CN104194851B - A kind of coke-stove gas is through the technique of methanation in presence of sulfur synthetic natural gas - Google Patents
A kind of coke-stove gas is through the technique of methanation in presence of sulfur synthetic natural gas Download PDFInfo
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Abstract
A kind of coke-stove gas through the technique of methanation in presence of sulfur synthetic natural gas be by coke-stove gas after oil removing, the de-impurity such as naphthalene and de-benzene, support type molybdenio catalyst for methanation in presence of sulfur is made directly two-stage nitration methanation reaction, then after the thick desulfurization of oxidized ferrum and active-carbon finely desulfurization, carry out peace and quiet reaction by the reaction of Ni methylmethaneization, isolate N finally by cryogenic liquefying2��H2��H2O and a small amount of CO2Impurity after the methane content liquefied natural gas product up to 99%. The present invention has the advantage that technological process is simple, equipment investment is few, comprehensive energy consumption is low and gas product is excellent.
Description
Technical field
The technique that the invention belongs to a kind of synthetic natural gas, is specifically related to a kind of coke-stove gas technique through methanation in presence of sulfur synthetic natural gas.
Background technology
China is maximum in the world coke production, consumption and exported country. 2012, China's coke output reached 4.43 hundred million t, if producing 430m by producing one ton of coke3Coke-stove gas calculate, only the coke-stove gas of this year by-product is just up to 190,500,000,000 m3, wherein the coke-stove gas of about 70% is for coke oven heating and domestic gas, and remaining nearly 57,000,000,000 m3Coke-stove gas is not utilized, causes the serious wasting of resources and environmental pollution. Coal preparing natural gas is a kind of high-quality, efficient and safe clean energy resource. In recent years, along with increasing sharply of China's natural gas demand, domestic natural gas insufficiency of supply-demand is gradually increased, and then limits the stable and rapid development of Chinese national economy. Synthesizing natural gas from coke oven gas opens the new way that coke-stove gas efficiently utilizes, it is not only able to alleviate the situation of domestic natural gas shortage, and solve environmental pollution and the problem of resource waste that coke-stove gas discharge causes, have great importance with economic sustainable development to realizing recycling of china natural resources.
At present, the technology of synthesizing natural gas from coke oven gas mainly includes Physical and chemical method two kinds, and wherein the process route of Physical is: coke-stove gas �� purification �� pressure-variable adsorption/cryogenic separation �� compressed natural gas/liquefied natural gas; And chemical method adds methanation in the middle of Physical, particularly as follows: coke-stove gas �� purification �� methanation �� pressure-variable adsorption/cryogenic separation �� compressed natural gas/liquefied natural gas, although the process route that chemical method prepares natural gas is more complicated than Physical, but it is by most in oven gas CO, CO2And H2Convert for CH4Gas so that the yield of methane is increased to about 35% by 25%, and energy utilization rate is higher, becomes the optimization technique of current synthesizing natural gas from coke oven gas project. In coke-stove gas chemical method synthetic natural gas technique, the shortcoming that the Ni methylmethane catalyst owing to adopting exists not resistant to sulfur and easy carbon distribution so that the cleaning procedure of oven gas accounts for more than the 2/3 of whole flow process, idiographic flow See Figure.And sweetening process therein accounts for more than the 2/3 of whole purification technique, its basic reason is containing being difficult to the organic sulfur that removes in a large number in coke-stove gas, needs to be first H by Organic sulfur hydro-conversion2S just can be removed to below 0.1ppm, and then causes the complicated technology of multistage hydrogenation and Multistage desulfuration, significantly increases investment and the energy consumption of synthesizing natural gas from coke oven gas. Therefore, how to simplify the flow process of coal preparing natural gas, reduction energy consumption and investment and become the study hotspot of numerous mechanism.
Patent CN101597527A discloses a kind of method utilizing coke-stove gas to produce natural gas, and this invention fills into carbon source in the oven gas after thick desulfurization, makes synthesis gas meet (H2-3CO)/CO2The stoichiometric proportion of �� 4, then passes through fine de-sulfur and methanation has prepared natural gas, further increases the productivity of natural gas. The technique that patent CN101649232A discloses a kind of gas employing methanation of coke oven synthetic natural gas, this invention obtains after first passing through the ammonia in preliminary clearning elimination coke-stove gas, cyanide, aromatic hydrocarbons, tar and dust and slightly purifies oven gas, then must meet the natural gas of natural gas GB (GB17820-1999) after two-stage nitration methanation reaction and pressure-variable adsorption or membrance separation. Patent CN101391935A discloses a kind of method utilizing coke-stove gas synthesizing methane, by purifying and dedusting, compress heat exchange, add steam, the step such as three sections of methane and PSA separation of methane, obtain the gas product of methane concentration more than 90%. Although above-mentioned patent simplifies technological process to a certain extent by improving the mode of technological process and benefit carbon and improves natural gas yield, but it does not fundamentally solve synthesizing natural gas from coke oven gas and purifies technique, the problem that especially sulfur removal technology is complicated.
Catalyst for methanation in presence of sulfur, mainly with Mo for active metal, adds Co, said components is carried on Al as auxiliary agent, active component and auxiliary agent with the method for dipping, kneading or collosol and gel by La, Zr, Ce and Fe etc. simultaneously2O3��ZrO2And SiO2Deng on carrier. Owing to the catalyst for methanation in presence of sulfur after sulfuration is with MoS2For active center, it is to the sulfur content no maximum requirement in synthesis gas, therefore without synthetic gas desulfurization just can carry out methanation reaction, provides new thinking for synthesis gas methanation technology. The present inventor is found by substantial amounts of experiment, and above-mentioned catalyst not only has good catalytic production of methane performance, also has organic sulfur hydrogenation simultaneously simultaneously and generate H in methanation2The process of S, and this catalyst is owing to having and sulphur-resistant conversion 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 oven gas before desulfurization first being carried out under the effect of above-mentioned sulfur resistant catalyst methanation reaction, then desulfurization is carried out again, avoid the multistage hydrogenation problem of organic sulfur existed in existing technique, enormously simplify the purification technique of coke-stove gas, reduce investment and the energy consumption of synthesizing natural gas from coke oven gas. Catalyst for methanation in presence of sulfur not only has methanation and the performance of organic sulfur hydrogenation, and it has water-gas shift and the catalytic performance of inverse water-gas shift, the water of methanation generation and the H of coke-stove gas simultaneously2Inevitably there is inverse water gas shift reation, and be finally reached balance, cause CO and the CO in synthesis gas2It is difficult to convert completely, and then affects natural gas yield; Existing catalyst for methanation in presence of sulfur is all the conversion for synthesis gas from coal gasification and the multifunction catalyst of methanation, owing to coke-stove gas is relatively big with the composition difference of synthesis gas from coal gasification, there is many uncertainties.
Summary of the invention
It is an object of the invention to develop a kind of technological process is simple, equipment investment is few, comprehensive energy consumption is low and gas product the is excellent coke-stove gas technique through methanation in presence of sulfur synthetic natural gas.
The present invention be by coke-stove gas after oil removing, the de-impurity such as naphthalene and de-benzene, support type molybdenio catalyst for methanation in presence of sulfur is made directly two-stage nitration methanation reaction, then after the thick desulfurization of oxidized ferrum and active-carbon finely desulfurization, carry out peace and quiet reaction by the reaction of Ni methylmethaneization, isolate N finally by cryogenic liquefying2��H2��H2O and a small amount of CO2Impurity after the methane content liquefied natural gas product up to 99%.
For reaching above-mentioned purpose, inventor herein is by catalyst preparing many times, activity rating, Theoretical Calculation and software simulation, grasp coke-stove gas methanation in presence of sulfur on support type molybdenio catalyst for methanation in presence of sulfur, the reaction rule of organic sulfur hydrogenation and water-gas shift, composition and the preparation method of the Mo base sulfur resistant catalyst being suitable for gas employing methanation of coke oven synthetic natural gas are filtered out, and combine coal preparing natural gas Engineering Design experience for many years, propose through oil removing, first coke-stove gas after de-naphthalene and de-benzene carries out two-stage methanation in presence of sulfur reaction, methane content is not only made to be greatly improved, and be H by more than 99% organic sulfur conversion2S gas; Then after the thick desulfurization of oxidized ferrum and active-carbon finely desulfurization, disposable by the H in oven gas2S content is reduced to below 0.1ppm, carries out peace and quiet reaction by the reaction of Ni methylmethaneization, isolates N finally by cryogenic liquefying2��H2��H2O and a small amount of CO2Impurity after the methane content liquefied natural gas product up to more than 97%. The technique of the coke-stove gas methanation in presence of sulfur synthetic natural gas that the present invention proposes, saves the unit of the multistage hydrogenation of organic sulfur so that synthesizing natural gas from coke oven gas technique is greatly simplified; And the interpolation of Ni methylmethane chemical industry sequence, while having played Mo base sulfur resistant catalyst methanation and Organic sulfur hydro-conversion function, avoid this catalyst owing to having vapour property against the current, and the problem that the efficiency of carbon con version that causes is relatively low, further increase methanation productivity.
A kind of coke-stove gas of disclosure is through the technique of methanation in presence of sulfur synthetic natural gas, and its process route is:
(1) coke-stove gas after oil removing, deamination, de-benzene and de-naphthalene first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter from top in methanation in presence of sulfur reactor I, support type molybdenio catalyst for methanation in presence of sulfur carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, work off one's feeling vent one's spleen through waste heat boiler I reclaim heat and with coke-stove gas heat exchange after, enter methanation in presence of sulfur reactor II;
(2) from the methanation in presence of sulfur reactor I reaction gas come after heat recovery, methanation in presence of sulfur reactor II is entered from top, support type molybdenio sulfur resistant catalyst carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, work off one's feeling vent one's spleen by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and after being cooled down by air cooler I, enter knockout drum I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, working off one's feeling vent one's spleen after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange through input and output material heat exchanger III and methanator I, and after steam heater heats, enter from top in the methanator catalyst based equipped with Ni,
(3) inlet gas carries out peace and quiet methanation reaction under the effect of Ni methylmethane catalyst, work off one's feeling vent one's spleen and reclaimed heat the gas converting heat come with fine de-sulfur tower by waste heat boiler III, then after air cooler II and water cooler cool down further, enter knockout drum II, condensed fluid is discharged from the bottom of knockout drum II, and gas phase is after knockout drum II top row goes out, the gas converting heat first discharged with knockout drum IV top through methane precooler, and after deep cooler 1 cools down further, enter knockout drum III and carry out gas-liquid separation, liquid phase is discharged from bottom, and gas phase from top discharge after after deep cooler II cools down further, enter knockout drum IV, gas phase is discharged from top, and liquid phase is liquefied natural gas product, it is sent to LNG tank standby.
Coke-stove gas through removing oil, deamination, de-benzene and de-naphthalene as above consists of H250��60%, CO5%��8%, CO21.5��4%, CH423%��27%, N23��7%, C2-4Hydro carbons 2��4%.
Support type molybdenio catalyst for methanation in presence of sulfur quality group as above becomes: active component MoO310��35wt%, auxiliary agent oxide 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 ��-Al2O3��SiO2, magnesium aluminate spinel, ZrO2��CeO2-Al2O3Complex carrier or Al2O3-ZrO2Complex carrier, and preferably magnesium aluminate, CeO2-Al2O3Complex carrier or Al2O3-ZrO2Complex carrier; Active component is carried on carrier by infusion process, coprecipitation or sol-gal process, and infusion process refers to patent 102463118A or CN103495421A, and coprecipitation refers to patent CN103480362A, and sol-gal process refers to patent CN101733115A.
Methanation in presence of sulfur reactor I described above and methanation in presence of sulfur reactor II is fixed bed adiabatic reactor, methanation in presence of sulfur reactor I inlet air temperature degree is 250��280 DEG C, temperature of working off one's feeling vent one's spleen is 500��650 DEG C, and reaction pressure is 2��6MPa, and air speed is 2000��8000h-1; Methanation in presence of sulfur reactor II entrance actuator temperature is 250��280 DEG C, and temperature of working off one's feeling vent one's spleen is 350��600 DEG C, and reaction pressure is identical with methanation in presence of sulfur reactor I, reaction velocity 2000��8000h-1��
The operation temperature of coarse iron oxide desulfurizing tower as above is 25��80 DEG C, operates pressure 2��6MPa, and air speed is 500��2000h-1; Active-carbon finely desulfurizing tower as above operation temperature, pressure are identical with coarse iron oxide desulfurizing tower with air speed.
The Ni that uses in methanator as above is catalyst based for the one in a kind of wide temperature range type methanation catalyst of the MCR-2X methanation catalyst of Top's rope, Davy company CEG-LH methanation catalyst or Dalian Physical and Chemical Inst. exploitation, and wherein the catalyst of Dalian Physical and Chemical Inst. exploitation becomes in the quality group of oxide: active component NiO10��75%, auxiliary agent La2O30.1��15% and carrier Al2O3-ZrO2Surplus, auxiliary agent is lanthana or the compositions of lanthana and nickel lanthanum compound, and carrier is the compositions that aluminium oxide is formed with zirconium oxide with nickel aluminide, and its preparation process and condition refer to patent CN102029162.
Methanator I described above is insulation fix bed reactor, and the temperature of gas access device is 250��280 DEG C, outlet temperature 300��400 DEG C, and reaction pressure is 2��6MPa, and reaction velocity is 2000��8000h-1��
As above from methanator I out and after recovered heat and water cooler cooling, gas is 2.0��4.5MPa at pressure, and temperature is 25-45 DEG C, isolates the solidifying water of technique, butane and a small amount of propane in knockout drum II;After the pre-cooled device of gas phase of knockout drum II and deep cooler I are cooled to-70��-85 DEG C, in knockout drum III, carry out gas-liquid separation in 2.0��4.5MPa, containing carbon dioxide, propane, a small amount of ethane and sulfide in isolated liquid phase; And gas phase is cooled to-160��-175 DEG C by deep cooler II further, cooled gas-liquid mixture carries out gas-liquid separation in 2.0��4.5MPa in knockout drum IV, isolates CO, H2And N2Deng gas, and liquid phase is liquefied natural gas (LNG) product.
The volume of the coke-stove gas as above synthesis gas after above-mentioned technique and condition consists of: CH497��98%, N20.3��1.0%, C2-3Hydro carbons 1.0��2.0%, CO2�� 100ppm, H2�� 100ppm, CO��10ppm.
Compared with prior art, the present invention has substantive distinguishing features to the present invention and marked improvement is in that:
(1) present invention is by arranging two-stage molybdenio methanation in presence of sulfur reaction member, not only makes CO and the CO in coke-stove gas2It is converted into methane, and makes the H that organic sulfur conversion is easily elimination of more than 99%2S gas, then pass through two-step desulfurization and the sulfur content in oven gas is removed to below 0.1ppm, thus saving independent hydrogenation unit, overcome the problem that the desulfurization operations of existing gas employing methanation of coke oven synthetic natural gas technique existence is loaded down with trivial details, the purification technique making coke-stove gas reduces about about 1/3, is greatly saved equipment investment and energy consumption.
(2) present invention is additionally arranged the catalyst based methanation unit of Ni after methanation in presence of sulfur and desulfurization, the unconverted carbon making the water-gas shift owing to catalyst for methanation in presence of sulfur has and cause converts completely, while having given play to methanation in presence of sulfur catalyst with base of molybdenum advantage, further increase methane yield, improve the utilization rate of coke-stove gas.
(3) after desulfurization unit is arranged at methanation in presence of sulfur by the present invention, owing to methanation is the reaction of volume-diminished so that the gas treatment amount of desulfurization process is only before methanation about 70%, greatly reduces equipment investment and the energy consumption of desulfurization process.
Therefore, a kind of coke-stove gas methanation in presence of sulfur synthetic natural gas technique disclosed by the invention is compared with the prior art, there is the advantage that technological process is simple, equipment investment is few and energy consumption is low, meet the policy of energy-saving and emission-reduction and sustainable development, there is huge industrialization potential quality and profound significance.
Accompanying drawing explanation
Fig. 1 is the process chart of prior art synthesizing natural gas from coke oven gas.
Fig. 2 is the coke-stove gas process chart through methanation in presence of sulfur synthetic natural gas.
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 methanator, 4 is knockout drum I, 5 coarse iron oxide desulfurizing towers, 6 is active-carbon finely desulfurizing tower, 7 is knockout drum II, 8 is knockout drum III, 9 is knockout drum IV, 10 is air cooler I, 11 is air cooler II, 12 is waste heat boiler I, 13 is waste heat boiler II, 14 is waste heat boiler III, 15 are into and out material heat exchanger I, 16 are into and out material heat exchanger II, 17 are into and out material heat exchanger III, 18 is steam heater, 19 is water cooler, 20 is methane precooler, 21 is deep cooler I, 22 is deep cooler II.
Detailed description of the invention
The proposition of present invention process and condition is all propose on the basis to numerous Mo base sulfur resistant catalysts and Ni methylmethane chemical industry catalyst screening, if catalyst model can be provided for the industrial catalyst present invention in implementation process, if from the catalyst 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 that the 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 catalyst that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO313wt%-ZrO214.5wt%/��-Al2O3The catalyst of 72.5wt%, active component MoO3With auxiliary agent ZrO2It is carried on ��-Al by the mode of co-precipitation2O3On, concrete preparation method and technique are shown in CN103480362A embodiment 7; Nickel-base catalyst quality group in methanator becomes NiO40wt%-La2O37wt%-Al2O343wt%-ZrO27wt%, concrete preparation method and step are shown in CN102029162A embodiment 5. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of250%, CO8%, CO24%, CH427%, N27% and C2-4The coke-stove gas of hydrocarbon 4% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 250 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 6MPa and air speed is 8000h in pressure-1When, at support type catalyst with base of molybdenum MoO313wt%-ZrO214.5wt%/��-Al2O372.5wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 650 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 280 DEG C with coke-stove gas heat exchange, enter methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 6MPa and air speed is 8000h in pressure-1When, at support type catalyst with base of molybdenum MoO313wt%-ZrO214.5wt%/��-Al2O372.5wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 600 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 80 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 80 DEG C, 6MPa and 2000h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 250 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 6MPa and 8000h-1When, at NiO40wt%-La2O37wt%-Al2O343wt%-ZrO2Peace and quiet methanation reaction is carried out under 7wt% methanation catalyst effect, temperature be 400 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 45 DEG C, enter knockout drum II, gas-liquid separation is carried out when 4.5MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-70 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-160 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 2
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyst that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO335wt%-Co2O3+KO22wt%/ZrO2The catalyst of 63wt%, active component MoO3With auxiliary agent Co2O3+KO2It is carried on carrier ZrO by the mode impregnated2On, concrete preparation method and technique are shown in CN103495421A embodiment 14; Nickel-base catalyst in methanator adopts the CEG-LH catalyst of Davy. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of253.8%, CO7.3%, CO23.7%, CH425%, N26.7% and C2-4The coke-stove gas of hydrocarbon 3.5% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 255 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 5.5MPa and air speed is 7500h in pressure-1When, at support type catalyst with base of molybdenum MoO335wt%-Co2O3+KO22wt%/ZrO263wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 613 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 275 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 5.5MPa and air speed is 7500h in pressure-1When, at support type catalyst with base of molybdenum MoO335wt%-Co2O3+KO22wt%/ZrO263wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 578 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 70 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 70 DEG C, 5.3MPa and 1800h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 255 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 5.5MPa and 7500h-1When, peace and quiet methanation reaction is carried out under CEG-LH methanation catalyst effect, temperature be 385 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 40 DEG C, enter knockout drum II, gas-liquid separation is carried out when 4.0MPa, the water of condensation is discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-75 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase CO2With part C2-4Hydro carbons from bottom discharge, and gas phase from top discharge after after deep cooler II is cooled further to-165 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 3
The catalyst used in methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II in the present embodiment is identical, and its oxide mass consists of MoO330wt%-Co2O3+Fe2O3+ NiO20wt%/CeO2-Al2O3The catalyst of 50wt%, active component MoO3With auxiliary agent Co2O3+Fe2O3+ NiO is carried on support C eO by the mode impregnated2-Al2O3On, concrete preparation method and technique are shown in CN102463118A embodiment 5; Nickel-base catalyst quality group in methanator becomes NiO75wt%-La2O37wt%-Al2O315wt%-ZrO23wt%, concrete preparation method and step are shown in CN102029162A embodiment 4. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of254.7%, CO6.9%, CO23.5%, CH425.6%, N26.1% and C2-4The coke-stove gas of hydro carbons 3.2% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 260 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 5.0MPa and air speed is 7000h in pressure-1When, at support type catalyst with base of molybdenum MoO330wt%-Co2O3+Fe2O3+ NiO20wt%/CeO2-Al2O350wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 613 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 270 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 5.0MPa and air speed is 7000h in pressure-1When, at support type catalyst with base of molybdenum MoO330wt%-Co2O3+Fe2O3+ NiO20wt%/CeO2-Al2O350wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 554 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 65 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 65 DEG C, 5.0MPa and 1500h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 260 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 5.0MPa and 7000h-1When, at NiO75wt%-La2O37wt%-Al2O315wt%-ZrO2Peace and quiet methanation reaction is carried out under 3wt% methanation catalyst effect, temperature be 365 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 35 DEG C, enter knockout drum II, gas-liquid separation is carried out when 3.75MPa, the water of condensation is discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-80 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase CO2With part C2-4Hydro carbons from bottom discharge, and gas phase from top discharge after after deep cooler II is cooled further to-170 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 4
The catalyst used in methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II in the present embodiment is identical, and its oxide mass consists of MoO325wt%-Co2O3+ZrO215wt%/CeO2-Al2O3The catalyst of 60wt%, active component MoO3With auxiliary agent Co2O3+ZrO2It is carried on support C eO by the mode impregnated2-Al2O3On, concrete preparation method and technique are shown in CN102463118A embodiment 5; Nickel-base catalyst in methanator adopts the MCR-2X catalyst of Top's rope. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of256.2%, CO6.4%, CO23.4%, CH425.1%, N25.7% and C2-4The coke-stove gas of hydro carbons 3.2% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 265 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 4.5MPa and air speed is 6500h in pressure-1When, at support type catalyst with base of molybdenum MoO325wt%-Co2O3+ZrO215wt%/CeO2-Al2O360wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 575 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 275 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 4.5MPa and air speed is 6500h in pressure-1When, at support type catalyst with base of molybdenum MoO325wt%-Co2O3+ZrO215wt%/CeO2-Al2O360wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 570 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 60 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 60 DEG C, 4.5MPa and 1200h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 265 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 4.5MPa and 6500h-1When, peace and quiet methanation reaction is carried out under MCR-2X methanation catalyst effect, temperature be 350 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 30 DEG C, enter knockout drum II, gas-liquid separation is carried out when 3.5MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-85 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-175 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 5
The catalyst used in methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II in the present embodiment is identical, and its oxide mass consists of MoO310wt%-Co2O35wt%/Al2O3-ZrO2The catalyst of 85wt%, active component MoO3With auxiliary agent Co2O3It is carried on carrier Al by the mode of co-precipitation2O3-ZrO2On, concrete preparation method and technique are shown in CN101733115A embodiment 3; Nickel-base catalyst in methanator adopts the MCR-2X catalyst of Top's rope. Adopting above-mentioned catalyst, its specific embodiment and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of257.4%, CO6.2%, CO23.0%, CH424.7%, N25.5% and C2-4The coke-stove gas of hydro carbons 3.2% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 270 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 4.0MPa and air speed is 6000h in pressure-1When, at support type catalyst with base of molybdenum MoO310wt%-Co2O35wt%/Al2O3-ZrO285wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 550 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 265 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 4.0MPa and air speed is 6000h in pressure-1When, at support type catalyst with base of molybdenum MoO310wt%-Co2O35wt%/Al2O3-ZrO285wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 510 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 55 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 55 DEG C, 4.0MPa and 1100h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 270 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 4.0MPa and 6000h-1When, peace and quiet methanation reaction is carried out under MCR-2X methanation catalyst effect, temperature be 340 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 25 DEG C, enter knockout drum II, gas-liquid separation is carried out when 3.0MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-75 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-165 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 6
The catalyst used in methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II in the present embodiment is identical, and its oxide mass consists of MoO315wt%-Co2O3+La2O3The catalyst of 10wt%/magnesium aluminate spinel 75wt%, active component MoO3With auxiliary agent Co2O3+La2O3Being carried on carrier magnesium aluminate spinel by the mode of collosol and gel, concrete preparation method and technique are shown in CN101733115A embodiment 6; Nickel-base catalyst in methanator adopts the MCR-2X catalyst of Top's rope. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of257.8%, CO5.7%, CO22.6%, CH424.2%, N25.8% and C2-4The coke-stove gas of hydro carbons 3.9% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 275 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 3.5MPa and air speed is 5500h in pressure-1When, at support type catalyst with base of molybdenum MoO315wt%-Co2O3+La2O310wt%/magnesium aluminate spinel 75wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 525 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 260 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 3.5MPa and air speed is 5500h in pressure-1When, at support type catalyst with base of molybdenum MoO315wt%-Co2O3+La2O310wt%/magnesium aluminate spinel 75wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 450 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 50 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 50 DEG C, 3.5MPa and 900h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 275 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 3.5MPa and 5500h-1When, peace and quiet methanation reaction is carried out under MCR-2X methanation catalyst effect, temperature be 320 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 30 DEG C, enter knockout drum II, gas-liquid separation is carried out when 2.5MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-70 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-170 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 7
The catalyst used in methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II in the present embodiment is identical, and its oxide mass consists of MoO320wt%-Co2O3+Ce2O312wt%/��-Al2O3The catalyst of 68wt%, active component Mo2O3With auxiliary agent Co2O3+Ce2O3It is carried on carrier ��-Al by the mode of collosol and gel2O3On, concrete preparation method and technique are shown in CN101733115A embodiment 4; Nickel-base catalyst in methanator adopts the MCR-2X catalyst of Top's rope. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of260%, CO5.3%, CO22.7%, CH423.7%, N24.6% and C2-4The coke-stove gas of hydro carbons 3.7% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 280 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 3.0MPa and air speed is 4500h in pressure-1When, at support type catalyst with base of molybdenum MoO320wt%-Co2O3+Ce2O312wt%/��-Al2O368wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 500 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 255 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 3.0MPa and air speed is 4500h in pressure-1When, at support type catalyst with base of molybdenum MoO320wt%-Co2O3+Ce2O312wt%/��-Al2O368wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 400 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 40 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 40 DEG C, 3.0MPa and 900h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 280 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 3.0MPa and 4500h-1When, peace and quiet methanation reaction is carried out under MCR-2X methanation catalyst effect, temperature be 300 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 25 DEG C, enter knockout drum II, gas-liquid separation is carried out when 2.0MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-70 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-170 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 8
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyst that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO327wt%-Co2O3+La2O3The catalyst of 8wt%/magnesium aluminate spinel 65wt%, active component MoO3With auxiliary agent Co2O3+La2O3Being carried on carrier magnesium aluminate spinel by the mode impregnated, concrete preparation method and technique are shown in CN103495421A embodiment 14; Nickel-base catalyst in methanator adopts the CEG-LH catalyst of Davy. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of260%, CO6.0%, CO21.5%, CH423.3%, N26.6% and C2-4The coke-stove gas of hydro carbons 2.6% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 255 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 2.5MPa and air speed is 3500h in pressure-1When, at support type catalyst with base of molybdenum MoO327wt%-Co2O3+La2O38wt%/magnesium aluminate spinel 65wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 500 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 250 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 2.5MPa and air speed is 3500h in pressure-1When, at support type catalyst with base of molybdenum MoO327wt%-Co2O3+La2O38wt%/magnesium aluminate spinel 65wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 350 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 30 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 30 DEG C, 2.5MPa and 500h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 270 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 2.5MPa and 3500h-1When, peace and quiet methanation reaction is carried out under CEG-LH methanation catalyst effect, temperature be 300 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 30 DEG C, enter knockout drum II, gas-liquid separation is carried out when 2.5MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-70 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-170 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 9
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyst that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO323wt%-Co2O3+ZrO2+CeO27wt%/��-Al2O3The catalyst of 70wt%, active component MoO3With auxiliary agent Co2O3+ZrO2+CeO2It is carried on carrier ��-Al by the mode of co-precipitation2O3On, concrete preparation method and technique are shown in CN103480362A embodiment 2; Nickel-base catalyst in methanator adopts the CEG-LH catalyst of Davy. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of260%, CO5.0%, CO24.0%, CH423.0%, N26.0% and C2-4The coke-stove gas of hydro carbons 2.0% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 255 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 2.0MPa and air speed is 2500h in pressure-1When, at support type catalyst with base of molybdenum MoO323wt%-Co2O3+ZrO2+CeO27wt%/��-Al2O370wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 550 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 260 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 2.0MPa and air speed is 2500h in pressure-1When, at support type catalyst with base of molybdenum MoO323wt%-Co2O3+ZrO2+CeO27wt%/��-Al2O370wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 500 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 25 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 25 DEG C, 2.0MPa and 1000h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 270 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 2.0MPa and 2500h-1When, peace and quiet methanation reaction is carried out under CEG-LH methanation catalyst effect, temperature be 300 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 30 DEG C, enter knockout drum II, gas-liquid separation is carried out when 2.0MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-70 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-170 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Embodiment 10
In the present embodiment, methanation in presence of sulfur reactor I is identical with the catalyst that methanation in presence of sulfur reactor II uses, and its quality group becomes MoO313wt%-Co2O3+CeO214.5wt%/��-Al2O3The catalyst of 72.5wt%, active component MoO3With auxiliary agent Co2O3+ZrO2+CeO2It is carried on carrier ��-Al by the mode of co-precipitation2O3On, concrete preparation method and technique are shown in CN103480362A embodiment 5; Nickel-base catalyst quality group in methanator becomes NiO75wt%-La2O37wt%-Al2O315wt%-ZrO23wt%, concrete preparation method and step are shown in CN102029162A embodiment 4. Adopting above-mentioned catalyst, its concrete technical process and condition are as follows:
(1) after oil removing, deamination, de-benzene and de-naphthalene, H is consisted of259.6%, CO5.0%, CO23.0%, CH425.8%, N23.0% and C2-4The coke-stove gas of hydro carbons 3.6% first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange reaches 255 DEG C then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter in methanation in presence of sulfur reactor I from top, be 3.0MPa and air speed is 2000h in pressure-1When, at support type catalyst with base of molybdenum MoO313wt%-Co2O3+CeO214.5wt%/��-Al2O372.5wt% carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, temperature be 550 DEG C work off one's feeling vent one's spleen after first after waste heat boiler I reclaims heat and reaches 260 DEG C with coke-stove gas heat exchange, remove methanation in presence of sulfur reactor II;
(2) after heat recovery, enter methanation in presence of sulfur reactor II from top from the methanation in presence of sulfur reactor I reaction gas come, be 3.0MPa and air speed is 2000h in pressure-1When, at support type catalyst with base of molybdenum MoO313wt%-Co2O3+CeO214.5wt%/��-Al2O372.5wt% carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, temperature be 500 DEG C reaction gas by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and enter knockout drum I after being undertaken being cooled to 25 DEG C by air cooler I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum top laggard enter in coarse iron oxide desulfurizing tower, and at 25 DEG C, 2.0MPa and 1000h-1When carry out thick desulfurization, reaction gas after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, and under the reaction condition identical with thick desulfurizing tower, carry out fine de-sulfur, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange in methanator through input and output material heat exchanger III, and after steam heater heating is to 270 DEG C, enter equipped with methanator I catalyst based for Ni from top;
(3) reaction gas is in 2.0MPa and 2000h-1When, at NiO75wt%-La2O37wt%-Al2O315wt%-ZrO2Peace and quiet methanation reaction is carried out under 3wt% methanation catalyst effect, temperature be 300 DEG C work off one's feeling vent one's spleen by waste heat boiler III reclaim heat and with fine de-sulfur tower come gas converting heat after, then after air cooler II and water cooler are cooled to 30 DEG C, enter knockout drum II, gas-liquid separation is carried out when 2.0MPa, the water of condensation, butane and a small amount of propane are discharged from the bottom of knockout drum II, and gas phase goes out from knockout drum II top row, first through methane precooler and the gas converting heat discharged from knockout drum IV top, and after deep cooler I is cooled to-70 DEG C, enter knockout drum III and carry out gas-liquid separation, liquid phase carbon dioxide, propane, a small amount of ethane and sulfide are discharged from bottom, and gas phase from top discharge after after deep cooler II is cooled further to-170 DEG C, enter knockout drum IV, gas phase H2��N2Discharge from top with trace amounts of CO, and liquid phase is liquefied natural gas product, is sent to LNG tank standby.
The gas product composition for details see attached table 1 of synthesis under the reaction condition of the present embodiment.
Subordinate list 1
Note: in "-" representative products, this content of material is lower than 100ppm.
Claims (16)
1. a coke-stove gas is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that comprise the steps:
(1) coke-stove gas after oil removing, deamination, de-benzene and de-naphthalene first passes through input and output material heat exchanger II and methanation in presence of sulfur reactor II and works off one's feeling vent one's spleen heat exchange, work off one's feeling vent one's spleen after heat exchange then through input and output material heat exchanger I and methanation in presence of sulfur reactor I, enter from top in methanation in presence of sulfur reactor I, support type molybdenio catalyst for methanation in presence of sulfur carries out first order methanation in presence of sulfur and organic sulfur hydrogenation reaction, work off one's feeling vent one's spleen through waste heat boiler I reclaim heat and with coke-stove gas heat exchange after, enter methanation in presence of sulfur reactor II;
(2) from the methanation in presence of sulfur reactor I reaction gas come after heat recovery, methanation in presence of sulfur reactor II is entered from top, support type molybdenio sulfur resistant catalyst carries out the hydrogenation reaction of second level methanation in presence of sulfur and organic sulfur, work off one's feeling vent one's spleen by waste heat boiler II reclaim heat and with coke-stove gas heat exchange, and after being cooled down by air cooler I, enter knockout drum I and carry out gas-liquid separation, condensed fluid is discharged bottom knockout drum I, and gas phase discharge from knockout drum I top laggard enter in coarse iron oxide desulfurizing tower, working off one's feeling vent one's spleen after thick desulfurization enters active-carbon finely desulfurizing tower from bottom, working off one's feeling vent one's spleen after fine de-sulfur is first worked off one's feeling vent one's spleen heat exchange through input and output material heat exchanger III and methanator, and after steam heater heats, enter from top in the methanator catalyst based equipped with Ni,
(3) inlet gas carries out peace and quiet methanation reaction under the effect of Ni methylmethane catalyst, work off one's feeling vent one's spleen and reclaimed heat the gas converting heat come with fine de-sulfur tower by waste heat boiler III, then after air cooler II and water cooler cool down further, enter knockout drum II, condensed fluid is discharged from the bottom of knockout drum II, and gas phase is after knockout drum II top row goes out, the gas converting heat first discharged with knockout drum IV top through methane precooler, and after deep cooler I cools down further, enter knockout drum III and carry out gas-liquid separation, liquid phase is discharged from bottom, and gas phase from top discharge after after deep cooler II cools down further, enter knockout drum IV, gas phase is discharged from top, and liquid phase is liquefied natural gas product, it is sent to LNG tank standby.
2. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that the described coke-stove gas percent by volume through oil removing, deamination, de-benzene and de-naphthalene consists of H250��60%, CO5%��8%, CO21.5��4%, CH423%��27%, N23��7%, C2-4Hydro carbons 2��4%.
3. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that described support type molybdenio catalyst for methanation in presence of sulfur quality group becomes: active component MoO310��35wt%, auxiliary agent oxide 2��20wt%, carrier 50��85wt%; Wherein auxiliary agent is one or more in Co, La, Ce, Zr, Fe, Ni or K, and carrier is ��-Al2O3��SiO2, magnesium aluminate spinel, ZrO2��CeO2-Al2O3Complex carrier or Al2O3-ZrO2Complex carrier.
4. a kind of coke-stove gas as claimed in claim 3 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that described auxiliary agent is Co, La, Ce or Fe.
5. a kind of coke-stove gas as claimed in claim 3 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that described carrier is magnesium aluminate spinel, CeO2-Al2O3Complex carrier or Al2O3-ZrO2Complex carrier.
6. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that described methanation in presence of sulfur reactor I and methanation in presence of sulfur reactor II is fixed bed adiabatic reactor.
7. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described methanation in presence of sulfur reactor I inlet air temperature degree is 250��280 DEG C, temperature of working off one's feeling vent one's spleen is 500��650 DEG C, and reaction pressure is 2��6MPa, and air speed is 2000��8000h-1��
8. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described methanation in presence of sulfur reactor II inlet air temperature degree is 250��280 DEG C, temperature of working off one's feeling vent one's spleen is 350��600 DEG C, reaction pressure is identical with methanation in presence of sulfur reactor I, reaction velocity 2000��8000h-1��
9. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that the operation temperature of described coarse iron oxide desulfurizing tower is 25��80 DEG C, operates pressure 2��6MPa, and air speed is 500��2000h-1��
10. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that described active-carbon finely desulfurizing tower operation temperature, pressure are identical with coarse iron oxide desulfurizing tower with air speed.
11. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that the catalyst based MCR-2X methanation catalyst for Top's rope of Ni used in described methanator, the catalyst of Davy company CEG-LH methanation catalyst or the exploitation of Dalian Physical and Chemical Inst., wherein the catalyst of Dalian Physical and Chemical Inst. exploitation becomes in the quality group of oxide: active component NiO10��75%, auxiliary agent 0.1��15%, carrier is surplus, auxiliary agent is lanthana or the compositions of lanthana and nickel lanthanum compound, carrier is the compositions that aluminium oxide is formed with zirconium oxide with nickel aluminide.
12. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described methanator is insulation fix bed reactor, the temperature of gas access is 250��280 DEG C, outlet temperature 300��400 DEG C, reaction pressure is 2��6MPa, and reaction velocity is 2000��8000h-1��
13. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that described after methanator work off one's feeling vent one's spleen recovered heat and water cooler cooling out, gas is 2.0��4.5MPa at pressure, temperature is 25-45 DEG C, isolates the solidifying water of technique, butane and a small amount of propane in knockout drum II.
14. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that the gas phase of knockout drum II is after methane precooler and deep cooler I are cooled to-70��-85 DEG C, carries out gas-liquid separation in 2.0��4.5MPa in knockout drum III.
15. a kind of coke-stove gas as claimed in claim 1 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterized in that the isolated gas phase of knockout drum III is cooled to-160��-175 DEG C by deep cooler II further, cooled gas-liquid mixture carries out gas-liquid separation in 2.0��4.5MPa in knockout drum IV.
16. a kind of coke-stove gas as described in any one of claim 1-15 is through the technique of methanation in presence of sulfur synthetic natural gas, it is characterised in that the volume of described coke-stove gas synthesis gas after above-mentioned technique and condition consists of: CH497��98%, N20.3��1.0%, C2-3Hydro carbons 1.0��2.0%, CO2�� 100ppm, H2�� 100ppm, CO��10ppm.
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