CN104164263A - Method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas - Google Patents

Method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas Download PDF

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CN104164263A
CN104164263A CN201410407692.1A CN201410407692A CN104164263A CN 104164263 A CN104164263 A CN 104164263A CN 201410407692 A CN201410407692 A CN 201410407692A CN 104164263 A CN104164263 A CN 104164263A
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gas
methanation
sulfur
coke
oven
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CN104164263B (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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Shanxi Institute of Coal Chemistry of CAS
Sedin Engineering Co Ltd
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Shanxi Institute of Coal Chemistry of CAS
Sedin Engineering Co Ltd
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Abstract

The invention provides a method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas. The method is characterized by subjecting the coke-oven gas to direct three-stage methanation reactions on a supported molybdenum-based sulphur-tolerant methanation catalyst after removing the impurities such as oil, naphthalene, benzene and the like from the coke-oven gas, then removing the impurities such as sulphur, CO2, C2-4 hydrocarbons and the like once through rectisol, and finally separating N2, H2 and the like through one-time subzero liquefaction, thus obtaining the LNG with methane content higher than 97%. The method has the advantages of simple process flow, small equipment investment, low comprehensive energy consumption and excellent natural gas products.

Description

A kind of coke(oven)gas methanation in presence of sulfur is prepared the method for natural gas liquids
Technical field
The invention belongs to a kind of method of preparing natural gas liquids, be specifically related to a kind of method that coke(oven)gas methanation in presence of sulfur is prepared 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 producing 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 70% left and right heats and domestic gas for coke oven, and remaining nearly 57,000,000,000 m 3coke-oven gas is not utilized, and has caused 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 Sweet natural gas insufficiency of supply-demand increases gradually, and then has limited the stable and rapid development of Chinese national economy.Synthesizing natural gas from coke oven gas, especially synthetic LNG Technology has been opened up the efficient new way of utilizing of coke-oven gas, not only can alleviate the situation of domestic Sweet natural gas shortage, and solved coke-oven gas and discharge the environmental pollution and the wasting of resources problem that cause, have great importance to realizing the recycle of china natural resources and economic Sustainable development.
At present, the technology of the synthetic natural gas liquids of coke-oven gas mainly comprises two kinds of Physical and chemical methods, and wherein the operational path of Physical is: coke-oven gas → purification → low temperature separation process → natural gas liquids; And chemical method has increased methanation in Physical, be specially: coke-oven gas → purification → methanation → low temperature separation process → natural gas liquids, although chemical method is prepared the operational path of natural gas liquids than Physical complexity, it is by most CO, CO in coke(oven)gas 2and H 2transform for CH 4gas, makes the yield of methane be increased to 35% left and right by 25%, and energy utilization rate is higher, becomes the optimization technique of the synthetic natural gas liquids project of current coke-oven gas.But because the composition of coke-oven gas is very complicated, in gas, remove CH 4, CO, CO 2and H 2outside available gas composition, also contain the etching apparatuses such as tar, naphthalene, benzene, ammonia and sulphur and affect the impurity of Ni methylmethane catalyzer, in the gas after methanation simultaneously, still there are a large amount of N 2, H 2and C 2-4hydro carbons hydro carbons etc. affects the component of natural gas liquids quality.Because poison resistance, the especially resistance to sulphur ability of Ni methylmethane catalyzer that prior art adopts is poor, sulphur content in requirement methanation gas must be lower than 0.1ppm, but in coke(oven)gas, contain and be difficult in a large number the organosulfur that removes, need multistage hydrogenation organosulfur is converted into the H easily removing 2s, and just can make sulphur content reach above-mentioned requirements by the complicated technology of Multistage desulfuration; Simultaneously in order to isolate the N in gas after methanation 2, H 2and C 2-4the components such as hydro carbons hydro carbons, need to adopt multistage technique cooling and multistage liquefaction just can make the liquefied natural gas product that meets national requirements, and then cause the low temperature separation process operation after cleaning section and the methanation before methanation extremely complicated, its operation length accounts for the more than 3/4 of whole flow process (idiographic flow is shown in upper figure), has greatly increased facility investment and the energy consumption of the synthetic natural gas liquids of coke-oven gas.Therefore, how optimizing coke-oven gas liquefaction prepares the technical process of Sweet natural gas, reduces energy consumption and facility investment and become the study hotspot of numerous mechanisms.
Patent CN101597527A discloses a kind of method of utilizing coke-oven gas to produce Sweet natural gas, by fill into carbon source in coke(oven)gas, makes synthetic gas meet (H 2-3CO)/CO 2the stoichiometric ratio of ≈ 4, has then made Sweet natural gas by smart desulfurization and methanation, although this invention has further improved the productive rate of Sweet natural gas, and the purification process before itself and 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 compression, through preliminary cleaning, desulfurization, after two sections of methanation reactions and pressure-variable adsorption or membrane sepn, must meet the Sweet natural gas of Sweet natural gas GB (GB17820-1999), being introduced in of membrane sepn and pressure-variable adsorption improved the effect separating to a certain extent, 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, in 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 of 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 more than 90% gas product of methane concentration, but this invention also adopts the complicated technology of multistage hydrogenation and Multistage desulfuration, do not provide the effective ways of simplifying sulfur removal technology.Although above-mentioned patent has improved Sweet natural gas yield and separating effect to a certain extent by Optimization Technology, but it does not fundamentally solve the large problem of technical process complexity, energy consumption and facility investment of synthesizing natural gas from coke oven gas, especially natural gas liquids.
Catalyst for methanation in presence of sulfur, mainly taking Mo as active metal, adds Co, La, Zr, Ce and Fe etc. as auxiliary agent simultaneously, and active ingredient and auxiliary agent are carried on Al with the method for dipping, kneading or collosol and gel by said components 2o 3, ZrO 2and SiO 2on 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 just carrying out methanation reaction to synthetic gas desulfurization, for methanation synthetic natural gas technology provides new thinking.The inventor is by a large amount of experiment discoveries, 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 catalyst component similar to sulfur-resisting transformation, also shows the catalytic performance of extremely strong carbon monoxide water-gas shift.Consider the problem existing in gas employing methanation of coke oven synthetic natural gas technique, if the coke(oven)gas before desulfurization is first carried out under the effect of above-mentioned sulfur resistant catalyst to methanation reaction, and then carry out desulfurization, with regard to having avoided problem in existing technique, the problem includes: the multistage hydrogenation problem of organosulfur, greatly 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 a kind of technical process is simple, facility investment is few, comprehensive energy consumption is low and gas product is good coke(oven)gas methanation in presence of sulfur and prepare the method for natural gas liquids.
The present invention be by coke-oven gas after the impurity such as oil removing, de-naphthalene and de-benzene, on loading type molybdenum base catalyst for methanation in presence of sulfur, directly carry out three sections of methanation reactions, then once remove sulphur, CO through low-temperature rectisol 2and C 2-4the impurity such as hydro carbons, finally isolate N 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 catalyzer preparation 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 that is suitable for gas employing methanation of coke oven synthetic natural gas are filtered out, and combination coal preparing natural gas Engineering Design experience for many years, propose through oil removing, coke-oven gas after the impurity such as de-naphthalene and de-benzene directly carries out three grades of methanation in presence of sulfur reactions, not only make methane content greatly improve, and 99% above organosulfur is converted into H 2s gas, after cooling de-watering, gas is once removed to H by low-temperature rectisol 2s (≤0.1ppm), CO 2and C 4above heavy hydrocarbon, finally by the disposable N that isolates of cryogenic liquefying 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 is prepared the technique of natural gas liquids, in methanation in presence of sulfur, makes in gas 99% organosulfur be converted into H by hydrogenation and hydrolysis 2s, is then removed to sulphur below 0.1ppm through low-temperature rectisol, has avoided needing in prior art the complicated technology of 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 obtain liquefied natural gas product by a cryogenic liquefying, avoid needing in existing technique the Complicated Flow of multistep deep cooling, greatly simplified coke-oven gas methanation in presence of sulfur synthetic natural gas technical process, reduced facility investment and energy consumption, there is larger industrial prospect.
The invention discloses a kind of coke(oven)gas methanation in presence of sulfur and prepare the method for 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 and is carried out heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, work off one's feeling vent one's spleen after heat exchange through input and output material interchanger I and methanator I again, enter methanation in presence of sulfur reactor I 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, after inlet outlet heat exchanger I and coke-oven gas heat exchange, remove methanation in presence of sulfur reactor II again;
(2) reaction gas coming from methanation in presence of sulfur reactor I is after heat recuperation, enter methanation in presence of sulfur reactor II from top, on loading type molybdenum base sulfur resistant catalyst, carry 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 carry out entering after cooling through air cooler I and in knockout drum I, carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and gas phase self-separation tank top is discharged and is worked off one's feeling vent one's spleen after heat exchange 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) inlet gas is carried 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 enter knockout drum II through air-cooler II and water cooler after cooling respectively, water of condensation self-separation tank II discharges bottom, 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 is cooling, enter rectisol system and remove sulphur, carbonic acid gas, C 2-4the impurity such as hydro carbons, after deep cooler II is further cooling, enter knockout drum III through the gas phase of low-temperature rectisol, and gas phase is discharged from top, and liquid phase is liquefied natural gas product.
Coke-oven gas through de-oiling, deamination, de-benzene and de-naphthalene as above 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 as above and II use 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 preferred 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 through waste heat boiler III reclaim heat and water cooler cooling after, gas temperature is down to 25-45 DEG C, is 2.0～4.5MPa at pressure, isolates process condensate water in knockout drum II; The isolated gas phase of knockout drum II is cooled to after-30～-60 DEG C through precool heat exchanger device and deep cooler I, enters rectisol system, and under the condition of-30～-60 DEG C and 2.0～4.5MPa, the disposable H that removes 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 further cooled to-150～-165 DEG C 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, by three grades of molybdenum base methanation in presence of sulfur reaction members are set, not only makes more than 97% CO and CO in coke-oven gas 2be converted into methane, and make more than 99% organosulfur in methanation, be converted into the H easily removing 2s gas, then directly remove by low-temperature rectisol, avoid needing in prior art the problem of multistage hydrogenation and Multistage desulfuration complex process, made the purification process of coke-oven gas reduce by approximately 1/3 left and right, greatly saved 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, makes sublevel low temperature separation process become two-stage from three grades, saved 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, making the gas processing amount of desulfurization process is only 70% left and right before methanation, greatly reduces 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 advantages of 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.
Brief description of the drawings
Fig. 1 is the process flow sheet of the synthetic natural gas liquids of prior art coke-oven gas.
Fig. 2 is the process flow sheet that coke(oven)gas methanation in presence of sulfur of the present invention is prepared natural gas liquids.
As shown in the figure, the 1st, methanation in presence of sulfur reactor I, the 2nd, methanation in presence of sulfur reactor II, the 3rd, methanation in presence of sulfur reactor III, the 4th, rectisol system, the 5th, knockout drum I, the 6th, knockout drum II, the 7th, knockout drum III, the 8th, air-cooler I, the 9th, air-cooler II, the 10th, waste heat boiler I, the 11st, waste heat boiler II, the 12nd, waste heat boiler III, the 13rd, input and output material interchanger I, the 14th, input and output material interchanger II, the 15th, input and output material interchanger III, the 16th, water cooler, the 17th, precool heat exchanger device, the 18th, deep cooler I, the 19th, deep cooler II.
Embodiment
The proposition of technology and condition of the present invention is all to propose on to the basis of numerous Mo base catalyst for methanation in presence of sulfur screenings, in implementation process, commercial catalysts the present invention can provide catalyzer model if, 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 to scope of the present invention only limits to above-described embodiment.
Embodiment 1
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyzer using 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 270 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 6MPa and air speed are 8000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 315wt%-Co 2o 3+ La 2o 3on 10wt%/magnesium-aluminium spinel 75wt%, carry 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 reclaimed heat through waste heat boiler I, reach after 280 DEG C through input and output material interchanger I and coke-oven gas heat exchange again, enter methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 6.0MPa and air speed are 8000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 315wt%-Co 2o 3+ La 2o 3on 10wt%/magnesium-aluminium spinel 75wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 250 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 3on 60wt%, carry 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, after being cooled to 45 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 4.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-60 DEG C, be under the condition of-60 DEG C and 4.5MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.01ppm, and CO 2be removed to 20ppm, then gas phase is further cooled to-165 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 3mode by dipping is carried on carrier magnesium-aluminium spinel, and 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 275 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 5.5MPa and air speed are 7500h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 327wt%-Co 2o 3+ La 2o 3on 8wt%/magnesium-aluminium spinel 65wt%, carry 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 reclaimed heat through waste heat boiler I, reach after 275 DEG C through input and output material interchanger I and coke-oven gas heat exchange again, enter methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 5.5MPa and air speed are 7500h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 327wt%-Co 2o 3+ La 2o 3on 8wt%/magnesium-aluminium spinel 65wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 255 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 3on 55wt%, carry 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, after being cooled to 40 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 4.0MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-55 DEG C, be under the condition of-55 DEG C and 4.0MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.02ppm, and CO 2be removed to 25ppm, then gas phase is further cooled to-160 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 using 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 3be carried on carrier A l by the mode of co-precipitation 2o 3-ZrO 2upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 280 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 5.0MPa and air speed are 7000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 310wt%-Co 2o 35wt%/Al 2o 3-ZrO 2on 85wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 270 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 5.0MPa and air speed are 7000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 310wt%-Co 2o 35wt%/Al 2o 3-ZrO 2on 85wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 260 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 2on 50wt%, carry 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, after being cooled to 35 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 3.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-50 DEG C, be under the condition of-50 DEG C and 3.5MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.03ppm, and CO 2be removed to 34ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 using 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 2mode by dipping is carried on support C eO 2-Al 2o 3upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 280 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 4.5MPa and air speed are 6500h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 325wt%-Co 2o 3+ ZrO 215wt%/CeO 2-Al 2o 3on 60wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 280 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 4.5MPa and air speed are 6500h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 325wt%-Co 2o 3+ ZrO 215wt%/CeO 2-Al 2o 3on 60wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 265 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 3on 65wt%, carry 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, after being cooled to 30 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 3.0MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-45 DEG C, be under the condition of-45 DEG C and 3.0MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.04ppm, and CO 2be removed to 36ppm, then gas phase is further cooled to-150 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 using 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 3upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 285 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 4.0MPa and air speed are 6000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 330wt%-Co 2o 3+ Fe 2o 3+ NiO20wt%/CeO 2-Al 2o 3on 50wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 285 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 4.0MPa and air speed are 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 3on 50wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 270 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 3on 65wt%, carry 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, after being cooled to 25 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 2.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-40 DEG C, be under the condition of-40 DEG C and 2.5MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.05ppm, and CO 2be removed to 37ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 using 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 3be carried on carrier γ-Al by the mode of collosol and gel 2o 3upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 290 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 3.5MPa and air speed are 5500h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 320wt%-Co 2o 3+ Ce 2o 312wt%/γ-Al 2o 3on 68wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 290 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 3.5MPa and air speed are 5500h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 320wt%-Co 2o 3+ Ce 2o 312wt%/γ-Al 2o 3on 68wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 260 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 2on 70wt%, carry 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, after being cooled to 30 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 2.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-35 DEG C, be under the condition of-35 DEG C and 2.5MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.07ppm, and CO 2be removed to 39ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 2be carried on carrier γ-Al by the mode of co-precipitation 2o 3upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 295 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 3.0MPa and air speed are 5000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 323wt%-Co 2o 3+ ZrO 2+ CeO 27wt%/γ-Al 2o 3on 70wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 295 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 3.0MPa and air speed are 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 3on 70wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 260 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 2on 75wt%, carry 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, after being cooled to 35 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 2.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-30 DEG C, be under the condition of-30 DEG C and 2.5MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.08ppm, and CO 2be removed to 42ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 2be carried on carrier γ-Al by the mode of co-precipitation 2o 3upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 295 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 2.5MPa and air speed are 4000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 313wt%-Co 2o 3+ ZrO 2+ CeO 214.5wt%/γ-Al 2o 3on 72.5wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 300 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 2.5MPa and air speed are 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 3on 72.5wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 260 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 2on 80wt%, carry 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, after being cooled to 30 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 2.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-25 DEG C, be under the condition of-25 DEG C and 2.5MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.09ppm, and CO 2be removed to 45ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 2mode by dipping is carried on carrier ZrO 2upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 270 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 2.0MPa and air speed are 3000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 335wt%-Co 2o 3+ KO 22wt%/ZrO 2on 63wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 270 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 2.0MPa and air speed are 3000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 335wt%-Co 2o 3+ KO 22wt%/ZrO 2on 63wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 260 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 2on 85wt%, carry 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, after being cooled to 30 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 2.5MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-20 DEG C, be under the condition of-20 DEG C and 2.0MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.09ppm, and CO 2be removed to 48ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 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 2mode by co-precipitation is carried on γ-Al 2o 3upper, 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, technological process and condition that it is concrete are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, consist of H 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 and carry out heat exchange through input and output material interchanger II and methanation in presence of sulfur reactor II, reach after 270 DEG C through the heat exchange of working off one's feeling vent one's spleen of 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 that 3.0MPa and air speed are 2000h in pressure -1condition under, at loading type catalyst with base of molybdenum MoO 313wt%-ZrO 214.5wt%/γ-Al 2o 3on 72.5wt%, carry 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 reclaimed heat through waste heat boiler I, then reaches after 270 DEG C through input and output material interchanger I and coke-oven gas heat exchange, enters methanation in presence of sulfur reactor II;
(2) reaction gas coming from methanation in presence of sulfur reactor I, after heat recuperation and heat exchange, enters methanation in presence of sulfur reactor II from top, be that 3.0MPa and air speed are 2000h in pressure -1condition under, at loading type molybdenum base sulfur resistant catalyst MoO 313wt%-ZrO 214.5wt%/γ-Al 2o 3on 72.5wt%, carry 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 after cooling by air cooler I, enter knockout drum I and carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and discharge gas phase self-separation tank top and reach after 260 DEG C through input and output material interchanger III and the methanation in presence of sulfur reactor III heat exchange of working off one's feeling vent one's spleen, 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 2on 70wt%, carry 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, after being cooled to 30 DEG C, air-cooler II and water cooler enter knockout drum II respectively, under the pressure of 2.0MPa, carry out gas-liquid separation, discharge the bottom of process condensate water self-separation tank II, and after the discharge of gas phase self-separation tank II top, elder generation is through precool heat exchanger device and enter rectisol system from the expellant gas heat exchange of knockout drum III top and after deep cooler I is cooled to-40 DEG C, be under the condition of-40 DEG C and 2.0MPa in temperature, by the disposable H that removes of low-temperature rectisol 2s, CO 2, C 2-4the impurity such as naphthalene, benzene and the tar of hydro carbons and remnants, wherein H 2s is removed to 0.1ppm, and CO 2be removed to 50ppm, then gas phase is further cooled to-155 DEG C 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 knockout drum III bottom obtains liquefied natural gas product.Synthetic gas product composition for details see attached table 1 under the reaction conditions of the present embodiment.
Subordinate list 1
Note: in "-" representative products, this substances content is lower than 100ppm.

Claims (16)

1. coke(oven)gas methanation in presence of sulfur is prepared 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 and is carried out heat exchange by input and output material interchanger II and methanation in presence of sulfur reactor II, work off one's feeling vent one's spleen after heat exchange through input and output material interchanger I and methanator I again, enter methanation in presence of sulfur reactor I 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, after inlet outlet heat exchanger I and coke-oven gas heat exchange, remove methanation in presence of sulfur reactor II again;
(2) reaction gas coming from methanation in presence of sulfur reactor I is after heat recuperation, enter methanation in presence of sulfur reactor II from top, on loading type molybdenum base sulfur resistant catalyst, carry 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 carry out entering after cooling through air cooler I and in knockout drum I, carry out gas-liquid separation, phlegma self-separation tank I discharges bottom, and gas phase self-separation tank top is discharged and is worked off one's feeling vent one's spleen after heat exchange 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) inlet gas is carried 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 enter knockout drum II through air-cooler II and water cooler after cooling respectively, water of condensation self-separation tank II discharges bottom, 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 is cooling, enter rectisol system and remove sulphur, carbonic acid gas, C 2-4the impurity such as hydro carbons, after deep cooler II is further cooling, enter knockout drum III through the gas phase of low-temperature rectisol, and 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 is prepared 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 is prepared 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 use 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 is prepared 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 is prepared 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 is prepared the method for natural gas liquids, and the quality group of the loading type molybdenum base catalyst for methanation in presence of sulfur that the methanation in presence of sulfur reactor III described in it is characterized in that 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 is prepared 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 is prepared 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 is prepared 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 is prepared 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.
The inlet gas temperature of 11. 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.
12. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 are prepared the method for natural gas liquids, it is characterized in that described from methanation in presence of sulfur reactor III out and through waste heat boiler III reclaim heat and water cooler cooling after, gas temperature is down to 25-45 DEG C, be 2.0～4.5MPa at pressure, in knockout drum II, isolate process condensate water.
13. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 are prepared the method for natural gas liquids, it is characterized in that the described isolated gas phase of knockout drum II is cooled to after-30～-60 DEG C through precool heat exchanger device and deep cooler I, enter rectisol system, and under the condition of-30～-60 DEG C and 2.0～4.5MPa, the disposable H that removes 2s, CO 2and C 2-4hydro carbons and remaining naphthalene, benzene and tar.
14. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 13 are prepared 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.
15. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 are prepared the method for natural gas liquids, it is characterized in that and after low-temperature rectisol gas phase be further cooled to-150～-165 DEG C by deep cooler II, in knockout drum III, carry out gas-liquid separation in 0.5～1.2MPa.
16. a kind of coke(oven)gas methanation in presence of sulfur as claimed in claim 1 are prepared 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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