CN101805648A - Process method for preparing LNG from coke oven tail gas - Google Patents
Process method for preparing LNG from coke oven tail gas Download PDFInfo
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Abstract
The invention relates to a process method for preparing LNG from coke oven tail gas. The method comprises the following steps: storing coke oven gas subject to wet desulphurization pretreatment from a coke-oven plant in a gas holder to be used as the feed gas, enabling the feed gas to be subject to pressurization, normal-temperature oxidation and pre-desulphurization, two-stage catalytic hydrogenation conversion and dry desulphurization, converting CO and CO2 in the feed gas into CH4 by three-stage methanation reaction, removing residual moisture and CO2 by the adsorption of a molecular sieve, and carrying out two-stage throttling flash distillation and copious cooling liquefaction to obtain the LNG product. The invention has the characteristics of low total sulfur content, high liquefied gas quality and high calorific value.
Description
Technical field
The present invention relates to the coke(oven)gas is that unstripped gas prepares the LNG processing method, particularly adopts pressurization oil removing, thick desulfurization, smart desulfurization, shortening, methanation reaction, Hydrogen Separation, last cryogenic liquefying and make the processing method of LNG.
Background technology
The main component of natural gas liquids (LNG) is a methane, has calorific value height (＞31.4MJ/Nm
3) and the convenient characteristics that store and transport, can be used for gas supply, peak regulation and bailout gas, gas combustion automobile, bottled combustion gas, basic chemical industry raw material, industrial combustion gas etc.
Coke(oven)gas is one of main by product in coke-oven plant's coal destructive distillation Coking Process, and main component has hydrogen, methane, CO, CO
2Deng.The purifying treatment of existing coke(oven)gas generally adopts the washing de-oiling, washes naphthalene, desulfurization, takes off benzene etc., coal gas after the purification is mainly as town gas, industrial chemicals, industrial combustion gas etc., but still have more coke-oven plant not have coal-gas recovering and comprehensive utilization operation, with gas-fired emptying or directly discharging, its consequence is to cause toxic and harmful and the dust severe contamination to atmospheric environment.
At present, adopt following physical method that the methane separation in the coke(oven)gas is come out and is used usually: as, the Chinese patent literature of application number 2006101020385 adopts the deep refrigeration technology to produce LNG from coke(oven)gas; And for example, application number 200610102039.X, 200610102040.2 adopts transformation absorption and deep refrigeration technology that components such as methane are separated from coke(oven)gas; For another example, application number 200810135211.0 adopts the cooling fractionating technology to produce natural gas liquids from coke(oven)gas.The above-mentioned processing method characteristics of having nothing in common with each other still, all lack CO, CO in the coke(oven)gas
2The utilization of composition also exists total sulfur in the coke(oven)gas to remove the problem of measure shortcoming, thereby influence the quality of finished product LNG, makes its application all can be subjected to certain limitation (as, automobile fuel).
Summary of the invention
The purpose of this invention is to provide that a kind of total sulfur content is few, quality product is high, H
2, CO and CO
2A kind of coke(oven)gas process method for preparing LNG that all can be made full use of.
The object of the present invention is achieved like this: a kind of coke(oven)gas process method for preparing LNG, carry out according to the following steps in turn:
A), under pressurized conditions, normal temperature de-oiling desulfurization
The coke(oven)gas that adopts coke-oven plant's process preliminary cleaning processing is as unstripped gas, after compressed machine is compressed to 2.3～2.5MPa.G, after at first entering the tar jar and removing residu(al)tar, enter the pre-desulfurizer of normal temperature again, the ferric oxide by splendid attire in the desulfurizer removes partial vulcanization hydrogen and organosulfur;
B), three grades of shortenings transform the two-stage dry desulfurization
To be preheated to 280～320 ℃ through the unstripped gas after a step handles, enter pre-hydrocracking device, under iron-molybdic catalyst, carry out pre-hydrocracking, send into one-level hydrocracking device then, under iron-molybdic catalyst, most organosulfurs are converted into inorganic sulfur, then enter desulfurizer, carry out desulfurization by ferric oxide; Subsequently, enter secondary hydrocracking device, under the nickel cobalt-molybdenum catalyst, further the organosulfur with remnants is converted into inorganic sulfur, then enter the smart desulfurizer of zinc oxide, total sulfur in the unstripped gas is reduced to below the 0.1ppm (V), and above-mentioned two-step desulfurization service temperature is 350～400 ℃ that build-up of pressure is identical with a step;
C), three grades of methanation reactions
Go on foot CO and CO in the unstripped gas according to b
2Content, under catalyst action, adopt placed in-line three grades of methanation reactions, because methanation is a thermopositive reaction, therefore adopt heat exchanger to remove the heat that the upper level methanation produces at each inter-stage, control reflects the temperature of implication, adopts waste heat boiler to reclaim the heat that reaction produces simultaneously; Through the transformation adsorption operations Hydrogen Separation is wherein gone out CO in the final methanation gas again by the methanation gas behind three grades of methanation reactions
2Content should satisfy the needs of follow-up molecular sieve adsorption ability, and CO content should satisfy the requirement of natural gas liquids quality standard;
D), molecular sieve adsorption removes residual water-content and CO
2
C goes on foot methanation gas to remove residual water-content and CO through molecular sieve adsorption
2After, with CO in the gas
2Content is reduced to below the 0.0007mol%;
E), methanation gas cryogenic liquefying
E1), methanation gas at first passes through methanation gas filtration separator under 38～42 ℃, 1.5～1.7MPa.G condition, remove the free fluid and the mechanical impurity that may carry, and is compressed again to 5.0MPa.G;
E2), e1 goes on foot methanation gas to adopt three ADSORPTION IN A FIXED BED towers to carry out processed, wherein first tower carries out dehydration operation, second tower carries out the regeneration of sorbent material, the 3rd tower carries out the cooling of sorbent material, three tower blocked operations, adsorption cycle is 8h, and the adsorption tower outlet methanation gas after the purification is in the water content≤1ppm of weight fraction;
E3), enter before the liquefaction unit, methanation gas must adopt CO
2Content on line analyzer and H
2The on line analyzer of O content is analyzed, to guarantee CO in the gas gross
2Content＜0.0007mol% is in the H of weight fraction
2O is not more than 1ppm;
E4), refrigeration system adopts n-formyl sarcolysine alkane as refrigeration agent, refrigeration agent is compressed to 1.8MPa.G by recycle compressor, enters the multistage expansion system and make methane liquefaction after water cooling, enters the liquefaction ice chest again after water cooling;
Refrigeration agent cools off in the plate-type heat exchanger of liquefaction ice chest, is cooled to after the certain temperature major part and enters in the decompressor and expand, and the refrigeration agent of decompressor outlet turns back to the plate-type heat exchanger cold junction; From plate-type heat exchanger, extract out another small portion refrigeration agent continues cooling, condensation and is as cold as certain temperature excessively in interchanger after and enter throttling valve throttling step-down, as the re-heat in plate-type heat exchanger of one of the low-temperature receiver of interchanger, re-heat is joined with the refrigeration agent of decompressor outlet after certain temperature, cooling box behind the release low temperature cold enters the recycle compressor loop compression;
E5), the liquefied methane that comes out from the liquefaction ice chest enters the adiabatic primary and secondary storage tank of ordinary powder and stores pressure store 0.4MPa.G.
Above-mentioned a in the step from the unstripped gas of gas holder consisting of of percentage ratio: H by volume
2, 53; CO, 9.8; CO
2, 4; CH
4, 24; N
2, 6.1; CmHm, 2.6; O
2, 0.5.
Massage consisting of of percentage ratio meter in the above-mentioned e5 step liquefied methane product: methane, 96.0002; Ethane, 0.05; Propane, 0.002; Nitrogen, 3.8534; Hydrogen, 0.1382.
The unstripped gas of above-mentioned a step from gas holder passes through compressor compresses to 2.4MPa.G.
Above-mentioned e2 is in the step, and the low-pressure tail gas that employing liquefaction ice chest comes out is as cold blowing gas and resurgent gases, and it is 230～290 ℃ that resurgent gases is advanced the adsorption tower temperature, and it is 175～220 ℃ that resurgent gases goes out the adsorption tower temperature.
Compared with prior art, the present invention has following characteristics and advantage:
1, quality product height, total sulfur content are few
Adopt three grades of shortenings, organosulfur in the unstripped gas is converted into inorganic sulfur, and, make below total sulfur content＜0.1ppm in the finished product (V), be particularly useful for clean fuel for vehicle by thick desulfurization and smart desulfurization.
2, adopt three grades of methanation reactions, with the CO in the unstripped gas, CO
2Convert methane to, thereby become harmful, turn waste into wealth into useful.This product calorific value is up to 34MJ/Nm
3(standard is 31.4MJ/Nm
3).
3, the technology of the present invention advanced person, technical maturity are reliable, now enter the industrializing implementation stage.
LNG is the product that typically segments market, be convenient to transportation owing to have, the calorific value height cleans pure, easy to use, be convenient to advantages such as storage, will on the industrial chemicals and combustion gas market in future, occupy more and more heavier position, particularly along with the continuous expansion of the transformation of large-scale city Sweet natural gas, range of application and consumption, natural gas is supplied with shortage will occur in certain phase, and does not also have substitute in a short time, and LNG will have bright more prospect.
The main application of LNG:
1, city air feed gas source
LNG can be transported to the distant city that does not have gas distributing system by non-pipeline transportation, as the gas source in these cities.
2, city peak regulation source of the gas and bailout gas
LNG peak regulation air feed is compared with using original peak regulation plenum system, have to store and place, storing mode is flexible, and maneuvering ability is good, and it is few to store occupation of land, duration is short, easy to maintenance, therefore, city peak regulation source of the gas scale will be increasing, and for preventing that transporting air feed interrupts, the construction of bailout gas is also even more important.
3, satellite and rural air feed
The satellite of big and medium-sized cities is owing to transport source of the gas and transport pipeline construction, and gas pipe line is uneconomical, even does not have possibility.And because the LNG transportation is deposited efficiently flexibly, and the container unit storage capacity is big, and duration of service is long, be particularly suitable for middle sub-district and remote villages and small towns and use, have to build and transform value, to deposit soon, mode is flexible, and price is steady, is very suitable local plenum system.
4, factory's fuel gas source and bailout gas
Because LNG deposit is convenient, and calorific value is high, be convenient to industrial application and emergent replenishing and storage especially, therefore, as factory's guarantee fuel source of the gas, it is low to have an infrastructure investment, and storage is flexibly, and is easy to use, is convenient to procuring and provisioning simultaneously.
5, fuel for cleaning vehicle
With gasoline, diesel oil, LPG compares with LNG, and LNG has combustion value height, anti-knocking property are good, price is low, and one time filling weight is big, and actual service life is long, the advantage that tail gas pollution is little, as the fine clean fuel, along with the quickening of national cleaning vehicle action paces, the status of LNG in gas and fuel will be more and more important.
6, Chemical Manufacture basic material
As Chemical Manufacture basic materials such as petrochemical industry isomerization, charcoal element, hydrogen, acetylene, formaldehyde, methane chlorides.
7, mobile source of the gas:
As outdoor life, the purposes of life waterborne, LNG is because safety easy to carry, and easy to use, also more big market will be arranged.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Industrial scale
Handle coke oven coal: 30000m
3/ h
720,000 m
3/ d
Product: LNG:11000Nm
3/ h
Byproduct: H
2: 5000Nm
3/ h (according to a preliminary estimate) by present component
Year operation time: 8000h
Products scheme:
LNG：11000Nm
3/h??7.8712t/h(-135℃，0.6MPa·G)
62769.6t/a
H
2：5000m
3/h
16.56 ten thousand m
3/ d
The product technology quality index
The LNG product specification
Calorific value: index＞31.4MJ/Nm
3, this product surpasses 34MJ/N m
3H
2Technical indicator (refining back)
| Form | ??H 2 | ??CO+CO 2 | ??N 2 | ??CH 4 |
| ??V％ | ??≥99.9％ | ??≤20ppm | ??≤0.04％ | ??≤5ppm |
| ??O 2 | ??H 2O | ??NH 3 | ??C 2H 2 | |
| ??≤5ppm | ??≤2mg/m 3 | ??≤5ppm | ??≤10ppm | |
| Total S | ||||
| ??≤1ppm | ||||
| Pressure | ??≥1.4??MPa(G) |
| Form | ??H 2 | ??CO+CO 2 | ??N 2 | ??CH 4 |
| Temperature | ??≤40℃ |
Annotate: this process technology scheme wouldn't comprise that hydrogen is refining.If need to make with extra care, can increase pressure-swing absorption apparatus.
Process technology scheme:
(1) coke(oven)gas is formed
| Component | ??H 2 | ??CO | ??CO 2 | ?CH 4 | ??N 2 | ??C mH n | ??O 2 | ??H 2O | Lower heating value (KJ/m 3) | Remarks |
| Form (v%) (butt) | ??53 | ??9.8 | ??4 | ??24 | ??6.1 | ??2.6 | ??0.5 | |||
| Form (v%) (wet basis) |
(2) foreign matter content
H
2S≤20mg/Nm
3Organosulfur≤250mg/Nm
3NH
3＜6mg/Nm
3
(3) pressure normal pressure
40 ℃ of temperature
Tolerance 30000Nm
3/ h
Process program:
Referring to Fig. 1, from the coke-oven gas → gas holder after the wet desulphurization → pressurization → oil removing → desulfurization (the normal temperature iron oxide desulfurization → smart desulfurization of the pre-iron molybdenum hydrogenation → thick desulfurization of iron molybdenum hydrogenation (using Zinc oxide desulfurizer) → heat exchange → cobalt nickel molybdenum hydrogenation (iron molybdenum hydrogenation) → zinc oxide) → methanation → separation H2 → cryogenic liquefying methane
Brief description of the process:
From the coke(oven)gas of coke-oven plant, still contain micro-tar, benzene, naphthalene, ammonia, prussic acid, Cl through purifying treatment
-, H
2S, unsaturated olefin, thiophene, thioether, mercaptan, COS and CS
2Deng organosulfur.Unstripped gas from gas holder outside the battery limit (BL) is sent within battery limit through its gas fan, through compressor compresses to 2.3～2.5Mpa.G, as, after (2.4MPa.G gauge pressure), after at first entering the decoking oil tank and removing residu(al)tar, enter the pre-desulfurizer of normal temperature, remove partial vulcanization hydrogen and organosulfur after be preheated to about 300 ℃ (general 280～320 ℃), enter pre-hydrocracking, and then enter one-level hydrocracking device.After most organosulfurs are converted into inorganic sulfur, enter secondary hydrocracking device (two-stage hydrogen invert point is 350～400 ℃, is preferably 380 ℃), further the organosulfur with remnants is converted into inorganic sulfur, enters the smart desulfurizer of zinc oxide then.Enter methanation workshop section after total sulfur is brought down below 0.1ppm.In methanation workshop section, after three grades of methanations, will go out the CO+CO of methanation battery limit (BL)
2After reducing to below the 100ppm, enter follow-up low-temperature liquefaction centrifugal station.Behind methanation furnaces at different levels, be respectively equipped with waste heat boiler and superheater, removing the reaction heat of methanation, and recovery waste heat, control reaction temperature then.Enter the thick product gas of low temperature workshop section, at first after refrigerated separation is fallen most of phlegma, enter molecular sieve to remove remaining moisture content and CO
2After compressed machine rises to 5.0MPa, cooling and precooling, enter two-stage throttling flash system, isolating non-product gas, and obtain qualified liquid product gas.
Technology features
1) compression fine purification technique for coke oven gas:
Organosulfur complex shape stable chemical performance such as the thiophene that contains in the coke-oven gas, thioether, mercaptan, at first carry out the dry method hydrocracking, organosulfur is converted into inorganic sulfur, utilize dried sweetening agent that it is removed again, for prolonging the work-ing life of hydrogenation conversion catalyst, should will slough 20mg/m from the hydrogen sulfide in the coke oven of tail end coke-oven plant
3Slough low amounts of organic sulfur when as follows, to reduce the process cost of dry desulfurization.
Smart desulfurization technology scheme:
Advance the coarse raw materials coke-oven gas of battery limit (BL), removing residu(al)tar by the tar groove after compression, and by after the pre-desulfurization of normal temperature (catalyzer model TC-30X, Xibei Chemical Inst) slightly takes off, enter the high temperature desulfurizing section and carry out high temperature and slightly take off with essence and take off.Because of the chemical stability height that the coke(oven)gas that dispatches from the factory is brought into, the thiophene that is difficult to decompose, thioether, organosulfurs such as mercaptan.Therefore adopt hydrogenating conversion process, organosulfur is converted into inorganic sulfur.Need with hydrogenation conversion catalyst mainly contain the cobalt molybdenum, nickel cobalt molybdenum (model JT-1, Xibei Chemical Inst) and iron molybdenum type catalyst such as (model JT-8, Xibei Chemical Insts).
Because cobalt molybdenum hydrogenation conversion catalyst price is higher, and CO and CO
2The higher gas of content can produce analyses carbon and methanation side reaction.Therefore this scheme will not consider to adopt cobalt-molybdenum catalyst.
This scheme will adopt iron molybdenum hydrocracking to add the ferrimanganic absorption, and nickel cobalt molybdenum hydrocracking adds two kinds of absorption patterns of two-stage hydrocracking of zinc oxide desulfurization then.Operational condition is: 350～400 ℃ of temperature, technical process is, the smart desulfurization of iron molybdenum hydrocracking → ferric oxide desulfurization → nickel cobalt molybdenum hydrocracking → zinc oxide, thereby make the total sulfur volume fraction＜0.1ppm of unstripped gas, simultaneously unsaturated hydrocarbons is converted into stable hydrocarbon, and the micro amount of oxygen in unstripped gas reaction become water, thereby make unstripped gas satisfy follow-up methanation process requirement.
Methanation process
Methanation is mainly described by following equation and process:
CO+3H
2＝CH
4+H
2O+Q????CO2+4H
2＝CH
4+2H
2O+Q
Methanation is an exothermic process, therefore, control methanation reaction temperature also in time shifts out the heat that reflection produces, avoid too high temperature, prevent that (existing synthesis ammonia system touches coal with the conversion that gas making workshop section uses to catalyst, model is RHM-266, Xibei Chemical Inst) scaling loss is the key of methanation design.
According to CO and CO in the charging coke-oven gas
2Content, this programme adopts placed in-line three grades of methanation reactions, and adopts waste heat boiler and superheater at each inter-stage, the temperature that control upper level methanation is worked off one's feeling vent one's spleen also reclaims the heat that is produced, by the product gas behind three grades of methanation reactions, its CO
2Content satisfies the needs of follow-up molecular sieve (model 13X-APG) adsorptive power, and the CO trace satisfies the requirement of natural gas liquids quality standard.
3) natural gas liquefaction and Hydrogen Separation technology
Technical process is described:
A, methanation gas compression system
Methanation gas is at 40 ℃, (general 38～42 ℃ of about 1.6MPa.G, 1.5～1.7Mpa.G) enter this device under the condition, methanation gas at first passes through methanation gas filtration separator (sorbent material is a gac) and removes the free fluid and the mechanical impurity that may carry, the compressed again follow-up system that enters methanation liquefaction of gases device to 5.0MPa.G later on as far as possible.
Methanation gas motion device is provided with accident interlocking trip valve, cuts off the methanation gas of access to plant, the safety of assurance device, personnel and near facility.
The dehydration branch of B, methanation gas
The coke oven tail gas dehydration divides adopts three ADSORPTION IN A FIXED BED towers, and a tower carries out dehydration operation, and a tower carries out the regeneration of sorbent material, the cooling of another tower sorbent material, blocked operation.Adsorption cycle is 8h, methanation pneumatic outlet water content (weight fraction the meter)≤1ppm after the purification.Resurgent gases is advanced 230～290 ℃ of adsorption tower temperature, and resurgent gases goes out 175～220 ℃ of temperature of adsorption tower.
The low-pressure tail gas that comes out with ice chest is as cold blowing gas, resurgent gases, and cold blowing, resurgent gases are come out from the moisture eliminator top, gives off device after the cooling of resurgent gases water cooler.
The liquefaction of C, methanation gas and fractionation
Before entering liquefaction unit, methanation gas must be analyzed, and reaches the requirement that enters liquefaction unit to guarantee foreign matter content.
Enter the liquefaction ice chest and be equipped with following analysis meter before:
CO
2The content on line analyzer
H
2O content on line analyzer
Purify back methanation gas, enter in the interchanger of liquefaction ice chest cool off, condensation, the gas after the throttling step-down is sent ice chest after the interchanger re-heat, as the tail gas of device; Liquid after the throttling step-down is sent into storage tank as the liquefied methane product and is stored (liquefied methane temperature-162 ℃ below).
D, refrigeration system
Refrigeration system adopts n-formyl sarcolysine alkane (n-formyl sarcolysine alkane mix refrigerant), and as refrigeration working medium, refrigeration agent is compressed to 1.8MPa.G by recycle compressor, enters the multistage expansion system and make methane liquefaction after water cooling, enters the liquefaction ice chest after water cooling.
Refrigeration agent cools off in the ice chest plate-type heat exchanger, is cooled to after the certain temperature major part and enters in the decompressor and expand, and the refrigeration agent of decompressor outlet turns back to the plate-type heat exchanger cold junction; From plate-type heat exchanger, extract out another small portion refrigeration agent continues cooling, condensation and is as cold as certain temperature excessively in interchanger after and enter throttling valve throttling step-down, as the re-heat in plate-type heat exchanger of one of the low-temperature receiver of interchanger, re-heat is joined with the refrigeration agent of decompressor outlet after certain temperature, cooling box behind the release low temperature cold enters the recycle compressor loop compression.
The storage of E, liquefied methane
The liquefied methane that comes out from the liquefaction ice chest enters the storage tank storage.
According to the output of liquefied methane, device is equipped with about 5-7 days storage capacity, promptly joins 1 2500m
3Ordinary powder adiabatic primary and secondary storage tank store.
Liquefied methane is stored and is adopted the adiabatic primary and secondary storage tank of ordinary powder, storage pressure 0.4MPaG, design pressure 0.6MPaG.
F, controlled function summary
Controlling System adopts the PLC system.Its function is:
Show dynamic process flow process, main technologic parameters and equipment running status.
Production process is monitored, guaranteed the normal operation of liquefied methane factory technics flow process and equipment.
The abnormal work state is carried out sound and light alarm, the safety of protection personnel and equipment.
But on-line setup, modification processing parameter.
Can instant recording, storage and printing related process parameter, equipment running status and alert event.
Can show real-time tendency curve and history curve.
Can regularly print various production reports.
Realizing manually reaching automatic emergency according to the accidental state in the production process turn-offs, promptly releases and the emergency logic.
Can carry out manual analyzing to the medium key ingredient, the automatic on-line Analysis for CO
2And H
2O content.
System has stronger opening, extendability.Communication interface with data upload.
The component of the finished product is:
LNG component table
Annotate: domestic Sweet natural gas standard code: superior calorific value should be greater than 31.4MJ/Nm
3, the superior calorific value of above-mentioned LNG is 36MJ/Nm
3
Main raw material(s), fuel and power consumption:
Press 1t or 1000m
3The LNG meter
| Sequence number | Project name | Unit | Hour amount/h | Feed ration/d | Year amount/a | Remarks |
| ??1 | Coke-oven gas (CH 4≥XX％S≤??XX％) | ??t | ||||
| Four | Utility power consumes | |||||
| ??1 | Supply water | |||||
| Fresh water (industrial water) | ??m 3 | |||||
| Recirculated water | ??m 3 | ??1850 | ||||
| ??2 | Power supply | |||||
| Installed capacity | ??kW | ??12000 | ||||
| Current consumption | ??kWh | 9,800,000 | ||||
| ??3 | Steam 1.96 * 105Pa (G) | ??t | ||||
| Five | Three wastes discharge amount | |||||
| ??1 | Waste gas | ??m 3 | ||||
| ??2 | Waste water | |||||
| Sanitary wastewater | ??m 3 | |||||
| Sewage | ??m 3 | |||||
| ??3 | ??t |
Claims (5)
1. process method for preparing LNG from coke oven tail gas is characterized in that: carry out in turn according to the following steps:
A), under pressurized conditions, normal temperature de-oiling desulfurization
Adopt the coke-oven plant to be stored in the gas holder as unstripped gas through the coke(oven)gas of purifying treatment, behind unstripped gas process compressor compresses to 2.3～2.5MPa.G from gas holder, after at first entering the tar jar and removing residu(al)tar, enter the pre-desulfurizer of normal temperature again, the ferric oxide by splendid attire in the desulfurizer removes partial vulcanization hydrogen and organosulfur;
B), three grades of shortenings transform the two-stage dry desulfurization
To be preheated to 280～320 ℃ through the unstripped gas after a step handles, enter pre-hydrocracking device, under iron-molybdic catalyst, carry out pre-hydrocracking, send into one-level hydrocracking device then, under iron-molybdic catalyst, most organosulfurs are converted into inorganic sulfur, then enter desulfurizer, carry out desulfurization by ferric oxide; Subsequently, enter secondary hydrocracking device, under the nickel cobalt-molybdenum catalyst, further the organosulfur with remnants is converted into inorganic sulfur, then enter the smart desulfurizer of zinc oxide, total sulfur volume fraction in the unstripped gas is reduced to below the 0.1ppm, and above-mentioned two-step desulfurization service temperature is 350～400 ℃ that build-up of pressure is identical with a step;
C), three grades of methanation reactions
Go on foot CO and CO in the unstripped gas according to b
2Content, under catalyst action, adopt placed in-line three grades of methanation reactions, adopt heat exchanger to remove the heat that the upper level methanation produces at each inter-stage, control reflects the temperature of implication, adopts waste heat boiler to reclaim the heat that reaction produces simultaneously; Through the transformation adsorption operations Hydrogen Separation is wherein gone out CO in the final methanation gas again by the methanation gas behind three grades of methanation reactions
2Content should satisfy the needs of follow-up molecular sieve adsorption ability, and CO content should satisfy the requirement of natural gas liquids quality standard;
D), molecular sieve adsorption removes residual water-content and CO
2
C goes on foot methanation gas to remove residual water-content and CO through molecular sieve adsorption
2After, with CO in the gas
2Content is reduced to below the 0.0007mol%;
E), methanation gas cryogenic liquefying
E1), methanation gas at first passes through methanation gas filtration separator under 38～42 ℃, 1.5～1.7MPa.G condition, remove the free fluid and the mechanical impurity that may carry, and is compressed again to 5.0MPa.G;
E2), e1 goes on foot methanation gas to adopt three ADSORPTION IN A FIXED BED towers to carry out processed, wherein first tower carries out dehydration operation, second tower carries out the regeneration of sorbent material, the 3rd tower carries out the cooling of sorbent material, three tower blocked operations, adsorption cycle is 8h, and the adsorption tower outlet methanation gas after the purification is in the water content≤1ppm of weight fraction;
E3), enter before the liquefaction unit, methanation gas must adopt CO
2Content on line analyzer and H
2The on line analyzer of O content is analyzed, to guarantee CO in the gas gross
2Content＜0.0007mol% is in the H of weight fraction
2O is not more than 1ppm;
E4), refrigeration system adopts n-formyl sarcolysine alkane as refrigeration agent, refrigeration agent is compressed to 1.8MPa.G by recycle compressor, enters the multistage expansion system and make methane liquefaction after water cooling, enters the liquefaction ice chest again after water cooling;
Refrigeration agent cools off in the plate-type heat exchanger of liquefaction ice chest, is cooled to after the certain temperature major part and enters in the decompressor and expand, and the refrigeration agent of decompressor outlet turns back to the plate-type heat exchanger cold junction; From plate-type heat exchanger, extract out another small portion refrigeration agent continues cooling, condensation and is as cold as certain temperature excessively in interchanger after and enter throttling valve throttling step-down, as the re-heat in plate-type heat exchanger of one of the low-temperature receiver of interchanger, re-heat is joined with the refrigeration agent of decompressor outlet after certain temperature, cooling box behind the release low temperature cold enters the recycle compressor loop compression;
E5), the liquefied methane that comes out from the liquefaction ice chest enters the adiabatic primary and secondary storage tank of ordinary powder and stores pressure store 0.4MPa.G.
2. according to the described process method for preparing LNG from coke oven tail gas of claim 1, it is characterized in that: described a in the step from the unstripped gas of gas holder consisting of of percentage ratio: H by volume
2, 53; CO, 9.8; CO
2, 4; CH
4, 24; N
2, 6.1; CmHm, 2.6; O
2, 0.5.
3. according to the described process method for preparing LNG from coke oven tail gas of claim 2, it is characterized in that: massage consisting of of percentage ratio meter in the described e5 step liquefied methane product: methane, 96.0002; Ethane, 0.05; Propane, 0.002; Nitrogen, 3.8534; Hydrogen, 0.1382.
4. according to the described process method for preparing LNG from coke oven tail gas of claim 3, it is characterized in that: the unstripped gas of described a step from gas holder passes through compressor compresses to 2.4MPa.G.
5. according to the described process method for preparing LNG from coke oven tail gas of claim 4, it is characterized in that: described e2 is in the step, the low-pressure tail gas that employing liquefaction ice chest comes out is as cold blowing gas and resurgent gases, and it is 230～290 ℃ that resurgent gases is advanced the adsorption tower temperature, and it is 175～220 ℃ that resurgent gases goes out the adsorption tower temperature.
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