CN102250658A - Method for preparing liquefied natural gas by converting raw materials of coke oven gas and blast furnace gas - Google Patents

Method for preparing liquefied natural gas by converting raw materials of coke oven gas and blast furnace gas Download PDF

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CN102250658A
CN102250658A CN2010101760028A CN201010176002A CN102250658A CN 102250658 A CN102250658 A CN 102250658A CN 2010101760028 A CN2010101760028 A CN 2010101760028A CN 201010176002 A CN201010176002 A CN 201010176002A CN 102250658 A CN102250658 A CN 102250658A
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China
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gas
methanation
blast furnace
coke
coal gas
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CN2010101760028A
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尹冬梅
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上海标氢气体技术有限公司
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Abstract

The invention discloses a method for preparing liquefied natural gas by converting raw materials of coke oven gas and blast furnace gas. In the technology, the coke oven gas and the blast furnace gas are taken as the raw materials, the raw materials are subjected to normal-temperature normal-pressure dry desulfurization, gas compression, gas adsorption purification, gas isothermal-adiabatic serial methanation, gas adsorption drying and demetalization, freezing liquefication separation and other technical processes, and high-quality liquefied natural gas with the purity of over 99 percent is produced. By the technology, harmful impurities such as sulfur, naphthalene, tar, benzene, mercury and the like in the gas can be efficiently and easily removed fully at low cost, and components with low value, such as H2, CO, CO2 and the like are completely converted into required CH4 component with high value, so the method has the characteristics of low requirement on quality of feed gas, high yield of liquefied natural gas product, high product purity, low production energy consumption, no environmental pollution, reliable flow, low investment, simple operation and good economic benefit.

Description

The method of coke-oven gas and blast furnace gas feedstock conversion preparing liquefied natural gas
[technical field]
The present invention relates to a kind of technical process method that fully utilizes coke-oven gas and a large amount of natural gas liquids of blast furnace gas conversion production.
[background technology]
China is maximum in the world coke production state, the a large amount of coke-oven gas (annual 800 billion cubic meters that surpass) of meeting by-product in producing the coke process, these coke-oven gas are done the fuel except that melting down about half, remaining half just needs to utilize in addition, as makes combustion gas, generating, production synthetic ammonia, methyl alcohol, dme etc.But because these utilize the big or not high problem of benefit of mode ubiquity investment, the still a large amount of directly burning and exhausting coke-oven gas of therefore many coke production enterprises have caused a large amount of wastes and the environmental pollution of resource.China is again simultaneously maximum in the world Iron and Steel Production big country, have maximum blast furnace ironmaking throughput, the a large amount of blast furnace gas of by-product in the time of blast furnace ironmaking, because its calorific value is very low, usually all be with the high heating value combustion gas mixing after do fuel or generating, but because blast furnace tolerance is huge, therefore many iron and steel enterprises also need to diffuse considerable blast furnace gas simultaneously, and this has also caused a large amount of wastes and the environmental pollution of resource.
And China is the country that needs very much Sweet natural gas simultaneously, annual a large amount of inlet pipeline Sweet natural gas and natural gas liquids (LNG), produce natural gas liquids (LNG) if therefore can utilize these coke-oven gas that diffuse and blast furnace gas simultaneously, not only can alleviate the situation of China's energy deficiency, and economic benefit is very objective.
Up to the present, the someone attempted utilizing the coke-oven gas direct liquefaction to produce the scheme of LNG, and this has related in patent 200820132075.5, but owing to contains a large amount of H in the coke-oven gas 2S, naphthalene, tar, CO 2, H 2Component such as O, mercury metal, so direct liquefaction in fact can not realize, can stop up the LNG ice chest, and quality of natural gas can not be up to state standards, and also the output of natural gas liquids is little, benefit is low.Mentioned also that in patent 200810055168.7 a kind of is the method for raw material production natural gas liquids with the coke-oven gas, but there is following problem in this method: 1) coke-oven gas needs to boost with gas blower earlier and do pre-treatment before compression, has so just prolonged flow process, has increased investment and running cost; 2) coke-oven gas needs to be provided with hydrolyzing process after compression, and hydrolyzing process adopts is that the chemical reaction mode changes into inorganic sulfur with organosulfur and removes, and investment is big, energy consumption is high, and the life-span of hydrolysis sweetening agent is also short, and flow process complexity, equipment are many; 3) also need to be provided with thick desulfurization workshop section and smart desulfurization workshop section behind hydrolysis process, thick desulfurization workshop section adopts low-temperature rectisol, polyoxyethylene glycol volume methyl ether method or MDEA technology, also belongs to the technology that investment is big, energy consumption is high; The ZnO desulfurization is adopted in smart desulfurization, and sweetening agent price height, Sulfur capacity is little, running cost is high; 4) technology that its patent adopted when thick desulfurization with CO 2Also removed simultaneously, rather than converted it into CH 4, so the CH of this technology 4Output is little, and is less economical; 5) its methanation process that adopts is three sections reaction technologies of Denmark Topsoe or German Lurgi, and temperature of reaction is up to 500~600 ℃, and flow process complexity, investment are high, and the operational load regulation range is narrow, more is difficult to adapt to contain a large amount of CO, CO after coke-oven gas is joined blast furnace gas 2The component situation of (surpassing 20%); 6) this patent is not provided with the demetalization reactor before deep cooling, will cause the ice chest heat-exchange equipment and corrode rapidly because of the mercury that exists in the coal gas, and equipment operation life is short.
[summary of the invention]
Technical problem to be solved by this invention is to overcome existing defective in the above-mentioned prior art, provide a kind of more efficient, easy, economic coke-oven gas and blast furnace gas to transform the process technology of producing a large amount of natural gas liquids, can be adapted to any CH of 1~30% that contains simultaneously 4, 1~15% CO, 1~15% CO 2With 5~60% H 2The mixed gas of component.
The present invention has adopted following technical proposal to solve its technical problem: the method for a kind of coke-oven gas of high-efficient simple and blast furnace gas feedstock conversion preparing liquefied natural gas, the mixed gas that it is characterized in that coke-oven gas and blast furnace gas passes through following processing step successively: normal temperature and pressure dry desulfurization, coal gas compression, coal gas adsorption cleaning, coal gas isothermal-adiabatic tandem methanation, coal gas adsorption dry and demetalization, cryogenic liquefaction separates, and produces purity greater than 99% high-quality natural gas liquids.
The present invention need not carry out any pre-treatment before compression, do not need to boost yet, directly through a normal temperature, non-pressurized dry desulfurization tower with H 2S takes off below the 10ppmv just can enter compression section, do not need to carry out the hydrolyzing process of chemical reaction after the compression yet, do not need to adopt low-temperature rectisol, the wet method crude desulfurization process of polyoxyethylene glycol volume methyl ether method or MDEA method, and follow-up smart desulfurization process, directly adopt simple T SA adsorption tower+PSA adsorption tower series connection purification process, utilize good sorbent material just with all naphthalenes, tar, benzene, remaining organosulfur, impurity such as inorganic sulfur are disposable to be removed totally, whole process is physical dry process completely, compare with wet process with aforesaid chemistry, flow process is simplified significantly, and is simple to operate, investment and working cost also will significantly reduce.
Isothermal of the present invention-adiabatic tandem methanation process, owing to wait hotbed may command temperature of reaction between 250~320 ℃, the therefore CO+CO in the raw material coal gas no matter 2The content height, how operational load changes, do not influence operation, so both can adapt to the gas mixture of coke-oven gas and blast furnace gas, also can adapt to independently coke-oven gas, and lack first stage reactor and two vapour generators than three sections traditional reaction process, temperature of reaction also reduces greatly, therefore investment and running cost descend significantly, and turndown ratio then increases (can reach 10-100%) greatly, and with the CO+CO in the coal gas 2Changed into CH all 4Product, reasonably proportioning coke-oven gas and blast furnace gas ratio can also also substantially all be converted into CH with the H2 in the coke-oven gas 4Therefore product has improved CH greatly 4Output and economic benefit.
Among the present invention, the coal gas after the methanation removes H through super-dry and demetalization reactor 2Enter the LNG ice chest behind O and the mercury, isolate normal pressure ,-163 ℃ natural gas liquids, the discharging gas that does not coagulate is sent the battery limit (BL) at last and is made fuel then as the resurgent gases of cleaning section.
The major advantage of this technology:
1) there are not unstripped gas booster fan and complicated pretreatment operation before the compression, there are not hydrolysis reaction operation and wet method crude desulfurization, the smart desulfurization process of ZnO after the compression, only by simple normal temperature and pressure dry desulfurization and adsorption type physical cleaning process, just that gas purification is clean, flow process is simple, easy and simple to handle, reduced investment, running cost are low.
2) owing to there has not been the complicated CO that takes off 2Operation, and in coke-oven gas, mixed an amount of low value blast furnace gas, therefore can be with CO, CO in the coke-oven gas 2And H 2All be converted into CH 4So liquefied natural gas (LNG)-throughput increases considerably (about 30%), economic benefit is better.
3) methanation process adopts independently developed isothermal-adiabatic tandem methanation process, first stage reactor and two vapour generators have been lacked, flow process is simplified significantly, temperature of reaction also reduces greatly, therefore investment and running cost descend significantly, turndown ratio then increases (can reach 10-100%) greatly, and the adaptability of raw material is improved greatly.
4) the demetalization reactor that is provided with before the LNG ice chest can be clean with the mercury removal in the coal gas, avoids the heat-exchange equipment corrosion of aluminium in the ice chest, the long period safe and stable operation of assurance device.
[description of drawings]
Accompanying drawing is a process flow sheet of the present invention.
Each sequence number is expressed as respectively among the figure:
The 1-thionizer; The 2-compressor; The 3a-TSA adsorption tower;
The 3b-TSA adsorption tower; The 4-well heater; The 5a-PSA adsorption tower;
The 5b-PSA adsorption tower; Hotbed methanators such as 6-;
7-adiabatic reactor methanator;
The 8-drum; The 9-interchanger; 10-de-salted water preheater;
The 11-water cooler; 12-divides flow container; The 13a-TSA drying tower;
The 13b-TSA drying tower; 14-demetalization reactor; The 15-well heater;
The 16-LNG ice chest; The 17-LNG storage tank; The 18-LNG Loading Pump.
[embodiment]
The invention will be further described below in conjunction with embodiment and accompanying drawing.
With reference to accompanying drawing, processing step of the present invention is as follows successively:
1) normal temperature and pressure dry desulfurization operation
Coke-oven gas and blast furnace gas are directly entering in the dry desulfurization tower 1 near under the non-pressurized situation, owing to wherein be filled with normal-temperature dry sweetening agent efficiently so the H in the coal gas 2S is under the effect of sweetening agent, with the O that contains in the coal gas 2Direct reaction generates elemental sulfur, rests in the thionizer, thereby makes through H in the coal gas behind the thionizer 2S content is less than 10ppm (v%).
2) compression section
Coal gas behind the dry desulfurization boosts to the adsorption cleaning operation that enters postorder behind 0.2~4.0MPa.G by compressor 2.
3) adsorption cleaning operation
The adsorption cleaning operation adopts TSA adsorption tower 3a, 3b series connection PSA adsorption tower 5a, 5b technology, and TSA and PSA are made up of 2-3 adsorption tower respectively, load sorbent materials such as activated alumina, silica gel, activated carbon and molecular sieve efficiently in the adsorption tower simultaneously.
Coal gas after the compression at first enters in the adsorption tower that is in adsorbed state among TSA adsorption tower 3a, the 3b (has an adsorption tower to be in adsorbed state in 2-3 adsorption tower forming the TSA purification) all the time, under high pressure and normal temperature state, the adsorbents adsorb that impurity such as the organosulfur of the naphthalene in the coal gas, tar, benzene and remnants, inorganic sulfur are wherein loaded is got off, after treating that adsorbents adsorb is saturated, computer automatically switches to other tower absorption, adsorbed saturated adsorption tower and then changed regenerative process over to, the regenerative process of TSA adsorption tower is as follows:
A) at first open the program-controlled valve of this adsorption tower bottom, adsorption column pressure is dropped to gaspipe network pressure (30KPa.G is following) against the absorption direction.
B) use the resurgent gases from the PSA operation to be heated to 120~220 ℃ of post-flush TSA beds through well heater 4 then, sorbent material is heated up, the impurity that is adsorbed just at high temperature desorbs.
C) after thermal regeneration is finished, use from the resurgent gases of PSA operation and do not pass through well heater 4, directly, make the temperature of sorbent material drop to normal temperature again with normal temperature state flushing TSA bed.
D) with the coal gas after purifying the TSA adsorption tower is boosted to adsorptive pressure again.
So far, this adsorption tower has just been finished whole regenerative processes, can adsorb again next time, and the above operation that hockets of 2-3 TSA adsorption tower just can realize the continuous purification of coal gas.
Precision in order to ensure purifying is in series with the PSA adsorption tower again behind the TSA adsorption tower.Enter the adsorption tower that is in adsorbed state among PSA adsorption tower 5a, the 5b interior (in 2-3 adsorption tower forming the PSA purification, also having an adsorption tower to be in adsorbed state all the time) through the coal gas after the purification of TSA adsorption tower, under high pressure and normal temperature state, the adsorbents adsorb that the organosulfur of naphthalene in the coal gas, tar, benzene and remnants, inorganic sulfur etc. are wherein loaded is got off, after treating that adsorbents adsorb is saturated, computer automatically switches to other tower absorption, adsorbed saturated adsorption tower and then changed regenerative process over to, the regenerative process of PSA adsorption tower is as follows:
E) at first open the program-controlled valve of this adsorption tower bottom, against the absorption direction adsorption column pressure is dropped to gaspipe network pressure (30KPa.G is following), the coal gas of step-down is just as the regeneration source of the gas of TSA adsorption tower.
F) use the flushing PSA adsorption tower that does not discharge gas with fixed attention from the LNG ice chest then, the impurities partial pressure in the tower is reduced, thereby desorb, the flushing stripping gas is also used as the regeneration source of the gas of TSA adsorption tower.
G) after flushing regeneration is finished, the PSA adsorption tower is boosted to adsorptive pressure again with the coal gas after purifying.
So far, this PSA adsorption tower has just been finished whole regenerative processes, can adsorb again next time, and the above operation that hockets of 2-3 PSA adsorption tower just can realize the continuous purification of coal gas.
Just can disposable whole adsorbing and removings such as the naphthalene in the coal gas, tar, benzene and remaining organosulfur, inorganic sulfur are clean by above simple physics absorption-desorption process, obtain qualified purification coal gas, naphthalene<0.1ppm wherein, tar<0.1ppm, benzene<1ppm, total sulfur<0.1ppm.
4) isothermal-adiabatic tandem methanation operation
Through the purification coal gas behind the adsorption cleaning, after entering the methanation operation, at first by the pyroreaction gas heat exchange behind interchanger 9 and the methanation reaction, be warmed up to 250~320 ℃, enter again etc. in the hotbed methanator 6, adopt tubular structure Deng hotbed methanator 6, filling nickel is methanation catalyst in tubulation, and tubulation feeds de-salted water outward and is used to take place steam, in tubulation under the catalysis of catalyzer, the CO in the coal gas, CO 2And H 2Reaction is converted into needed CH 4Product, the 3.0-10.0MPa.G saturation steam is taken away and produced to reaction institute liberated heat by the outer de-salted water of tubulation, saturation steam is sent outside after stablizing through drum 8 bufferings, thereby methanation reaction is maintained in 250~320 ℃ of temperature ranges all the time, enter again in the adiabatic reactor methanator 7 through the reacted coal gas of isothermal methanation, Zhuan Tian methanation catalyst catalysis therein continues methanation reaction down, finally makes CO+CO 2All change into CH 4, remaining CO+CO 2Content drop to below the 10ppm (v%), reasonably coke-oven gas and blast furnace gas proportioning can also make the H in the coke-oven gas 2Also substantially all change into CH 4Thereby, make the output of final Sweet natural gas reach maximum, most effective.After having finished coal gas behind the two-stage methanation reaction and reclaiming heats through interchanger 9, de-salted water preheater 10 again, be cooled to normal temperature, go postorder adsorption dry and demetalization operation through dividing a flow container 12 to separate water of condensation again through water cooler 11.
5) adsorption dry and demetalization operation
Adsorption dry and demetalization operation are made up of 2-3 platform drying tower, 1 well heater and 1 demetalization reactor.
Coal gas after the methanation at first enters the adsorption tower (having a drying tower to be in the adsorption dry state all the time) that is in the adsorption dry state among drying tower 13a, the 13b in 2-3 drying tower forming drying process, under high pressure and normal temperature state, the H after the methanation in the coal gas 2The molecular sieve desiccant that O is wherein loaded absorbs, wait to adsorb saturated after, computer automatically switches to the absorption of other towers, has adsorbed saturated drying tower and has then changed regenerative process over to, the regenerative process of drying tower is as follows:
H) at first open the program-controlled valve of this adsorption tower bottom, adsorption column pressure is dropped to gaspipe network pressure (30KPa.G is following) against the absorption direction.
I) use the discharged at lower temperature gas (<10 ℃) that do not coagulate from the LNG ice chest to be heated to 180~220 ℃ of post-flush drying tower beds through well heater 15 then, sorbent material is heated up, the H2O that is adsorbed just at high temperature desorbs.
J) after thermal regeneration is finished, use from the discharged at lower temperature flow of QI being obstructed that do not coagulate of LNG ice chest and cross well heater 15, directly, make the temperature of sorbent material drop to normal temperature again with low-temperature condition flushing siccative bed.
K) with dried methanation coal gas drying tower is boosted to adsorptive pressure again.
So far, this drying tower has just been finished whole regenerative processes, can carry out next time dryly again, and the above operation that hockets of 2-3 drying tower just can realize the successive drying of gas.The H of dry back gas 2O content is less than 1ppm.
Dried methanation gas enters in the demetalization reactor 14, at normal temperatures, mercury in the coal gas and the demercuration catalyst reaction that wherein loads, mercury removal is clean, in order to avoid cause the heat-exchange equipment corrosion of aluminium in the follow-up LNG ice chest.
6) cryogenic liquefaction separation circuit
Because the operation through the front has obtained totally (no naphthalene, tar, benzene, NH 3, sulphur, mercury etc.), drying and CH 4The very high Sweet natural gas of content, therefore liquefaction is very simple with regard to what become, after coal gas passes through the pre-cold-peace mix refrigerant refrigeration of interchanger of LNG ice chest 16 inside after the methanation, gas temperature is reduced, and utilizes CH 4And N 2, H 2Deng the boiling-point difference of component, CH at low temperatures 4, C 2+At first be liquefied Deng component, do not separate the CH after the liquefaction thereby do not coagulate component with other 4, C 2+Deng component is exactly needed natural gas liquids (LNG) product, under normal pressure and-163 ℃ of temperature, sends in the LNG storage tank 17 and stores, and sends entrucking outside by LNG Loading Pump 18 again, just can be used as product and has exported.
Not coagulating component (mainly is N 2, Ar etc.) then go adsorption cleaning operation and drying process as the regeneration source of the gas as discharging gas.
Concrete implementation column as shown in the figure, coke-oven gas unstripped gass such as (and blast furnace gases) at first enters the thionizer 1 from the bottom under near the normal pressure and temperature state, under the dry-desulphurizer effect therein with the H in the coal gas 2S takes off below the 10ppm (v%); The coal gas that comes out from thionizer 1 enters in the compressor 2, is pressurized to 0.2~4.0MPa.G by compressor 2; Then, coal gas enters among TSA adsorption tower 3a, the 3b by pipeline, utilize the sorbent material in the TSA adsorption tower that the most of adsorbing and removings of impurity such as the naphthalene in the coal gas, tar, benzene and remaining organosulfur, inorganic sulfur are fallen, adsorb sorbent material after saturated and then be used to resurgent gases from PSA adsorption tower 5a, 5b and heat up by well heater 4 and then the TSA adsorption tower is carried out thermal regeneration; Enter among PSA adsorption tower 5a, the 5b by pipeline again through the coal gas after TSA adsorption tower 3a, the 3b purification, utilize the sorbent material in the PSA adsorption tower further that the whole adsorbing and removings of impurity such as naphthalene, tar, benzene, organosulfur, inorganic sulfur are clean, the coal gas that is purified fully; Purifying coal gas delivers in the interchanger 9 by pipeline again, high-temperature coal gas heat exchange with after the methanation is warmed up to 250~320 ℃, enters etc. in the hotbed methanator 6 by pipeline then, under the catalysis of Zhuan Tian methanation catalyst, make CO, CO in the coal gas therein 2And H 2More methane is produced in reaction, and the reaction process liberated heat then is used for the hot water of reactor shell side is heated into steam, and steam is pooled in the drum 8 and sends the battery limit (BL); Gone out to wait hotbed methanator 6 coal gas afterwards to enter again and continued methanation reaction in the adiabatic reactor methanator 7, made CO, CO by pipeline 2Content be reduced to below the 10ppm (v%); Then, the coal gas of finishing after the thorough methanation enters in the interchanger 9 by pipeline, and heat transferred is purified coal gas; Enter in the de-salted water preheater 10 by pipeline again, with remaining heat heating de-salted water; Enter in the water cooler 11 by pipeline, the water cooling that is cooled is to normal temperature again; Enter in the branch flow container 12 by pipeline then and separate phlegma; Then, enter among TSA drying tower 13a, the 13b, the siccative that loads in the tower that is dried absorbs moisture content, adsorbs saturated drying tower and utilizes ice chest discharging gas to pass through well heater 15 with the siccative thermal regeneration; The dry gas that has gone out TSA drying tower 13a, 13b enters in the demetalization reactor 14 by pipeline again, utilizes catalyst for demetalation wherein at normal temperatures the mercury in the coal gas to be taken off; And then send in the LNG ice chest 16 by pipeline, by cryogenic refrigeration with the CH in the coal gas 4, C 2+Deng composition deliquescence, the CH that has liquefied 4, C 2+Deng component is exactly our needed product: natural gas liquids (LNG); Natural gas liquids send in the LNG storage tank 17 by pipeline and stores, and just can send outside by Loading Pump 18 entruckings at last.
Embodiment 1
Coke-oven gas 8500Nm is arranged 3/ h, component is as follows:
In order to produce more coke-oven gas, allocate the 1700Nm of low value into 3/ h blast furnace gas, composed as follows:
After two kinds of coal gas mix, directly approaching to enter thionizer under 40 ℃ of the non-pressurized 2KPa.G pressure, normal temperature, with H wherein 2S takes off below the 10ppm, enter reciprocating type gas compressor then, be compressed to 1.6MPa.G, enter TSA+PSA adsorption cleaning operation again, disposable whole adsorbing and removings such as the naphthalene in the coal gas, tar, benzene and remaining organosulfur, inorganic sulfur are fallen, obtain naphthalene<0.1ppm, tar<0.1ppm, benzene<1ppm, total sulfur<0.1ppm, pressure 1.5MPa.G, the purification coal gas demethanization operation that temperature is 40 ℃.
In the methanation operation,, make the CO+CO in the mixed gas by isothermal-adiabatic tandem methanation reaction 2All change into CH 4, remaining CO+CO 2Content<10ppm (v%), remaining H 2Content 1.44 (v%), pressure are 1.4MPa.G, and 40 ℃ of temperature enter dry and demetalization operation, dry back H 2O content is less than 1ppm, and mercury content enters the LNG ice chest again and isolates CH less than 0.1ppm after the demetalization 4Content 93.29%, C 2+Content 6.02%, N 2The LNG product of content 0.69% send LNG storage tank stores with-163 ℃ of temperature, normal pressures.The output of natural gas liquids (LNG) is 3478Nm 3/ h.
Because blast furnace gas is a low heat value discharging gas, its value and price are all very low, after the employing present technique changes into LNG, have increased substantially LNG output, its value is greatly improved, so economic benefit are very good.
Embodiment 2
Coke-oven gas 8500Nm is arranged equally 3/ h, component is as follows:
Not having under the situation of blast furnace gas, is raw material with the coke-oven gas only, can adopt present technique equally.
At this moment coke-oven gas directly enters thionizer under 40 ℃ of 2KPa.G pressure, normal temperature, with H wherein 2S takes off below the 10ppm, enter reciprocating type gas compressor then, be compressed to 1.6MPa.G, enter TSA+PSA adsorption cleaning operation again, disposable whole adsorbing and removings such as the naphthalene in the coal gas, tar, benzene and remaining organosulfur, inorganic sulfur are fallen, obtain naphthalene<0.1ppm, tar<0.1ppm, benzene<1ppm, total sulfur<0.1ppm, pressure 1.5MPa.G, the purification coal gas demethanization operation that temperature is 40 ℃.In the methanation operation,, make the CO+CO in the mixed gas by isothermal-adiabatic tandem methanation reaction 2All change into CH 4, remaining CO+CO 2Content<10ppm (v%), remaining H 2Content 42.65 (v%), pressure are 1.4MPa.G, and 40 ℃ of temperature enter dry and demetalization operation, and dry back H2O content is less than 1ppm, and mercury content enters the LNG ice chest again and isolates CH less than 0.1ppm behind the demercuration 4Content 91.59%, C 2+Content 7.65%, N 2The LNG product of content 0.76% send LNG storage tank stores with-163 ℃ of temperature, normal pressures.The output of natural gas liquids (LNG) is 2672Nm 3/ h.
Under the condition of present embodiment, also can produce qualified liquefied natural gas product easily, but output can be lacked about 24% than embodiment 1.

Claims (8)

1. the method for the coke-oven gas of a high-efficient simple and blast furnace gas feedstock conversion preparing liquefied natural gas, the mixed gas that it is characterized in that coke-oven gas and blast furnace gas passes through following processing step successively: normal temperature and pressure dry desulfurization, coal gas compression, coal gas adsorption cleaning, coal gas isothermal-adiabatic tandem methanation, coal gas adsorption dry and demetalization, cryogenic liquefaction separates, and produces purity greater than 99% high-quality natural gas liquids.
2. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas, it is characterized in that: described raw material can be the mixed gas of coke-oven gas and blast furnace gas, can only be coke-oven gas also, as long as contain 1~30% CH in the raw material coal gas 4, 1~15% CO, 1~15% CO 2With 5~60% H 2Component all is applicable to present technique.
3. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas, it is characterized in that: the smart thionizer of coal gas dry-method (1) is worked under normal temperature, normal pressure in the described normal temperature and pressure dry desulfurizing process, by the solid Fe that loads in the thionizer 2O 3One step of sweetening agent is with the H in the coal gas 2S takes off below the 10ppm (v%).
4. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas is characterized in that: gas compressor (2) is compressed to 0.2~4.0MPa.G with coal gas and enters coal gas adsorption cleaning operation in the described coal gas compression process; Coal gas adsorption cleaning operation adopts TSA adsorption tower (3a, 3b) series connection PSA adsorption tower (5a, 5b) technology, TSA adsorption tower and PSA adsorption tower are made up of 2~3 adsorption towers respectively, load activated alumina efficiently in the adsorption tower simultaneously, silica gel, activated carbon and adsorbent of molecular sieve are with the naphthalene in the coal gas, tar, benzene, organosulfur with remnants, the disposable whole adsorbing and removings of inorganic sulfur impurity get off, obtain qualified purification coal gas, the adsorption process of TSA adsorption tower and PSA adsorption tower is carried out at normal temperatures, belong to pure physical process, the adsorbent reactivation of TSA adsorption tower carries out under 120~220 ℃, and the adsorbent reactivation of PSA adsorption tower carries out at normal temperatures.
5. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas, it is characterized in that: comprise isothermal methanation reactor (6) and adiabatic methanation reactor (7) in described isothermal-adiabatic tandem methanation operation, this two reactors in series is formed, purify the pyroreaction gas heat exchange after coal gas at first enters interchanger (9) and methanation reaction, be warmed up to 250~320 ℃, enter again etc. in the hotbed methanator (6), adopt tubular structure Deng hotbed methanation reaction (6), filling nickel is methanation catalyst in tubulation, tubulation feeds de-salted water outward and is used to take place steam, in tubulation under the catalysis of catalyzer, the CO in the coal gas, CO 2All and H 2Reaction is converted into needed CH 4Product, the heat that reaction is emitted is taken away and is produced 3.0~10.0MPa.G steam by the outer de-salted water of tubulation and sends outside, enter again in the adiabatic methanation reactor (7) through the reacted coal gas of isothermal methanation, Zhuan Tian methanation catalyst catalysis therein continues methanation reaction down, produces more CH 4, finally make CO+CO 2All change into CH 4, remaining CO+CO 2Content drop to below the 10ppm (v%), after having finished coal gas behind the two-stage methanation reaction and passing through interchanger (9), de-salted water preheater (10) again and reclaim heat, be cooled to normal temperature through water cooler (11), go the back operation through dividing flow container (12) to separate water of condensation again.
6. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas is characterized in that: coal gas need pass through absorbed type drying (13) general H wherein after the described methanation 2O content is reduced to below the 1ppm (v%), and absorbed type drying (13) can be made up of 2~3 adsorption towers, and filling molecular sieve desiccant in the adsorption tower is at normal temperatures with the H in the gas after the methanation 2O absorbs, and is warmed up to 160~220 ℃ of regeneration again.
7. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas is characterized in that: described dried methanation gas needs remove mercury in the coal gas through a demetalization reactor (14) again.
8. the method for coke-oven gas as claimed in claim 1 and blast furnace gas feedstock conversion preparing liquefied natural gas is characterized in that: in the described cryogenic liquefaction separating technology coal gas after the exsiccant methanation behind the demercuration is directly entered in the LNG ice chest (16), utilize CH 4And N 2, H 2Deng the boiling-point difference of component, make CH at low temperatures 4, C 2+Deng composition deliquescence, thereby separate the CH after the liquefaction with other components 4, C 2+Deng component is exactly needed natural gas liquids (LNG) product, under normal pressure and-163 ℃ of temperature, sends in the LNG storage tank (17) and stores, and the LNG ice chest adopts the mix refrigerant circulation technology of band precooling.
CN2010101760028A 2010-05-19 2010-05-19 Method for preparing liquefied natural gas by converting raw materials of coke oven gas and blast furnace gas CN102250658A (en)

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CN102559285A (en) * 2012-02-27 2012-07-11 重庆钢铁(集团)有限责任公司 Coke oven gas finely-purifying process for multiple combustion engines
CN102827657A (en) * 2012-08-27 2012-12-19 东华工程科技股份有限公司 Isothermal methanation process method for coal to substitute natural gas
CN102887480A (en) * 2012-10-08 2013-01-23 中国石油化工集团公司 CO shift technique by connecting isothermal shift and thermal insulation shift in series
CN102887481A (en) * 2012-10-08 2013-01-23 中国石油化工集团公司 Low water-gas ratio pre-conversion constant-temperature CO conversion technology
CN102942972A (en) * 2012-11-14 2013-02-27 中国电子工程设计院 Method for producing liquefied natural gas by coke oven gas
CN103146447A (en) * 2013-03-20 2013-06-12 神华集团有限责任公司 System for producing CH4-enriched gas and method for producing CH4-enriched gas by employing system
CN103773525A (en) * 2012-10-19 2014-05-07 中冶焦耐工程技术有限公司 Manufacturing method of liquefied natural gas
CN104031710A (en) * 2014-06-27 2014-09-10 中国海洋石油总公司 Process for producing liquefied natural gas by using coke-oven gas
CN104152200A (en) * 2014-08-20 2014-11-19 北京创时能源技术有限公司 Water-saving type compressed natural gas production system and production method thereof
CN104164263A (en) * 2014-08-19 2014-11-26 赛鼎工程有限公司 Method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas
WO2015015069A1 (en) * 2013-07-31 2015-02-05 IFP Energies Nouvelles Process for capturing a heavy metal contained in a wet gas incorporating a heat pump for cooling the gas before removal of the water
CN105349193A (en) * 2015-12-10 2016-02-24 西南化工研究设计院有限公司 Method for making methane-enriched gas in low-temperature and heat exchange mode
CN108102727A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 For the method for coke oven gas purification recycling aromatic hydrocarbons
CN108102728A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The removal methods of organic sulfur in coke-stove gas
CN108102733A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The method of comprehensive utilization of coke-stove gas
CN108102729A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN108130137A (en) * 2017-07-19 2018-06-08 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN108165322A (en) * 2017-07-19 2018-06-15 湖北申昙环保新材料有限公司 The purification method of coke-stove gas
CN108165323A (en) * 2017-07-19 2018-06-15 湖北申昙环保新材料有限公司 The purification method of coal gas
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Publication number Priority date Publication date Assignee Title
CN102559285A (en) * 2012-02-27 2012-07-11 重庆钢铁(集团)有限责任公司 Coke oven gas finely-purifying process for multiple combustion engines
CN102827657A (en) * 2012-08-27 2012-12-19 东华工程科技股份有限公司 Isothermal methanation process method for coal to substitute natural gas
CN102887480A (en) * 2012-10-08 2013-01-23 中国石油化工集团公司 CO shift technique by connecting isothermal shift and thermal insulation shift in series
CN102887481A (en) * 2012-10-08 2013-01-23 中国石油化工集团公司 Low water-gas ratio pre-conversion constant-temperature CO conversion technology
CN103773525A (en) * 2012-10-19 2014-05-07 中冶焦耐工程技术有限公司 Manufacturing method of liquefied natural gas
CN102942972A (en) * 2012-11-14 2013-02-27 中国电子工程设计院 Method for producing liquefied natural gas by coke oven gas
CN102942972B (en) * 2012-11-14 2014-10-15 中国电子工程设计院 Method for producing liquefied natural gas by coke oven gas
CN103146447A (en) * 2013-03-20 2013-06-12 神华集团有限责任公司 System for producing CH4-enriched gas and method for producing CH4-enriched gas by employing system
WO2015015069A1 (en) * 2013-07-31 2015-02-05 IFP Energies Nouvelles Process for capturing a heavy metal contained in a wet gas incorporating a heat pump for cooling the gas before removal of the water
FR3009202A1 (en) * 2013-07-31 2015-02-06 IFP Energies Nouvelles Method of capturing heavy metal content in wet gas integrating heat pump for cooling gas before water removal
CN104031710A (en) * 2014-06-27 2014-09-10 中国海洋石油总公司 Process for producing liquefied natural gas by using coke-oven gas
CN104031710B (en) * 2014-06-27 2016-06-22 中国海洋石油总公司 A kind of technique utilizing oven gas to produce liquefied natural gas
CN104164263A (en) * 2014-08-19 2014-11-26 赛鼎工程有限公司 Method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas
CN104152200A (en) * 2014-08-20 2014-11-19 北京创时能源技术有限公司 Water-saving type compressed natural gas production system and production method thereof
CN105349193A (en) * 2015-12-10 2016-02-24 西南化工研究设计院有限公司 Method for making methane-enriched gas in low-temperature and heat exchange mode
CN108165322A (en) * 2017-07-19 2018-06-15 湖北申昙环保新材料有限公司 The purification method of coke-stove gas
CN108102728A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The removal methods of organic sulfur in coke-stove gas
CN108102733A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The method of comprehensive utilization of coke-stove gas
CN108102729A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN108130137A (en) * 2017-07-19 2018-06-08 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN108102727A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 For the method for coke oven gas purification recycling aromatic hydrocarbons
CN108165323A (en) * 2017-07-19 2018-06-15 湖北申昙环保新材料有限公司 The purification method of coal gas
CN108219863A (en) * 2017-07-19 2018-06-29 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN108342228A (en) * 2017-07-19 2018-07-31 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN108559549A (en) * 2017-07-19 2018-09-21 湖北申昙环保新材料有限公司 The electricity-generating method of coke-stove gas
CN109111341A (en) * 2018-07-25 2019-01-01 戴乐亭 The method of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG
WO2020237563A1 (en) * 2019-05-30 2020-12-03 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and apparatus for the separation of two gaseous streams each containing carbon monoxide, hydrogen and at least one acid gas
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