 2.0%, CO 2≤ 100ppm, H 2≤ 100ppm, CO≤10ppm.
Compared with prior art, the present invention has substantive distinguishing features and marked improvement is in the present invention:
(1) the present invention is by arranging three grades of molybdenum base methanation in presence of sulfur reaction members, not only makes CO and CO of more than 97% in coke-oven gas 2be converted into methane, and make the organosulfur of more than 99% while methanation, be converted into the H easily removed 2s gas, then directly removed by low-temperature rectisol, avoid in prior art the problem needing multistage hydrogenation and Multistage desulfuration complex process, make the purification process of coke-oven gas reduce about about 1/3, greatly save investment and the energy consumption of coke oven gas purification equipment.
(2) the present invention is by optimizing separating technology and the condition of gas after methanation, by CO 2, liquefaction C 2-4, remaining benzene, naphthalene and tar all removes by low-temperature rectisol unit is disposable, make sublevel low temperature separation process become two-stage from three grades, save facility investment and the energy consumption of separating unit.
(3) after desulfurization unit is arranged at methanation in presence of sulfur by the present invention, because methanation is the reaction of volume-diminished, make the gas processing amount of desulfurization process be only about 70% before methanation, greatly reduce facility investment and the energy consumption of desulfurization process.
In sum, a kind of coke(oven)gas methanation in presence of sulfur disclosed by the invention is prepared liquefied natural gas process and is had the advantage that technical process is simple, facility investment is few and energy consumption is low, meets the policy of energy-saving and emission-reduction and Sustainable development, has great industrialization potential quality.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of prior art coke-oven gas synthesis natural gas liquids.
Fig. 2 is the process flow sheet that coke(oven)gas methanation in presence of sulfur of the present invention prepares natural gas liquids.
As shown in the figure, 1 is methanation in presence of sulfur reactor I, 2 is methanation in presence of sulfur reactor II, 3 is methanation in presence of sulfur reactor III, 4 is rectisol systems, 5 is knockout drum I, 6 is knockout drum II, 7 is knockout drum III, 8 is air-cooler I, 9 is air-cooler II, 10 is waste heat boiler I, 11 is waste heat boiler II, 12 is waste heat boiler III, 13 is input and output material interchanger I, 14 is input and output material interchanger II, 15 is input and output material interchanger III, 16 is water coolers, 17 is precool heat exchanger devices, 18 is deep cooler I, 19 is deep cooler II.
Embodiment
The proposition of present invention process and condition is all propose on the basis to numerous Mo base catalyst for methanation in presence of sulfur screening, if 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 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 3be carried on carrier magnesium-aluminium spinel by the mode of collosol and gel, concrete preparation method and technique are shown in CN101733115A embodiment 6; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 310wt%-La 2o 330wt%/γ-Al 2o 360wt%, preparation method and technique are shown in CN102463118A embodiment 4.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 250.0%, CO8.0%, CO 24.0%, CH 427.0%, N 27.0% and C 2-4the coke-oven gas of hydro carbons 4.0%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 270 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 6MPa and air speed in pressure is 8000h -1condition under, at loading type catalyst with base of molybdenum MoO 315wt%-Co 2o 3+ La 2o 310wt%/magnesium-aluminium spinel 75wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 650 DEG C work off one's feeling vent one's spleen first reclaims heat through waste heat boiler I, again after input and output material interchanger I and coke-oven gas heat exchange reach 280 DEG C, enter methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 6.0MPa and air speed is 8000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 315wt%-Co 2o 3+ La 2o 310wt%/magnesium-aluminium spinel 75wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 550 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 250 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 6.0MPa and 8000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 310wt%-La 2o 330wt%/γ-Al 2o 360wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 320 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 45 DEG C, gas-liquid separation is carried out under the pressure of 4.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-60 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-60 DEG C and 4.5MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.01ppm, and CO 2be removed to 20ppm, then gas phase is cooled to-165 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 0.5MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
Embodiment 2
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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 315wt%-ZrO 230wt%/CeO 2-Al 2o 355wt%, preparation method and technique are shown in CN102463118A embodiment 5.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 253.8%, CO7.3%, CO 23.7%, CH 425%, N 26.7% and C 2-4the coke-oven gas of hydro carbons 3.5%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 275 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 5.5MPa and air speed in pressure is 7500h -1condition under, at loading type catalyst with base of molybdenum MoO 327wt%-Co 2o 3+ La 2o 38wt%/magnesium-aluminium spinel 65wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 633 DEG C work off one's feeling vent one's spleen first reclaims heat through waste heat boiler I, again after input and output material interchanger I and coke-oven gas heat exchange reach 275 DEG C, enter methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 5.5MPa and air speed is 7500h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 327wt%-Co 2o 3+ La 2o 38wt%/magnesium-aluminium spinel 65wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 536 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 255 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 5.5MPa and 7500h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 315wt%-ZrO 230wt%/CeO 2-Al 2o 355wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 311 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 40 DEG C, gas-liquid separation is carried out under the pressure of 4.0MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-55 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-55 DEG C and 4.0MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.02ppm, and CO 2be removed to 25ppm, then gas phase is cooled to-160 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 0.7MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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 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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 320wt%-CeO 2+ La 2o 330wt%/Al 2o 3-ZrO 250wt%, preparation method and technique are shown in CN102463118A embodiment 6.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 254.7%, CO6.9%, CO 23.5%, CH 425.6%, N 26.1% and C 2-4the coke-oven gas of hydro carbons 3.2%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 280 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 5.0MPa and air speed in pressure is 7000h -1condition under, at loading type catalyst with base of molybdenum MoO 310wt%-Co 2o 35wt%/Al 2o 3-ZrO 285wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 621 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 270 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 5.0MPa and air speed is 7000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 310wt%-Co 2o 35wt%/Al 2o 3-ZrO 285wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 518 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 5.0MPa and 7000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 320wt%-CeO 2+ La 2o 330wt%/Al 2o 3-ZrO 250wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 307 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 35 DEG C, gas-liquid separation is carried out under the pressure of 3.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-50 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-50 DEG C and 3.5MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.03ppm, and CO 2be removed to 34ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 0.8MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 325wt%-CeO 2+ La 2o 310wt%/γ-Al 2o 365wt%, preparation method and technique are shown in CN102463118A embodiment 2.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 256.2%, CO6.4%, CO 23.4%, CH 425.1%, N 25.7% and C 2-4the coke-oven gas of hydro carbons 3.2%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 280 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 4.5MPa and air speed in pressure is 6500h -1condition under, at loading type catalyst with base of molybdenum MoO 325wt%-Co 2o 3+ ZrO 215wt%/CeO 2-Al 2o 360wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 607 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 280 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 4.5MPa and air speed is 6500h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 325wt%-Co 2o 3+ ZrO 215wt%/CeO 2-Al 2o 360wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 502 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 265 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 4.5MPa and 6500h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 325wt%-CeO 2+ La 2o 310wt%/γ-Al 2o 365wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 304 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 30 DEG C, gas-liquid separation is carried out under the pressure of 3.0MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-45 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-45 DEG C and 3.0MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.04ppm, and CO 2be removed to 36ppm, then gas phase is cooled to-150 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 0.9MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 330wt%-ZrO 2+ La 2o 35wt%/γ-Al 2o 365wt%, preparation method and technique are shown in CN102463118A embodiment 3.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 257.4%, CO6.2%, CO 23.0%, CH 424.7%, N 25.5% and C 2-4the coke-oven gas of hydro carbons 3.2%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 285 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 4.0MPa and air speed in pressure is 6000h -1condition under, at loading type catalyst with base of molybdenum MoO 330wt%-Co 2o 3+ Fe 2o 3+ NiO20wt%/CeO 2-Al 2o 350wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 584 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 285 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 4.0MPa and air speed is 6000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 330wt%-Co 2o 3+ Fe 2o 3+ NiO20wt%/CeO 2-Al 2o 350wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 481 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 270 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 4.0MPa and 6000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 330wt%-ZrO 2+ La 2o 35wt%/γ-Al 2o 365wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 301 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 25 DEG C, gas-liquid separation is carried out under the pressure of 2.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-40 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-40 DEG C and 2.5MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.05ppm, and CO 2be removed to 37ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 1.0MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
Embodiment 6
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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 325wt%-La 2o 35wt%/ZrO 270wt%, preparation method and technique are shown in CN102463118A embodiment 3.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 257.8%, CO5.7%, CO 22.6%, CH 424.2%, N 25.8% and C 2-4the coke-oven gas of hydro carbons 3.9%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 290 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 3.5MPa and air speed in pressure is 5500h -1condition under, at loading type catalyst with base of molybdenum MoO 320wt%-Co 2o 3+ Ce 2o 312wt%/γ-Al 2o 368wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 569 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 290 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 3.5MPa and air speed is 5500h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 320wt%-Co 2o 3+ Ce 2o 312wt%/γ-Al 2o 368wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 457 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 3.5MPa and 5500h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 325wt%-La 2o 35wt%/ZrO 270wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 304 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 30 DEG C, gas-liquid separation is carried out under the pressure of 2.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-35 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-35 DEG C and 2.5MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.07ppm, and CO 2be removed to 39ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 1.1MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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 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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 320wt%-CeO 25wt%/ZrO 275wt%, preparation method and technique are shown in CN103480362A embodiment 14.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 260%, CO5.3%, CO 22.7%, CH 423.7%, N 24.6% and C 2-4the coke-oven gas of hydro carbons 3.7%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 295 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 3.0MPa and air speed in pressure is 5000h -1condition under, at loading type catalyst with base of molybdenum MoO 323wt%-Co 2o 3+ ZrO 2+ CeO 27wt%/γ-Al 2o 370wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 548 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 295 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 3.0MPa and air speed is 5000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 323wt%-Co 2o 3+ ZrO 2+ CeO 27wt%/γ-Al 2o 370wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 427 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 3.0MPa and 5000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 320wt%-CeO 25wt%/ZrO 275wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 297 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 35 DEG C, gas-liquid separation is carried out under the pressure of 2.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-30 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-30 DEG C and 2.5MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.08ppm, and CO 2be removed to 42ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 1.2MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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 313wt%-Co 2o 3+ ZrO 2+ 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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 315wt%-CeO 25wt%/ZrO 280wt%, preparation method and technique are shown in CN103480362A embodiment 8.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 260%, CO6.0%, CO 21.5%, CH 423.3%, N 26.6% and C 2-4the coke-oven gas of hydro carbons 2.6%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 295 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 2.5MPa and air speed in pressure is 4000h -1condition under, at loading type catalyst with base of molybdenum MoO 313wt%-Co 2o 3+ ZrO 2+ CeO 214.5wt%/γ-Al 2o 372.5wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 536 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 300 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 2.5MPa and air speed is 4000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 313wt%-Co 2o 3+ ZrO 2+ CeO 214.5wt%/γ-Al 2o 372.5wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 408 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 2.5MPa and 4000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 315wt%-CeO 25wt%/ZrO 280wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 290 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 30 DEG C, gas-liquid separation is carried out under the pressure of 2.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-25 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-25 DEG C and 2.5MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.09ppm, and CO 2be removed to 45ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 1.0MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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 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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 310wt%-La 2o 35wt%/Al 2o 3-ZrO 285wt%, preparation method and technique are shown in CN103480362A embodiment 7.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 260%, CO5.0%, CO 24.0%, CH 423.0%, N 26.0% and C 2-4the coke-oven gas of hydro carbons 2.0%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 270 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 2.0MPa and air speed in pressure is 3000h -1condition under, at loading type catalyst with base of molybdenum MoO 335wt%-Co 2o 3+ KO 22wt%/ZrO 263wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 508 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 270 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 2.0MPa and air speed is 3000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 335wt%-Co 2o 3+ KO 22wt%/ZrO 263wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 359 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 2.0MPa and 3000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 310wt%-La 2o 35wt%/Al 2o 3-ZrO 285wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 290 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 30 DEG C, gas-liquid separation is carried out under the pressure of 2.5MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-20 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-20 DEG C and 2.0MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.09ppm, and CO 2be removed to 48ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 0.9MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
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; The catalyst for methanation in presence of sulfur quality group that methanation in presence of sulfur reactor III uses becomes MoO 320wt%-La 2o 310wt%/Al 2o 3-ZrO 270wt%, preparation method and technique are shown in CN103480362A embodiment 8.Adopt above-mentioned catalyzer, its concrete technological process and condition as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of 259.6%, CO5.0%, CO 23.0%, CH 425.8%, N 23.0% and C 2-4the coke-oven gas of hydro carbons 3.6%, first work off one's feeling vent one's spleen through input and output material interchanger II and methanation in presence of sulfur reactor II and carry out heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 270 DEG C through input and output material interchanger I and methanation in presence of sulfur again, enter methanation in presence of sulfur reactor I from top, coke(oven)gas is 3.0MPa and air speed in pressure is 2000h -1condition under, at loading type catalyst with base of molybdenum MoO 313wt%-ZrO 214.5wt%/γ-Al 2o 372.5wt% carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction, temperature is that 500 DEG C work off one's feeling vent one's spleen first is reclaimed heat through waste heat boiler I, then after input and output material interchanger I and coke-oven gas heat exchange reach 270 DEG C, entered methanation in presence of sulfur reactor II;
(2) reaction gas come from methanation in presence of sulfur reactor I is after heat recuperation and heat exchange, and entering methanation in presence of sulfur reactor II from top, be 3.0MPa and air speed is 2000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 313wt%-ZrO 214.5wt%/γ-Al 2o 372.5wt% carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, temperature is that the reaction gas of 350 DEG C first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter knockout drum I after being cooled by air cooler I and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top is discharged and work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C through input and output material interchanger III and methanation in presence of sulfur reactor III, enter methanation in presence of sulfur reactor III from top;
(3) reaction gas is in 2.5MPa and 4000h -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 320wt%-La 2o 310wt%/Al 2o 3-ZrO 270wt% carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur, temperature be after the reaction of 295 DEG C gas by waste heat boiler III reclaim heat and with inlet gas heat exchange after, knockout drum II is entered respectively after air-cooler II and water cooler are cooled to 30 DEG C, gas-liquid separation is carried out under the pressure of 2.0MPa, the bottom of process condensate water self-separation tank II is discharged, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device with after deep cooler I is cooled to-40 DEG C, enter rectisol system from the expellant gas heat exchange of knockout drum III top, be under the condition of-40 DEG C and 2.0MPa in temperature, H is removed by low-temperature rectisol is disposable 2s, CO 2, C 2-4the naphthalene of hydro carbons and remnants, the impurity such as benzene and tar, wherein H 2s is removed to 0.1ppm, and CO 2be removed to 50ppm, then gas phase is cooled to-155 DEG C further through deep cooler II, carries out gas-liquid separation, gas phase H in knockout drum III under the pressure of 0.9MPa 2, N 2discharge from top with trace amounts of CO, and obtain liquefied natural gas product bottom knockout drum III.The gas product composition for details see attached table 1 synthesized under the reaction conditions of the present embodiment.
Subordinate list 1
Note: in "-" representative products, this substances content is lower than 100ppm.

Claims (15)

1. coke(oven)gas methanation in presence of sulfur prepares a method for natural gas liquids, it is characterized in that comprising the steps:
(1) coke-oven gas after oil removing, deamination, de-benzene and de-naphthalene is first worked off one's feeling vent one's spleen by input and output material interchanger II and methanation in presence of sulfur reactor II and is carried out heat exchange, again after input and output material interchanger I and methanator I works off one's feeling vent one's spleen heat exchange, methanation in presence of sulfur reactor I is entered from top, coke-oven gas carries out first step methanation in presence of sulfur and organosulfur hydrogenation reaction on loading type molybdenum base catalyst for methanation in presence of sulfur, work off one's feeling vent one's spleen and first reclaim heat through waste heat boiler I, again after inlet outlet heat exchanger I and coke-oven gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) reaction gas from methanation in presence of sulfur reactor I is after heat recuperation, methanation in presence of sulfur reactor II is entered from top, loading type molybdenum base sulfur resistant catalyst carries out the hydrogenation reaction of second stage methanation in presence of sulfur and organosulfur, reaction gas first reclaims heat by waste heat boiler II, again through input and output material interchanger II and coke-oven gas heat exchange, then enter in knockout drum I after air cooler I cools and carry out gas-liquid separation, discharge bottom phlegma self-separation tank I, and gas phase self-separation tank top discharge and after input and output material interchanger III and methanation in presence of sulfur reactor III works off one's feeling vent one's spleen heat exchange, methanation in presence of sulfur reactor III is entered from top,
(3) inlet gas carries out the hydrogenation reaction of third stage methanation in presence of sulfur and organosulfur on loading type molybdenum base sulfur resistant catalyst, reacted gas reclaims heat by waste heat boiler III, and through inlet outlet heat exchanger III and inlet gas heat exchange, then after air-cooler II and water cooler cooling, knockout drum II is entered respectively, discharge bottom water of condensation self-separation tank II, and after the discharge of gas phase self-separation tank II top, first through precool heat exchanger device and from the expellant gas heat exchange of knockout drum III top, and after deep cooler I cools, enter rectisol system and remove sulphur, carbonic acid gas, C 2-4the impurity such as hydro carbons, through the gas phase of low-temperature rectisol after deep cooler II cools further, enter knockout drum III, gas phase is discharged from top, and liquid phase is liquefied natural gas product.
2. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, it is characterized in that the described coke-oven gas through de-oiling, deamination, de-benzene and de-naphthalene consists of H 250 ~ 60%, CO5% ~ 8%, CO 21.5 ~ 4%, CH 423% ~ 27%, N 23 ~ 7%, C 2-4hydro carbons 2 ~ 4%.
3. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, it is characterized in that the loading type molybdenum base catalyst for methanation in presence of sulfur quality group that described methanation in presence of sulfur reactor I or II uses becomes: active ingredient MoO 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 or K; 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 coke(oven)gas methanation in presence of sulfur as claimed in claim 3 prepares the method for natural gas liquids, it is characterized in that described auxiliary agent is Co, La, Ce or Fe.
5. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 3 prepares the method for natural gas liquids, 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 coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, it is characterized in that the quality group of the loading type molybdenum base catalyst for methanation in presence of sulfur that described methanation in presence of sulfur reactor III uses becomes: active ingredient MoO 310 ~ 30wt%, auxiliary agent oxide compound 5 ~ 30wt%, carrier 50 ~ 85wt%; Auxiliary agent be La, Zr or Ce one or more; Carrier is γ-Al 2o 3, Al 2o 3-ZrO 2complex carrier, ZrO 2or CeO 2-Al 2o 3complex carrier.
7. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, it is characterized in that described methanation in presence of sulfur reactor I, methanation in presence of sulfur reactor II or methanation in presence of sulfur reactor III are insulation fix bed reactor.
8. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, the inlet gas temperature that it is characterized in that described methanation in presence of sulfur reactor I is 270 ~ 300 DEG C, temperature out is 500 ~ 650 DEG C, and reaction pressure is 2 ~ 6MPa, and reaction velocity is 2000 ~ 8000h -1.
9. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, the inlet gas temperature that it is characterized in that described methanation in presence of sulfur reactor II is 270 ~ 300 DEG C, temperature out is 350 ~ 550 DEG C, and reaction pressure is 2 ~ 6MPa, and reaction velocity is 2000 ~ 8000h -1.
10. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepares the method for natural gas liquids, the inlet gas temperature that it is characterized in that described methanation in presence of sulfur reactor III is 250 ~ 270 DEG C, temperature out is 290 ~ 320 DEG C, reaction pressure is 2 ~ 6MPa, and reaction velocity is 2000 ~ 8000h -1.
11. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepare the method for natural gas liquids, it is characterized in that described from methanation in presence of sulfur reactor III out and reclaim after heat and water cooler cooling through waste heat boiler III, gas temperature is down to 25-45 DEG C, be 2.0 ~ 4.5MPa at pressure, in knockout drum II, isolate process condensate water.
12. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepare the method for natural gas liquids, it is characterized in that the described isolated gas phase of knockout drum II is after precool heat exchanger device and deep cooler I are cooled to-30 ~-60 DEG C, enter rectisol system, and under the condition of-30 ~-60 DEG C and 2.0 ~ 4.5MPa, disposablely remove H 2s, CO 2and C 2-4hydro carbons and remaining naphthalene, benzene and tar.
13. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 12 prepare the method for natural gas liquids, it is characterized in that H in the gas after low-temperature rectisol 2s is removed to 0.01 ~ 0.1ppm, CO 2be removed to 20 ~ 50ppm.
14. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepare the method for natural gas liquids, to it is characterized in that and gas phase is cooled to-150 ~-165 DEG C further by deep cooler II after low-temperature rectisol, in knockout drum III, carry out gas-liquid separation in 0.5 ~ 1.2MPa.
15. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 prepare the method for natural gas liquids, it is characterized in that described coke-oven gas consists of through above-mentioned technique and reacted natural gas liquids: CH 497 ~ 99%, N 20.3 ~ 1.0%, C 2-3hydro carbons 0.5 ~ 2.0%, CO 2≤ 100ppm, H 2≤ 100ppm, CO≤10ppm.
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