CN202626134U - Process device for preparing liquefied natural gas (LNG) and hydrogen simultaneously through coke oven gas - Google Patents
Process device for preparing liquefied natural gas (LNG) and hydrogen simultaneously through coke oven gas Download PDFInfo
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- CN202626134U CN202626134U CN 201220294198 CN201220294198U CN202626134U CN 202626134 U CN202626134 U CN 202626134U CN 201220294198 CN201220294198 CN 201220294198 CN 201220294198 U CN201220294198 U CN 201220294198U CN 202626134 U CN202626134 U CN 202626134U
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Abstract
The utility model relates to a process device for preparing liquefied natural gas (LNG) and hydrogen simultaneously through coke oven gas. The process device for preparing the LNG and the hydrogen simultaneously through the coke oven gas comprises a compression device, an oil-removing naphthalene-removing device, a coarse desulfurization device, a fine desulfurization device, a deacidification device, a dewatering device, a cryogenic liquefaction separation device, a rich hydrogen pressure swing adsorption (PSA) hydrogen-extraction device and the like, the coke oven gas is pressurized by the compression device and then sequentially passes through each purifying, liquefaction and separation device by means of pressure difference, so that the LNG and the high-purity hydrogen are obtained at last, the hydrogen content in the LNG <=2000 parts per million, the nitrogen content in the LNG <= 4%, the carbon monoxide content <= 6%, and the purity of the hydrogen reaches 99.99%. The process device for preparing the LNG and the hydrogen simultaneously through the coke oven gas overcomes the defects of an existing device, and saves power consumption compared with the existing device.
Description
Technical field
The utility model relates to the purification and the liquefaction of coke-oven gas to be produced, and being specifically related to the coke-oven gas is that raw material pressurization de-oiling, thick desulfurization, smart desulfurization, depickling, dehydration, cryogenic liquefying separate, and last PSA carries hydrogen and produces the process unit of LNG and co-producing hydrogen.
Background technology
The staple 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 staple has hydrogen, methane, CO, CO
2Deng, its impurity has tar, naphthalene, benzene, hydrogen sulfide, organosulfur etc.The flow process shown in accompanying drawing 1 is adopted in the processing of existing coke-oven gas more, successively through water elution oil wash naphthalene, desulfurization, then carries hydrogen production device through PSA again and extracts the hydrogen in the virgin gas, and liquefaction at last separates system LNG.Methane gas is that stripping gas pressure is normal pressure in the hydrogen process because PSA carries, and for satisfying the processing requirement of next workshop section, needs to increase a cover compression set supercharging, has therefore increased power consumption.In addition, because the demand of hydrogen has vast market, so the utility model provides a kind of new process unit also in continuous increase.
The utility model content
The utility model provides the process unit of a kind of coke-oven gas system LNG and co-producing hydrogen.
This process unit comprises successively:
The naphthalene device is taken off in the compression of virgin gas and normal temperature de-oiling, and this device comprises that a stage compressor and thick de-oiling take off the naphthalene device, two stage compressor or secondary and three-stage compressor, and the naphthalene device is taken off in smart de-oiling;
Thick desulfurizer;
The device of hydrocracking and smart desulfurization; It comprises: the one-level hydrocracking device of iron molybdenum hydrogenation catalyst is housed, fills the desulfurizer of zinc oxide or middle temperature ferrimanganic sweetening agent, randomly; The secondary hydrocracking device of nickel molybdenum hydrogenation catalyst is housed, fills the smart desulfurizer of zinc oxide; As after the one-level hydrogenating desulfurization, total sulfur content can be reduced to target value in the virgin gas, then can save the secondary hydrodesulfurization unit;
The optional hydramine method deacidifying device that exists; As not containing CO in the virgin gas
2Or CO
2Content is lower than 50ppm (mark by volume), then can save this deacidifying device;
The adsorption dewatering device;
The isolating device of purified gas cryogenic liquefying, it comprises that hybrid refrigeration liquefying plant and low temperature fractionation tripping device maybe can realize other low temperature separation units with low temperature fractionation tripping device identical separation effect;
With
Pressure swing adsorption process is carried hydrogen production device.
Preferably, to take off the naphthalene device be to have filled 2-16 adsorbent bed adsorption tower in thick de-oiling.Preferably, to take off the naphthalene device be to have filled 2-16 adsorbent bed adsorption tower in smart de-oiling.Sorbent material described here is gac preferably.
Preferably, thick sweetener is the thick thionizer that adopts the gac dry desulfurizing process.
Preferably, the adsorption dewatering device is isobaric adsorption dry device or transformation adsorption dry device; Be more preferably isobaric adsorption dry device, further the isobaric adsorption dry device of two towers or three towers preferably.More preferably, the isobaric adsorption dry device of this three tower comprises three drying towers, a well heater, a water cooler, a gas-liquid separator; Two is the dryer tower in three drying towers, a drying aid tower.
Preferably, said adsorption dewatering device comprises:
First drying tower and second drying tower, the two alternately is in drying process and regenerative process first drying tower and second drying tower,
The 3rd drying tower,
Well heater,
Gas-liquid separator and
Water cooler,
Each drying tower has one or two or a plurality of sorbent material composite bed,
The transfer lime of virgin gas is divided into two branch roads i.e. first branch road and second branch road, and first valve wherein is set on first branch road; After first valve, divide three the tunnel to lead to liquefaction system via ingress pipe, first drying tower and the 3rd valve of second valve, first drying tower respectively again; Ingress pipe, second drying tower and the 5th valve via the 4th valve, second drying tower lead to liquefaction system, and are connected to the derivation port of water cooler via the ingress pipe of the delivery line of optional valve, gas-liquid separator, gas-liquid separator, gas-liquid separator; Above-mentioned second branch road is connected to the ingress pipe of water cooler respectively via the tenth valve and the 11 valve with via the 12 valve and the 13 valve; Between first drying tower and the 3rd valve, draw arm and between second drying tower and the 5th valve, draw arm; These two arms are respectively via converging an end that is connected to well heater after the 8th valve and the 9th valve; The other end of well heater is connected to an end of the 3rd drying tower, the other end of drying tower via pipe connection on the pipeline between the 12 valve and the 13 valve; Between first drying tower and second valve, draw arm and between second drying tower and the 4th valve, draw arm, these two arms are connected on the pipeline between the tenth valve and the 11 valve via converging after the 6th valve and the 7th valve respectively.
Preferably, the hybrid refrigeration liquefying plant comprises that liquefaction is with ice chest and mix refrigerant compression cycle system; The low temperature fractionation tripping device is the combination of cryogenic high pressure rectifying tower and low-temp low-pressure rectifying tower; As adopt other low temperature separation units that can realize the identical separation purpose, and then be the separate unit rectifying tower, the combination of flashing tower and rectifying tower, perhaps combination of flashing tower etc.
Preferably, the isolating device of said purified gas cryogenic liquefying comprises: an ice chest, a low-pressure distillation tower; A high-pressure rectification tower, first separator, second separator, this low-pressure distillation tower comprises overhead condenser and tower bottom reboiler; This high-pressure rectification tower comprises tower still and overhead condenser
Wherein, this ice chest comprises:
Liquid-phase mixing cryogen inlet, it is connected with first liquid channel of ice chest, and the end of an a specific order (the for example first step) of this first liquid channel interchanger from ice chest is drawn a pipeline, via the first throttle valve, is connected with a cryogen backward channel of ice chest,
Gas phase cryogen inlet, it is connected with first gas phase channel of ice chest, and this first gas phase channel is drawn a pipeline from the end of another a specific order (the for example second stage) of interchanger, via the 3rd throttling valve, is connected with above-mentioned cryogen backward channel,
A high methane gas import and a methane-rich liquid outlet of being connected with second gas phase channel of ice chest, this methane-rich liquid outlet is connected with the methane-rich liquid inlet of the tower bottom reboiler of low-pressure distillation tower,
With the channel attached mixed flow thigh inlet of the mixed flow thigh of ice chest and a mixed flow thigh outlet; This mixed flow thigh inlet is positioned at the ice chest intermediate heat; This mixed flow thigh inlet is connected with the methane-rich liquid outlet of the tower bottom reboiler of low-pressure distillation tower; This mixed flow thigh outlet is connected with the mixed flow thigh inlet of high-pressure rectification Tata still
With a channel attached natural gas liquids inlet of the natural gas liquids of ice chest and a natural gas liquids outlet, this natural gas liquids inlet is positioned at the ice chest intermediate heat, be connected with the bottom of the tower bottom reboiler of the low-pressure distillation tower gas outlet that liquefies,
With channel attached liquid nitrogen inlet of the liquid nitrogen of ice chest and liquid nitrogen outlet, the liquid nitrogen outlet is drawn a pipeline and is connected with the low-pressure distillation tower overhead condenser via the 4th throttling valve, be connected with high pressure distillation column overhead condensing surface via the 5th throttling valve,
Export gentle nitrogen inlet with the channel attached gas nitrogen of the gas nitrogen of ice chest, this gas nitrogen inlet is connected with the top exit of low-pressure distillation tower overhead condenser with high-pressure rectification column overhead condensing surface,
With channel attached hydrogen rich gas outlet of the hydrogen rich gas of ice chest and hydrogen rich gas inlet, this hydrogen rich gas inlet is connected with the top exit of second separator,
The rich nitrogen outlet and the rich nitrogen inlet that are connected with the rich channel of nitrogen of ice chest, this richness nitrogen inlet is connected with the top exit of first separator,
The tower bottom reboiler of low-pressure distillation tower comprises: a methane-rich liquid inlet, a methane-rich liquid outlet, a bottom liquefaction gas outlet.
The overhead condenser of low-pressure distillation tower is connected with an inlet of first separator, and its top exit is connected with the gas nitrogen inlet of ice chest,
The tower still of high-pressure rectification tower has outlet at bottom, and this outlet at bottom is connected with the middle part of low-pressure distillation tower via the 6th throttling valve, and has an inlet, be connected with the mixed flow thigh outlet of ice chest,
The evaporator overhead condenser of high-pressure rectification tower is connected with an inlet of second separator, and its top exit is connected with the gas nitrogen inlet of ice chest,
The outlet at bottom of first separator is connected with low-pressure distillation tower, and its top exit is connected with the rich nitrogen inlet of ice chest
The outlet at bottom of second separator is connected with the high-pressure rectification tower, and its top exit is connected with the hydrogen rich gas inlet of ice chest.
Adopt the process method of the device of the utility model to carry out in order according to the following steps:
A) naphthalene is taken off in virgin gas compression and normal temperature de-oiling
This step comprises: compress through a compressor (i.e. a stage compressor) one-level from the coke-oven gas outside the battery limit (BL) (virgin gas) and (for example boost to 0.1～0.5MPa) and get into thick de-oiling and take off and carry out preliminary de-oiling in the naphthalene device and take off naphthalene; Passing through another compressor (be two stage compressor, or secondary and three-stage compressor) then continues to boost (for example to 0.45～3.0MPa) and enter into smart de-oiling and take off the further de-oiling and take off naphthalene of naphthalene device.
Should remove the naphthalene that possibly work the mischief to back workshop section, tar, dust etc. before the postorder workshop section earlier and be prone to coagulate or easy crystalline material delivering to from the coke-oven gas outside the battery limit (BL).Virgin gas after coke-oven gas compressor one-level compression get into thick de-oiling take off the naphthalene device (can fill 2 to 16, preferred 4-14, more preferably 6-14, preferred especially 8-12 adsorbent bed; This sorbent material is gac preferably) in; With the gac is that naphthalene is taken off in the thick de-oiling of sorbent material; After (or secondary and three grades) continues to boost after the compressor secondary; Send into smart de-oiling take off the naphthalene device (can fill 2 to 16, preferred 4-14, more preferably 6-14, preferred especially 8-12 adsorbent bed, this sorbent material also can be a gac) further de-oiling and take off naphthalene.Wherein through preliminary de-oiling and taking off after the naphthalene, tar content is less than 5mg/Nm
3, preferably less than 2mg/Nm
3And naphthalene content is less than 50mg/Nm
3, preferably less than 30mg/Nm
3, be more preferably less than 20mg/Nm
3, further preferably less than 10mg/Nm
3And wherein take off after the naphthalene tar content less than 1mg/Nm through smart de-oiling
3, be more preferably less than 0.5mg/Nm
3And naphthalene content is less than 5mg/Nm
3, more further preferably less than 1mg/Nm
3, most preferably less than 0.5mg/Nm
3Most preferably, the coal-tar middle oil total content＜1mg/Nm with naphthalene of virgin gas after naphthalene is taken off in smart de-oiling
3Smart de-oiling is a protection operation hydrogenation conversion catalyst afterwards with the purpose of taking off naphthalene.
Charcoal absorption is taken off in the naphthalene device in thick de-oiling needs regeneration after saturated: utilize the superheated vapour that is heated to about 250 ℃～350 ℃ that the naphthalene device is taken off in smart de-oiling and be heated to more than 220～320 ℃; Carry out cold blowing with normal temperature nitrogen again and cool to about 40 ℃, outside the out-of-bounds of cold blowing pneumatic transmission.Sorbent material is changed once approximately half a year under nominal situation.
B) thick desulfurization
This step comprises: the coke(oven)gas (being virgin gas) that de-oiling is taken off behind the naphthalene is sent in the thick desulfurizer (for example thick thionizer); Adopt dry desulfurizing process; Adopt gac as desulfuration adsorbent in the thionizer, the inorganic sulfur in the coke(oven)gas (being inorganic sulfocompound) is removed.Thick desulfurization is difficult to organic sulfide removal (being sulfur-containing organic compound), need be at follow-up c) adopt hydroconversion process that organosulfur is transformed (for example being converted into inorganic sulfur) in the stage further to remove afterwards.
C) hydrocracking and smart desulfurization
This step comprises: the virgin gas from abovementioned steps gets in the one-level hydrocracking device; (for example air speed 500～1500/h) under iron molybdenum hydrogenation catalyst (the for example JT-8 type hydrogenation catalyst of Xibei Chemical Inst's development) effect, to carry out the one-level hydrocracking; So that the organosulfur of the overwhelming majority is converted into inorganic sulfur; Then get in the desulfurizer of filling zinc oxide (or middle temperature ferrimanganic sweetening agent), through zinc oxide (or middle temperature ferrimanganic sweetening agent) with the inorganic sulfur absorbing and removing; Subsequently; Randomly; Get into secondary hydrocracking device, (air speed 500～2000/h) is further with the organosulfur conversion (generally being converted into inorganic sulfur) of remnants at nickel molybdenum hydrogenation catalyst (the for example JT-1 type hydrogenation catalyst of Xibei Chemical Inst's development) effect carrying out down hydrocracking; Then get in the smart desulfurizer of filling zinc oxide hydrogen sulfide absorption, the volume(tric)fraction of total sulfocompound in the virgin gas is reduced to below the 4ppm.The temperature in one-level hydrocracking and two stages of secondary hydrocracking can be 200 ℃～400 ℃, preferred 250～380 ℃, and more preferably 300～350 ℃.
In step, adopt one-level iron molybdenum (the for example JT-8 type hydrogenation catalyst of Xibei Chemical Inst's development) hydrocracking to add zinc oxide (or middle temperature ferrimanganic sweetening agent) desulfurization, secondary nickel molybdenum (like the JT-1 type hydrogenation catalyst of Xibei Chemical Inst's development) hydrocracking adds the zinc oxide desulfurization flow process.The one-level hydrogenating desulfurization can remove the above sulphur of 99v% in the virgin gas, and as after the one-level hydrogenating desulfurization, total sulfur content can be reduced to target value promptly below the 4 volume ppm in the virgin gas, then can save the secondary hydrodesulfurization unit.
The temperature of smart desulfurizer exit gas (promptly leaving the gas of smart desulfurizer) is generally 350～400 ℃ (for example being about 380 ℃).Smart desulfurizer exit gas is at first sent to follow-up d) stage is as hydramine regenerated thermal source in the hydramine method depickling system; Leave behind hydramine method depickling system or the device gas further with the virgin gas heat exchange that gets into before the one-level hydrocracking device; And virgin gas is preheated to certain temperature (for example 250～280 ℃), thereby rational Match cold fluid and hot fluid heat.
Under nominal situation, catalytic hydrogenation catalyst was changed once in 1 year or 2 years.
D) hydramine method depickling
This step comprises: the virgin gas after the desulfurization enters into hydramine method depickling system or device, so that with the CO in the virgin gas
2Content is reduced to below following, the preferred 40ppm of 50ppm (volume(tric)fraction).As not containing CO in the virgin gas
2Or CO
2Content is lower than 50ppm (mark by volume), then can save deacidifying device.
General this area hydramine method commonly used that adopts is taken off CO
2Technology (being also referred to as deacidifying process or acid gas removal body technology) is that 15%～45% hydramine (for example MDEA, the methyldiethanolamine) aqueous solution is as absorption agent with mass concentration for example; One section absorption; One section regeneration recycles after the regeneration of MDEA solution, with the CO in the virgin gas
2Content is reduced to below the 50ppm.This process also can further remove the residual H of possibility in the operation
2S.
E) adsorption dewatering
This step comprises: gets in adsorption dewatering system or the device from the virgin gas of last operation, and can be with moisture removal to dew points at normal pressure≤-76 ℃.Said adsorption dewatering device for example adopts isobaric adsorption dry device or transformation adsorption dry device.
This adsorption dewatering step can adopt this area adsorption dewatering technology or device commonly used, and for example isobaric adsorption dry technology or transformation adsorption dry technology preferably adopt isobaric adsorption dry technology.Isobaric adsorption dry technology of two towers that wherein preferred employing is described below for isobaric adsorption dry technology or isobaric adsorption dry device or three towers or device.
Preferably, when the adsorption dry device adopts two towers equipressure adsorption dry flow process:
From the virgin gas of last operation access road, at first be divided into the two-way air-flow through the adsorption dry device; Wherein first via gas is as first adsorption tower or second adsorption tower of the direct place to go of process gas in drying process; Hocket adsorption process and regenerative process of first adsorption tower and second adsorption tower wherein; Be in the sorbent material that loads in the adsorption tower of drying process the water adsorption in the gas is got off, the gas that is not adsorbed removes the exit passageway of adsorption dry device;
The second road gas gets into regenerative process as resurgent gases, and wherein the regenerative process of adsorption tower comprises thermal regeneration and two steps of cold blowing; In the thermal regeneration step; After this second road gas heater via is warming up to certain temperature (for example 200～300 ℃); Be used for heating and need regenerated second adsorption tower or first adsorption tower, sorbent material is heated up, moisture wherein is able to desorb; Stripping gas mixes with first via gas behind cooling and separatory again, and drying is carried out in the adsorption tower of drying process in the place to go then; In the cold blowing process; From second adsorption tower or first adsorption tower of the direct place to go of the regeneration gas of process gas in regenerative process; The adsorption tower temperature is reduced to normal temperature; Regeneration gas mixes with another road gas as process gas behind cooling and separatory then, and drying is carried out in first adsorption tower or second adsorption tower of drying process in the place to go at last.
Preferably, when the adsorption dry device adopts three towers equipressure adsorption dry flow process:
From the virgin gas of last operation,, at first be divided into the two-way air-flow through the access road of adsorption dry device; Wherein first via gas is as first adsorption tower or second adsorption tower of the direct place to go of process gas in drying process; Hocket adsorption process and regenerative process of first adsorption tower and second adsorption tower wherein; Be in the sorbent material that loads in the adsorption tower of drying process the water adsorption in the gas is got off, the gas that is not adsorbed removes the exit passageway of adsorption dry device;
The second road gas gets into regenerative process as resurgent gases, and wherein the regenerative process of adsorption tower comprises thermal regeneration and two steps of cold blowing; In the thermal regeneration step, this second road gas at first carries out drying through the 3rd adsorption tower, and heater via is warming up to (for example 200～300 ℃ of certain temperatures then; Especially 250～280 ℃) after; Be used for heating and need regenerated second adsorption tower or first adsorption tower, sorbent material is heated up, moisture wherein is able to desorb; Stripping gas mixes with first via gas behind cooling and separatory again, and drying is carried out in the adsorption tower of drying process in the place to go then; In the cold blowing process; From second adsorption tower or first adsorption tower of the direct place to go of the regeneration gas of process gas in regenerative process; The adsorption tower temperature is reduced to normal temperature, and then remove said the 3rd adsorption tower after the heater via heating, the sorbent material in the 3rd adsorption tower is carried out heat drying; Regeneration gas mixes with another road gas as process gas behind cooling and separatory then, and drying is carried out in first adsorption tower or second adsorption tower of drying process in the place to go at last.
In a preferred embodiment; Wherein the adsorption dry device adopts two towers or the isobaric adsorption dry technology of three towers; Wherein each drying tower have independently 2～16, preferred 3～12, more preferably 3～8 adsorbent bed; The adsorbent bed filling independently of each of each drying tower is selected from one or more in 3A or 4A molecular sieve, the activated alumina, can be with moisture removal to dew points at normal pressure≤-76 ℃.
In addition, if adsorption dewatering adopts transformation adsorption dry technology, also belong to the protection domain of this patent, the regeneration of sorbent material can adopt rich carbon monoxide tail gas that postorder liquefaction separating unit comes out as resurgent gases.
F) the purified gas cryogenic liquefying separates
This step comprises: dried raw material gas gets into experience hybrid refrigeration liquefaction process and low temperature fractionation separating technology in the cryogenic liquefying tripping device; Obtained natural gas liquids respectively; The gas of rich carbon monoxide and nitrogen, and hydrogen rich gas (promptly being rich in the gas of hydrogen).
The cryogenic liquefying of virgin gas separates employing hybrid refrigeration liquefaction process and low temperature fractionation separating technology; Purify qualified virgin gas and get into the liquefaction separating unit, in ice chest, liquefy, and adopt foreign gases such as two-tower rectification flow process separating hydrogen gas by means of the high and low pressure rectifying tower, carbon monoxide, nitrogen.
Wherein, In this step f); Virgin gas after ice chest, low-pressure distillation tower bottom reboiler, ice chest will methane component liquefaction wherein, gets into rectifying in the high and low pressure rectifying tower successively in order, and the top from high-pressure tower is isolated the air-flow that is rich in hydrogen and isolated the air-flow that is rich in carbon monoxide and nitrogen from the top of lower pressure column; Obtain natural gas liquids (LNG) from the bottom of low-pressure distillation tower; Its hydrogen content≤2000ppm (preferred≤1000ppm), a nitrogen content≤4% (preferred≤2%), carbon monoxide≤6% (preferred≤3%).This LNG is sent to the LNG storage device stores; In addition, the gas of rich carbon monoxide, nitrogen is sent to the gas that out-of-bounds acts as a fuel, or part goes dewatering unit as transformation absorption regeneration gas; And hydrogen rich gas gets into postorder PSA and carries hydrogen unit extraction hydrogen.
Liquefaction ice chest institute chilling requirement is provided by the mix refrigerant recycle system, and mix refrigerant is by C1～C5 and N
2(be selected from C1, C2, C3, C4 and C5 paraffinic hydrocarbons and N usually
2In four kinds, five kinds or six kinds; They are according to the arbitrary volume ratio or according to the volume ratio that approximately is equal to) form; Utilize in the ice chest that do not coexist of each component boiling point cooling and after throttling valve throttling, cooling; Return the cold junction of ice chest as the refrigeration agent that backflows, cool off the virgin gas and the drag flow refrigeration agent of different warm areas successively, turn back to the mix refrigerant compressor compresses after the refrigeration agent re-heat of backflowing.
As adopting other refrigeration techniques such as the swell refrigeration technology except that above-mentioned hybrid refrigeration liquefaction process; For liquefaction system provides cold; Or adopt other low temperature separating process of realizing identical purpose except that above-mentioned low temperature fractionation separating technology, also belong to the protection domain of this patent.
G) PSA carries hydrogen (being that pressure swing adsorption process is put forward hydrogen technology)
This step comprises: the hydrogen rich gas entering PSA from above-mentioned cryogenic liquefying tripping device carries in the hydrogen production device, obtains product hydrogen after the adsorption through sorbent material (for example molecular sieve).The purity of product hydrogen generally can reach more than 98%, and more preferably purity can reach 99.90%, and further preferred purity can reach 99.99%.
The patent No. is that 92110918 patent " technology of pressure-changed adsorption concentrating hydrogen " provides a kind of PSA of hydrogeneous virgin gas that is applicable to carry ten tower process of dense hydrogen, and this technology application in the art at present is very ripe.
Paper " 50000m in " gas chemical industry "
3The design of/h transformation absorption hydrogen purifying plant " in propose the description of hydrogen production device relevant for the PSA that adopts the 10-3-4/v mode.
Adsorption tower experiences absorption successively at absorption, regenerated different time, multistagely all falls, contraryly put, find time, multistage all liters, step such as fill eventually.The hydrogen rich gas that contains small amount of nitrogen, methane, carbon monoxide gets into PSA and carries the hydrogen unit, at the bottom of adsorption tower, gets into, and under the effect of sorbent materials such as molecular sieve, the foreign gas in the gas mixture is absorbed, and obtains product hydrogen from cat head, and its purity can reach 99.99%; The regeneration of adsorption tower adopt contraryly put, the mode of vacuum desorption, the low pressure stripping gas is that the gas mixture of nitrogen, methane, carbon monoxide etc. can be sent to the gas that out-of-bounds acts as a fuel after compressor boost.
" drying tower " and " adsorption tower " interchangeable use in this application." choosing " expression in this application wantonly " is with or without ".
The advantage of the utility model:
1, PSA being carried the hydrogen unit places whole process flow last; Virgin gas relies on pressure difference to carry hydrogen production device through each refining plant, liquefaction tripping device and PSA in order; Avoided PSA in the existing technology to put forward the Vacuum solutions air-breathing (promptly being carried the adsorbed high methane gas of hydrogen production device) of hydrogen production device by PSA; Need secondary booster to satisfy the situation of postorder high methane gas liquefaction and separation system, saved the second-compressed system, reduced unnecessary power consumption the pressure requirement;
2, produce LNG and hydrogen simultaneously, the marketable value that the two equal tool is very high, market outlook are wide.
Description of drawings
Fig. 1 is the process flow diagram of prior art;
Fig. 2 is the said process unit sketch of the utility model.
Fig. 3 is the isobaric adsorption dry devices of three towers that are used for adsorption dewatering of the utility model.
Fig. 4 be the utility model be used for the isolating two-tower rectification device of purified gas cryogenic liquefying.
Embodiment
The process unit of the utility model comprises:
As shown in Figure 2, the naphthalene device is taken off in the compression of virgin gas and normal temperature de-oiling, and this device comprises that a stage compressor and thick de-oiling take off the naphthalene device, and the naphthalene device is taken off in secondary (or secondary and three grades) compressor and smart de-oiling;
Thick desulfurizer;
The device of hydrocracking and smart desulfurization; It comprises: the one-level hydrocracking device of iron molybdenum hydrogenation catalyst is housed, fills the desulfurizer of zinc oxide (or middle temperature ferrimanganic sweetening agent), randomly; The secondary hydrocracking device of nickel molybdenum hydrogenation catalyst is housed, fills the smart desulfurizer of zinc oxide; As after the one-level hydrogenating desulfurization, total sulfur content can be reduced to target value in the virgin gas, then can save the secondary hydrodesulfurization unit;
Hydramine method deacidifying device; As not containing CO in the virgin gas
2Or CO
2Content is lower than 50ppm (mark by volume), then can save deacidifying device;
The adsorption dewatering device;
The isolating device of purified gas cryogenic liquefying, it comprises that hybrid refrigeration liquefying plant and low temperature fractionation tripping device maybe can realize other low temperature separation units with low temperature fractionation tripping device identical separation effect;
With
Pressure swing adsorption process is carried hydrogen production device.
Preferably, as shown in Figure 3, the adsorption dewatering device of the utility model comprises:
First drying tower (T1) and second drying tower (T2), the two alternately is in drying process and regenerative process first drying tower and second drying tower,
The 3rd drying tower (T3) (that is, the drying aid tower),
Well heater (E1),
Gas-liquid separator (T4) and
Water cooler (E2),
Each drying tower has one or two or a plurality of sorbent material composite bed, 3-20 bed for example, and 4-18 bed, 5-16 bed, 6-14 bed or 8-12 bed,
The transfer lime of virgin gas is divided into two branch roads i.e. first branch road and second branch road, and first valve V1 wherein is set on first branch road; After first valve V1, divide three the tunnel to lead to liquefaction system via ingress pipe (ingress pipe when referring to that this tower is in drying process), the first drying tower T1 and the 3rd valve V3 of second valve V2, the first drying tower T1 respectively again; Ingress pipe, the second drying tower T2 and the 5th valve V5 via the 4th valve V4, the second drying tower T2 lead to liquefaction system, and are connected to the derivation port of water cooler E2 via the ingress pipe of the delivery line of optional valve (not shown), gas-liquid separator T4, gas-liquid separator T4, gas-liquid separator T4; Above-mentioned second branch road is connected to the ingress pipe of water cooler E2 respectively via the tenth valve V10 and the 11 valve V11 with via the 12 valve V12 and the 13 valve V13; Between first drying tower T1 and the 3rd valve V3, draw arm and between second drying tower T2 and the 5th valve V5, draw arm; These two arms are respectively via converging an end (port or lower port) that is connected to well heater E1 after the 8th valve V8 and the 9th valve V9; The other end of well heater is connected to the end (port or lower port) of the 3rd drying tower T3, the other end of drying tower T3 via pipe connection on the pipeline between the 12 valve V12 and the 13 the valve V13; Between first drying tower T1 and second valve V2, draw arm and between second drying tower (T2) and the 4th valve (V4), draw arm, these two arms are connected on the pipeline between the tenth valve V10 and the 11 valve V11 via converging after the 6th valve V6 and the 7th the valve V7 respectively.
Preferably, as shown in Figure 4, the isolating device of this purified gas cryogenic liquefying comprises: an ice chest E1 '; A low-pressure distillation tower T1 '; A high-pressure rectification tower T2 ', the first separator T3 ', the second separator T4 ', this low-pressure distillation tower comprises overhead condenser E2 ' and tower bottom reboiler E4 '; This high-pressure rectification tower comprises tower still and overhead condenser E3 '
Wherein, this ice chest E1 ' comprising:
Liquid-phase mixing cryogen inlet; It is connected with first liquid channel of ice chest, and the end of an a specific order (the for example first step) of this first liquid channel interchanger from ice chest is drawn a pipeline, via first throttle valve V1 '; Be connected with a cryogen backward channel of ice chest
Gas phase cryogen inlet, it is connected with first gas phase channel of ice chest E1 ', and this first gas phase channel is drawn a pipeline from the end of another a specific order (the for example second stage) of interchanger, via the second throttling valve V2 ', is connected with above-mentioned cryogen backward channel,
A high methane gas import and a methane-rich liquid outlet of being connected with second gas phase channel of ice chest E1 ', this methane-rich liquid outlet is connected with the methane-rich liquid inlet of the tower bottom reboiler E4 ' of low-pressure distillation tower T1 ',
With the channel attached mixed flow thigh inlet of the mixed flow thigh of ice chest E1 ' and a mixed flow thigh outlet; This mixed flow thigh inlet is positioned at the ice chest intermediate heat; This mixed flow thigh inlet is connected with the methane-rich liquid outlet of the tower bottom reboiler E4 ' of low-pressure distillation tower T1 '; This mixed flow thigh outlet is connected with the mixed flow thigh inlet of high-pressure rectification T2 ' Tata still
With the channel attached natural gas liquids inlet of the natural gas liquids of ice chest E1 ' and a natural gas liquids outlet; This natural gas liquids inlet is positioned at the ice chest intermediate heat; Be connected with the bottom liquefaction gas outlet of the tower bottom reboiler E4 ' of low-pressure distillation tower T1 '
With channel attached liquid nitrogen inlet of the liquid nitrogen of ice chest E1 ' and liquid nitrogen outlet; The liquid nitrogen outlet is drawn a pipeline and is connected with low-pressure distillation tower overhead condenser E2 ' via the 4th throttling valve V4 '; Be connected with high pressure distillation column overhead condensing surface E3 ' via the 5th throttling valve V5 '
Export gentle nitrogen inlet with the channel attached gas nitrogen of the gas nitrogen of ice chest E1 ', this gas nitrogen inlet is connected with the top exit of high-pressure rectification column overhead condensing surface E3 ' with low-pressure distillation tower overhead condenser E2 ',
With channel attached hydrogen rich gas outlet of the hydrogen rich gas of ice chest E1 ' and hydrogen rich gas inlet, this hydrogen rich gas inlet is connected with the top exit of the second separator T4 ',
The rich nitrogen outlet and the rich nitrogen inlet that are connected with the rich channel of nitrogen of ice chest E1 ', this richness nitrogen inlet is connected with the top exit of the first separator T3 ',
The tower bottom reboiler E4 ' of low-pressure distillation tower T1 ' comprising: a methane-rich liquid inlet, a methane-rich liquid outlet, a bottom liquefaction gas outlet.
The overhead condenser E2 ' of low-pressure distillation tower T1 ' is connected with the inlet of the first separator T3 ', and its top exit is connected with the gas nitrogen inlet of ice chest E1 ',
The tower still of high-pressure rectification tower T2 ' has outlet at bottom, and this outlet at bottom is connected with the middle part of low-pressure distillation tower T1 ' via the 3rd throttling valve V3 ', and has an inlet, be connected with the mixed flow thigh outlet of ice chest,
The evaporator overhead condenser E3 ' of high-pressure rectification tower T2 ' is connected with the inlet of the second separator T4 ', and its top exit is connected with the gas nitrogen inlet of ice chest,
The outlet at bottom of the first separator T3 ' is connected with low-pressure distillation tower T1 ', and its top exit is connected with the rich nitrogen inlet of ice chest E1 '
The outlet at bottom of the second separator T4 ' is connected with high-pressure rectification tower T2 ', and its top exit is connected with the hydrogen rich gas inlet of ice chest E1 '.
Adopt the process method of this process unit to be described below:
As shown in Figure 2, experience compression successively and naphthalene, thick desulfurization, the smart desulfurization of hydrocracking, depickling (CO are taken off in de-oiling from the coke-oven gas outside the battery limit (BL)
2), dehydration, cryogenic liquefying separate, PSA carries hydrogen production device, accomplishes whole flow process.
1) naphthalene is taken off in coke-oven gas compression and de-oiling
Compress through a compressor (i.e. a stage compressor) one-level from the coke-oven gas outside the battery limit (BL) (virgin gas) and (for example to boost to 0.1～0.5MPa) and get into thick de-oiling and take off and carry out preliminary de-oiling in the naphthalene device and take off naphthalene; Passing through another compressor (be two stage compressor, or secondary and three-stage compressor) then continues to boost (for example to 0.45～3.0MPa) and enter into smart de-oiling and take off the further de-oiling and take off naphthalene of naphthalene device.
Naphthalene is taken off in thick de-oiling: take off in the naphthalene device in thick de-oiling and accomplish, purpose is to guarantee the steady running of compression function.
With the gac is sorbent material, and naphthalene, tar and part sulphur, the benzene of the overwhelming majority is removed.Coke(oven)gas from bottom to top gets into thick de-oiling and takes off the naphthalene device, to the coal-tar middle oil content of purified gas less than 5mg/Nm
3(preferably less than 2mg/Nm
3, be more preferably less than 0.5mg/Nm
3), naphthalene content is less than 50mg/Nm
3(preferably less than 30mg/Nm
3, be more preferably less than 20mg/Nm
3, further preferably less than 10mg/Nm
3, more further preferably less than 1mg/Nm
3, most preferably less than 0.5mg/Nm
3) back gets into the back operation, adsorb saturated back fully up to sorbent material and the naphthalene device is taken off in thick de-oiling regenerate.
Charcoal absorption is taken off in the naphthalene device in thick de-oiling needs regeneration after saturated: utilize the superheated vapour that is heated to about 250 ℃～350 ℃ that the naphthalene device is taken off in smart de-oiling and be heated to more than 220～320 ℃; Carry out cold blowing with normal temperature nitrogen again and cool to about 40 ℃, outside the out-of-bounds of cold blowing pneumatic transmission.Sorbent material is changed once approximately half a year under nominal situation.
Naphthalene is taken off in smart de-oiling: coke(oven)gas takes off behind the naphthalene through thick de-oiling that tar, naphthalene etc. are provided with in order further to remove, and purpose is a protection operation hydrogenation conversion catalyst afterwards.Coke(oven)gas after compressor secondary (or secondary and three grades) is pressurized to 0.45～3.0MPa for example through 2 can go here and there, the smart de-oiling of parallel operation takes off the naphthalene device; With the gac is sorbent material; Remaining tar and naphthalene etc. are removed, and tar and naphthalene content＜1mg/Nm behind the naphthalene are taken off in smart de-oiling
3
2) the smart desulfurization of thick desulfurization and hydrocracking
Thick sulfur removal technology has dry method, the multiple flow process of wet method, and physical absorption has propene carbonate method, low-temperature rectisol, NHD etc. in the wet desulphurization.Preferably, adopt dry desulfurizing process, adopt gac in the thionizer, the inorganic sulfur in the coke(oven)gas (being inorganic sulfocompound) is removed as desulfuration adsorbent.
Because of containing organosulfurs such as the thiophene that is difficult to decompose, thioether, mercaptan in the coke(oven)gas, wet desulphurization is difficult to organic sulfide removal, therefore adopts hydrogenating conversion process, and organosulfur is converted into inorganic sulfur.Hydrogenation conversion catalyst commonly used mainly contains type catalyst such as cobalt molybdenum, nickel molybdenum and iron molybdenum.
The said smart desulfurization flow process of the utility model adopts one-level iron molybdenum (like the JT-8 type hydrogenation catalyst of Xibei Chemical Inst's development) hydrocracking to add zinc oxide (or middle temperature ferrimanganic sweetening agent) desulfurization; Randomly, secondary nickel molybdenum (like the JT-1 type hydrogenation catalyst of Xibei Chemical Inst's development) hydrocracking adds the zinc oxide desulfurization flow process.Operational condition is: 200 ℃～400 ℃ of temperature; Technical process is: virgin gas gets into one-level hydrocracking device; (carry out the one-level hydrocracking under 500～1500/h) effects of JT-8 type hydrogenation catalyst air speed at iron-molybdic catalyst; Most organosulfurs are converted into inorganic sulfur, then get into zinc oxide (or middle temperature ferrimanganic sweetening agent) desulfurizer, through zinc oxide (or middle temperature ferrimanganic sweetening agent) with the inorganic sulfur absorbing and removing; Subsequently; Randomly; Get into secondary hydrocracking device, (under 500～2000/h) effects of JT-1 type hydrogenation catalyst air speed, further the organosulfur with remnants is converted into inorganic sulfur at nickel molybdenum catalyst; Then get into the smart desulfurizer of zinc oxide with hydrogen sulfide absorption, total sulfur volume(tric)fraction in the virgin gas is reduced to below the 4ppm.The temperature in one-level hydrocracking and two stages of secondary hydrocracking can be 200 ℃～400 ℃, preferred 250～380 ℃, and more preferably 300～350 ℃.
The one-level hydrogenating desulfurization can remove the above organosulfur of 99v% in the virgin gas, and as after the smart desulfurization of one-level hydrogenation, total sulfur content can be reduced to target value promptly below the 4 volume ppm in the virgin gas, then can save the secondary hydrodesulfurization unit.
Smart desulfurizer Outlet Gas Temperature is about 380 ℃ (being generally 350～400 ℃).Smart desulfurizer exit gas is at first sent to follow-up d) stage is as hydramine regenerated thermal source in the hydramine method depickling system; Leave behind hydramine method depickling system or the device gas further with the virgin gas heat exchange that gets into before the one-level hydrocracking device; And virgin gas is preheated to certain temperature (for example 250～280 ℃); Thereby rational Match cold fluid and hot fluid heat cuts down the consumption of energy.
Under nominal situation, catalytic hydrogenation catalyst was changed once in 1 year or 2 years.
3) MDEA (N methyldiethanol amine) method depickling
Adopt this area hydramine method commonly used to take off CO
2Technology (concrete visible Gu Anzhong etc. outstanding " natural gas liquids technology " the said 2.2.2.1 hydramine of P49 method); For example with mass concentration be 15%～45% the MDEA aqueous solution as absorption agent, one section absorption, one section regeneration; Recycle after the regeneration of MDEA solution, with the CO in the virgin gas
2Content is reduced to below the 50ppm.This process also can further remove the residual H of possibility in the operation
2S.
As not containing CO in the virgin gas
2Or CO
2Content is lower than 50ppm (mark by volume), then can save deacidifying device.
4) adsorption dewatering
Virgin gas entering adsorption dry unit from last operation adopts two towers or the isobaric adsorption dry technology of three towers to remove moisture wherein;
Preferably, when the adsorption dry device adopts two towers equipressure adsorption dry flow process:
From the Sweet natural gas of last operation,, at first be divided into the two-way air-flow through the access road of adsorption dry device; Wherein first via gas is as first adsorption tower or second adsorption tower of the direct place to go of process gas in drying process; Hocket adsorption process and regenerative process of first adsorption tower and second adsorption tower wherein; Be in the sorbent material that loads in the adsorption tower of drying process the water adsorption in the gas is got off, the gas that is not adsorbed removes the exit passageway of adsorption dry device;
The second road gas gets into regenerative process as resurgent gases, and wherein the regenerative process of adsorption tower comprises thermal regeneration and two steps of cold blowing; In the thermal regeneration step; After this second road gas heater via is warming up to certain temperature; Be used for heating and need regenerated second adsorption tower or first adsorption tower, sorbent material is heated up, moisture wherein is able to desorb; Stripping gas mixes with first via gas behind cooling and separatory again, and drying is carried out in the adsorption tower of drying process in the place to go then; In the cold blowing process; From second adsorption tower or first adsorption tower of the direct place to go of the regeneration gas of process gas in regenerative process; The adsorption tower temperature is reduced to normal temperature; Regeneration gas mixes with another road gas as process gas behind cooling and separatory then, and drying is carried out in first adsorption tower or second adsorption tower of drying process in the place to go at last.
Preferably, when the adsorption dry device adopts three towers equipressure adsorption dry flow process:
It is as shown in Figure 3,
The adsorption dry device comprises three drying tower T1, T2 and T3, a well heater E1, a water cooler E2, a gas-liquid separator T4; Two is dryer tower T1, T2 in three drying towers, a drying aid tower T3; Dryer tower drying and regeneration hocket; Regeneration divides heating and cooling two steps.
Be adsorbed as example with drying tower T1, its operating process is described at present:
From the virgin gas of last operation,, at first be divided into the two-way air-flow through the access road of adsorption dry device; The flow of two-way air-flow is regulated through regulating valve V1: the one tunnel as resurgent gases, and one the tunnel as mainstream gas.Wherein mainstream gas is directly removed drying tower T1 through valve V2, and siccative that loads among the drying tower T1 and heavy hydrocarbon remove agent moisture in the gas and heavy hydrocarbon are absorbed, and gas is accomplished to purify through valve V3 and gone postorder liquefaction operation.
Another drying tower T2 is in regenerative process, and the regenerative process of drying tower T2 comprises heating and two steps of cold blowing:
In the thermal regeneration step; Resurgent gases is successively through valve V12, drying tower T3, well heater E1, valve V9, drying tower T2, valve V7, valve V11, water cooler E2, gas-liquid separator T4; Converge with the process gas that is about to enter into the drying tower T1 that is in adsorption process again; Get into the drying tower T1 that is in adsorption process through valve V2, accomplish heat-processed drying tower T2.
Resurgent gases is taken from process gas, does not need external any carrier gas in the thermal regeneration process, and resurgent gases is returned process gas after regeneration step.When drying tower T2 was heated, regeneration gas cooled off predrying tower T3, drying tower T3 internal adsorption agent and material accumulation of heat is taken away got into well heater E1 again, reduced the required energy expenditure of thermal regeneration.Resurgent gases is before entering drying tower T2, and super-dry tower T3 is predrying, and the moisture content in the resurgent gases is (moisture content in the virgin gas has reduced 80-99% usually) seldom, reduces the drying load of drying tower T2.
In the cold blowing step; Resurgent gases is successively through valve V10, valve V7, drying tower T2, valve V9, well heater E1, drying tower T3, valve V13, water cooler E2, gas-liquid separator T4; Converge with the process gas that is about to enter into the drying tower T1 that is in adsorption process again; Be among the drying tower T1 of adsorption process through valve V2 entering, accomplish process of cooling drying tower T2.
Equally, resurgent gases is taken from process gas, does not need external any carrier gas in the thermal regeneration process, and resurgent gases is returned process gas after regeneration step.Drying tower T2 is being carried out refrigerative simultaneously, regeneration gas heats predrying tower T3, drying tower T2 internal adsorption agent and material accumulation of heat is taken away got into well heater E1 again, reduces the required energy expenditure of thermal regeneration.Resurgent gases is before entering drying tower T3, and super-dry tower T2 is predrying, and the moisture content in the resurgent gases seldom reduces the drying load of drying tower T3.
Drying tower T2 waits for getting into adsorption operations next time through after the above-mentioned heating and cooling process.
The regenerative process of the regenerative process of drying tower T1 and drying tower T2 is just the same, just needs the valve numbering of action different.Two drying towers replace absorption regeneration, realize operate continuously processing gas.
The composite bed of each drying tower can load in 3A or the sorbent materials such as 4A molecular sieve, activated alumina one or both or multiple.
Then, T2 is adsorbed as example with drying tower, and its operating process is described:
From the virgin gas of last operation access road, at first be divided into the two-way air-flow through the adsorption dry device; The flow of two-way air-flow is regulated through regulating valve V1: the one tunnel as resurgent gases, and one the tunnel as mainstream gas.Wherein mainstream gas is directly removed drying tower T2 through valve V4, and siccative that loads among the drying tower T2 and heavy hydrocarbon remove agent moisture in the gas and heavy hydrocarbon are absorbed, and gas is accomplished to purify through valve V5 and gone postorder liquefaction operation.
Another drying tower T1 is in regenerative process, and the regenerative process of drying tower T1 comprises heating and two steps of cold blowing:
In the thermal regeneration step, resurgent gases is successively through valve V12, drying tower T3, well heater E1, valve V
8, drying tower T1, valve V6, valve V11, water cooler E2, gas-liquid separator T4; Converge with the process gas that is about to enter into the drying tower T2 that is in adsorption process again; Get into the drying tower T2 that is in adsorption process through valve V4, accomplish heat-processed drying tower T1.
Resurgent gases is taken from process gas, does not need external any carrier gas in the thermal regeneration process, and resurgent gases is returned process gas after regeneration step.When drying tower T1 was heated, regeneration gas cooled off predrying tower T3, drying tower T3 internal adsorption agent and material accumulation of heat is taken away got into well heater E1 again, reduced the required energy expenditure of thermal regeneration.Resurgent gases is before entering drying tower T1, and it is predrying to have passed through predrying tower T3, and the moisture content in the resurgent gases seldom reduces the drying load of drying tower T1.
In the cold blowing step; Resurgent gases is successively through valve V10, valve V6, drying tower T1, valve V8, well heater E1, drying tower T3, valve V13, water cooler E2, gas-liquid separator T4; Converge with the process gas that is about to enter into the drying tower T2 that is in adsorption process again; Get into the drying tower T2 that is in adsorption process through valve V4, accomplish process of cooling drying tower T1.
Equally, resurgent gases is taken from process gas, does not need external any carrier gas in the thermal regeneration process, and resurgent gases is returned process gas after regeneration step.Drying tower T1 is being carried out refrigerative simultaneously, regeneration gas heats predrying tower T3, drying tower T1 internal adsorption agent and material accumulation of heat is taken away got into well heater E1 again, reduces the required energy expenditure of thermal regeneration.Resurgent gases is before entering drying tower T3, and super-dry tower T1 is predrying, and the moisture content in the resurgent gases seldom reduces the drying load of drying tower T3.
Drying tower T1 waits for getting into adsorption operations next time through after the above-mentioned heating and cooling process.
Randomly; The adsorption dry device adopts two towers or the isobaric adsorption dry technology dehydration of three towers; Each adsorption tower has 2-16, preferred 3-12, more preferably 3-8 is individual adsorbent bed; Wherein sorbent material adopts one or more in 3A molecular sieve, 4A molecular sieve and the activated alumina, can be with moisture removal to dew points at normal pressure≤-76 ℃.
Adopt transformation adsorption dry technology like adsorption dewatering, also belong to the protection domain of this patent, the regeneration of sorbent material can adopt rich carbon monoxide tail gas that postorder liquefaction separating unit comes out as resurgent gases.
5) cryogenic liquefying separates
Cryogenic liquefying separates can adopt this area refrigeration techniques commonly used such as swell refrigeration technology (this technology has description in " natural gas liquids technology " P60 of works such as Gu Anzhong).
Preferably, the cryogenic liquefying of virgin gas separates employing mix refrigerant refrigeration cycle technology provides cold, and adopts low temperature fractionation separating technology separating impurity gas; Purify in the ice chest of qualified virgin gas entering cryogenic liquefying tripping device, the cold that relies on mix refrigerant refrigeration cycle technology to provide liquefies methane component; The low temperature fractionation separating technology adopts the two-tower rectification flow process, removes hydrogen, nitrogen, carbon monoxide in the virgin gas.
The embodiment of mix refrigerant refrigeration cycle technology is following:
Mix refrigerant is by C1～C5 and N
2Form and (be selected from C1, C2, C3, C4 and C5 paraffinic hydrocarbons and N usually
2In four kinds, five kinds or six kinds; They are according to the arbitrary volume ratio or according to the volume ratio that approximately is equal to); Gas phase after the mix refrigerant compressor boost and liquid-phase mixing cryogen utilize in the ice chest that do not coexist of each component boiling point cooling and after throttling valve throttling, cooling; Return the cold junction of ice chest as the refrigeration agent that backflows, cool off the virgin gas and the positive flow refrigeration agent of different warm areas successively, turn back to the compression of mix refrigerant suction port of compressor after the refrigeration agent re-heat of backflowing.The flow process of mix refrigerant refrigeration cycle technology is explained with reference to accompanying drawing 4: one liquid-phase mixing cryogen at first gets into a liquid channel of ice chest; Therein by precooling to-30 ℃～-80 ℃ approximately, behind throttling valve V1 throttling to 0.2～0.8MPaA with ice chest in the mixed refrigerant stream thigh that backflows to converge and oppositely get into ice chest be that heat exchanger package provides cold.One gas phase refrigerant flow thigh is cooled to-135 ℃～-171 ℃ through a gas phase channel of ice chest, and the reverse ice chest that gets into provides cold for it behind throttling valve V2 ' throttling to 0.2～0.8MPaA again.
The embodiment of low temperature fractionation separating technology is following:
Adopt the two-tower rectification flow process; Referring to accompanying drawing 4: the high methane gas of hydrogen, nitrogen, carbon monoxide at first gets into ice chest E1 ' through the gas phase channel of ice chest E1 '; Gas mixture precooling cooling box E1 ' after-100～-140 ℃ gets into the tower bottom reboiler E4 ' of low-pressure distillation tower T1 ', for it heat is provided as the thermal source of low-pressure distillation tower T1 '; While self temperature is reduced to-105～-145 ℃; Return the ice chest E1 ' from the effusive stream thigh of the tower bottom reboiler E4 ' of low-pressure distillation tower T1 ', continue in the postorder heat exchanger package of ice chest E1 ', to cool off, remove high-pressure rectification tower T2 ' tower still after being cooled to-145～-170 ℃; Rectifying in high-pressure rectification tower T2 ', high-pressure rectification tower T2 ' working pressure is controlled at 1.0～5.0MPaA; The gas phase that high-pressure rectification tower T2 ' cat head is drawn gets into condensation among the overhead condenser E3 '; The back gets among first separator T4 '; Go into the high-pressure rectification tower T2 ' from the liquid-phase reflux that separator T4 ' bottom obtains; Skimmer T4 ' top obtains hydrogen rich gas, and hydrogen rich gas goes out liquefaction and separation system after ice chest E1 ' re-heat; The liquid phase that high-pressure rectification tower T2 ' draws the bottom through throttling valve V3 ' expenditure and pressure to 0.15～1.0MPaA, gets into the middle part rectifying of low-pressure distillation tower T1 ', and low-pressure distillation tower T1 ' working pressure is controlled at 0.15～1.0MPaA; Low-pressure distillation tower T1 ' draws at the top gas phase and sends into condensation among the overhead condenser E2 '; Then through the second separator T3 ' separatory; Separator T3 ' bottom liquid phases passes back among the low-pressure distillation tower T1 '; The top obtains rich carbon monoxide, nitrogen, and rich carbon monoxide, nitrogen reclaim cold through ice chest E1 ', go out liquefaction and separation system after the re-heat; Hydrogen content≤2000ppm among the LNG that low-pressure distillation tower T1 ' bottom obtains, nitrogen≤4%, carbon monoxide≤6%; The LNG that goes out low-pressure distillation tower T1 ' is the LNG product after returning and continuing to be chilled to-145～-170 ℃ among the ice chest E1 '.
Preferably; Low-pressure distillation tower T1 ' and high-pressure rectification tower T2 ' overhead condenser all adopt liquid nitrogen that cold is provided; Nitrogen is divided into two-way after ice chest E1 cooling; After throttling valve V4 ' and V5 ' throttling, form liquid nitrogen respectively and get into respectively among overhead condenser E2 ' and the E3 ' of low-pressure distillation tower and high-pressure rectification tower to rectifying tower provides cold, the two-way liquid nitrogen converges after gasifying with E2 ', E3 ' heat exchange respectively, through going out system after the ice chest E1 ' re-heat.
The virgin gas of hydrogen, nitrogen, carbon monoxide is successively after ice chest E1 ', low-pressure distillation tower bottom reboiler E4 ', ice chest E1 ' are with methane component liquefaction wherein; Get into successively that rectifying separation removes hydrogen, nitrogen, carbon monoxide in the high pressure, low-pressure distillation tower T2 ', T1 '; Obtain hydrogen rich gas from high-pressure rectification tower T2 ' top; From low-pressure distillation tower T1 ' top to rich nitrogen and carbon monoxide; Hydrogen content≤2000ppm from the LNG product that low-pressure distillation tower T1 ' bottom obtains, a nitrogen content≤4%, carbon monoxide≤6%.LNG sends to the LNG storage system stores; Rich carbon monoxide, nitrogen are sent to the gas that out-of-bounds acts as a fuel, or part is gone the resurgent gases of dewatering unit as transformation adsorption dewatering technology; Hydrogen rich gas gets into postorder PSA and carries the hydrogen system purifying hydrogen of hydrogen.
As adopting other refrigeration techniques such as the swell refrigeration technology except that above-mentioned hybrid refrigeration liquefaction process; For liquefaction system provides cold; Or adopt other low temperature separating process of realizing identical purpose except that above-mentioned low temperature fractionation separating technology, also belong to the protection domain of this patent.
6) PSA carries hydrogen production device
PSA carries hydrogen production device and is positioned at the last of a whole set of flow process; Hydrogen rich gas with cryogenic liquefying tripping device mesohigh rectifying tower top is as virgin gas; Adopt PSA to put forward hydrogen technology; Under the effect of sorbent materials such as molecular sieve, the foreign gas in the gas mixture is absorbed, thereby obtain product hydrogen, its purity can reach 99.99%.
As a kind of embodiment; PSA puies forward the mode of hydrogen process using 10-5-3/v, promptly adopts 10 towers all to press for 5 times, 3 towers charging simultaneously vacuum desorption technology; And can be according to the difference of the lifting capacity of virgin gas; Switch nine (9-3-4/V), eight (8-2-4/V), the mode of five (5-1-2/V) of adopting.Each adsorption tower alternate cycles operation is continuously imported to reach virgin gas, and product gas is continuously exported.Vacuum solutions is air-breathing to be that the gas mixture of nitrogen, methane, carbon monoxide etc. can be sent to the gas that out-of-bounds acts as a fuel, or part is gone the resurgent gases of dewatering system as transformation adsorption dewatering technology.The entire operation process is carried out at ambient temperature.
Each adsorber through absorption (A) step-down balance 1 (E1D), step-down balance 2 (E2D), step-down balance 3 (E3D), step-down balance 4 (E4D), step-down balance 5 (E5D), contraryly put (D), vacuumize (VC), the balance 5 of boosting (E5R), the balance 4 of boosting (E4R), the balance 3 of boosting (E3R), the balance 2 of boosting (E2R), the balance 1 of boosting (E1R), final pressurising (FR) wait adsorption cycle of 14 operation stepss completion.The purpose of vacuum pumping is to make the thorough desorb of waste gas, to satisfy plant yield height, requirement that hydrogen purity is high.Ten adsorption towers are carried out absorption and regenerative operation successively, and virgin gas is imported continuously, and product hydrogen is constantly exported.
Number of patent application is that the patent " technology of pressure-changed adsorption concentrating hydrogen " of 92110918.0 (CN1070840A) provides a kind of PSA of hydrogeneous virgin gas that is applicable to carry ten tower process of dense hydrogen, and this technology application in the art at present is very ripe.
Paper " 50000m in the periodical " gas chemical industry " (2000, the 4th phase, author Li Jie)
3The design of/h transformation absorption hydrogen purifying plant " in propose the description of hydrogen production device relevant for the PSA that adopts the 10-3-4/v mode.The difference of flow process that the utility model adopts and existing technical process is it and PSA is carried hydrogen production device place the last of whole process flow, simultaneously through the combination of above-mentioned each operation, optimizes whole flow process.The Vacuum solutions air-breathing (promptly being carried the adsorbed high methane gas of hydrogen production device by PSA) of carrying hydrogen production device because of PSA need further remove foreign gases such as nitrogen, carbon monoxide and liquefaction; As adopt existing technical process, need the high methane gas secondary booster with the requirement of the high methane gas liquefaction tripping device that satisfies postorder pressure; Adopt the said flow process of the utility model, virgin gas relies on pressure difference to carry hydrogen production device through each refining plant, liquefaction tripping device and PSA in order, has saved the secondary booster device, thereby can reduce unnecessary power consumption.
Claims (10)
1. a coke-oven gas prepares the process unit of natural gas liquids and co-producing hydrogen, it is characterized in that this process unit comprises successively:
The naphthalene device is taken off in the compression of virgin gas and normal temperature de-oiling, and this device comprises that a stage compressor and thick de-oiling take off the naphthalene device, two stage compressor or secondary and three-stage compressor; And the naphthalene device is taken off in smart de-oiling;
Thick desulfurizer;
The device of hydrocracking and smart desulfurization; It comprises: the one-level hydrocracking device of iron molybdenum hydrogenation catalyst is housed, and string is filled the desulfurizer of zinc oxide or middle temperature ferrimanganic sweetening agent, randomly; The secondary hydrocracking device of nickel molybdenum hydrogenation catalyst is housed, and string is filled the smart desulfurizer of zinc oxide;
The optional hydramine method deacidifying device that exists;
The adsorption dewatering device;
The isolating device of purified gas cryogenic liquefying, it comprises hybrid refrigeration liquefying plant and low temperature separation unit;
With
Pressure swing adsorption process is carried hydrogen production device.
2. according to the process unit of claim 1, it is characterized in that it is to have filled 2-16 adsorbent bed adsorption tower that the naphthalene device is taken off in thick de-oiling.
3. according to the process unit of claim 1, it is characterized in that it is to have filled 2-16 adsorbent bed adsorption tower that the naphthalene device is taken off in smart de-oiling.
4. according to the process unit of claim 1, it is characterized in that sorbent material is a gac.
5. according to the device of claim 1, it is characterized in that thick sweetener is the thick thionizer that adopts the gac dry method.
6. according to the process unit of claim 1, it is characterized in that the adsorption dewatering device is isobaric adsorption dry device or transformation adsorption dry device.
7. according to the process unit of claim 6, it is characterized in that this adsorption dewatering device comprises:
First drying tower and second drying tower, the two alternately is in drying process and regenerative process first drying tower and second drying tower,
The 3rd drying tower,
Well heater,
Gas-liquid separator and
Water cooler,
Each drying tower has one or two or a plurality of sorbent material composite bed, and the transfer lime of virgin gas is divided into two branch roads i.e. first branch road and second branch road, and first valve wherein is set on first branch road; After first valve, divide three the tunnel to lead to liquefaction system via ingress pipe, first drying tower and the 3rd valve of second valve, first drying tower respectively again; Ingress pipe, second drying tower and the 5th valve via the 4th valve, second drying tower lead to liquefaction system, and are connected to the derivation port of water cooler via the ingress pipe of the delivery line of optional valve, gas-liquid separator, gas-liquid separator, gas-liquid separator; Above-mentioned second branch road is connected to the ingress pipe of water cooler respectively via the tenth valve and the 11 valve with via the 12 valve and the 13 valve; Between first drying tower and the 3rd valve, draw arm and between second drying tower and the 5th valve, draw arm; These two arms are respectively via converging an end that is connected to well heater after the 8th valve and the 9th valve; The other end of well heater is connected to an end of the 3rd drying tower, the other end of drying tower via pipe connection on the pipeline between the 12 valve and the 13 valve; Between first drying tower and second valve, draw arm and between second drying tower and the 4th valve, draw arm, these two arms are connected on the pipeline between the tenth valve and the 11 valve via converging after the 6th valve and the 7th valve respectively.
8. according to any one the process unit of claim 1-7; It is characterized in that; The hybrid refrigeration liquefying plant comprises liquefaction with ice chest and mix refrigerant compression cycle device, and low temperature separation unit is the combination of separate unit rectifying tower, flashing tower and rectifying tower or the combination of flashing tower.
9. according to the process unit of claim 1, it is characterized in that low temperature separation unit is the low temperature fractionation tripping device, this low temperature fractionation tripping device comprises the combination of cryogenic high pressure rectifying tower and low-temp low-pressure rectifying tower.
10. according to Claim 8 process unit; It is characterized in that: the isolating device of this purified gas cryogenic liquefying comprises: an ice chest, a low-pressure distillation tower, a high-pressure rectification tower; First separator, second separator; This low-pressure distillation tower comprises overhead condenser and tower bottom reboiler, and this high-pressure rectification tower comprises tower still and overhead condenser
Wherein, this ice chest comprises:
Liquid-phase mixing cryogen inlet, it is connected with first liquid channel of ice chest, and the end of this first liquid channel a specific order of interchanger from ice chest is drawn a pipeline, via the first throttle valve, is connected with a cryogen backward channel of ice chest,
Gas phase cryogen inlet, it is connected with first gas phase channel of ice chest, and this first gas phase channel is drawn a pipeline from the end of another a specific order of interchanger, via the 3rd throttling valve, is connected with above-mentioned cryogen backward channel,
A high methane gas import and a methane-rich liquid outlet of being connected with second gas phase channel of ice chest, this methane-rich liquid outlet is connected with the methane-rich liquid inlet of the tower bottom reboiler of low-pressure distillation tower,
With the channel attached mixed flow thigh inlet of the mixed flow thigh of ice chest and a mixed flow thigh outlet; This mixed flow thigh inlet is positioned at the ice chest intermediate heat; This mixed flow thigh inlet is connected with the methane-rich liquid outlet of the tower bottom reboiler of low-pressure distillation tower; This mixed flow thigh outlet is connected with the mixed flow thigh inlet of high-pressure rectification Tata still
With a channel attached natural gas liquids inlet of the natural gas liquids of ice chest and a natural gas liquids outlet, this natural gas liquids inlet is positioned at the ice chest intermediate heat, be connected with the bottom of the tower bottom reboiler of the low-pressure distillation tower gas outlet that liquefies,
With channel attached liquid nitrogen inlet of the liquid nitrogen of ice chest and liquid nitrogen outlet, the liquid nitrogen outlet is drawn a pipeline and is connected with the low-pressure distillation tower overhead condenser via the 4th throttling valve, be connected with high pressure distillation column overhead condensing surface via the 5th throttling valve,
Export gentle nitrogen inlet with the channel attached gas nitrogen of the gas nitrogen of ice chest, this gas nitrogen inlet is connected with the top exit of low-pressure distillation tower overhead condenser with high-pressure rectification column overhead condensing surface,
With channel attached hydrogen rich gas outlet of the hydrogen rich gas of ice chest and hydrogen rich gas inlet, this hydrogen rich gas inlet is connected with the top exit of second separator,
The rich nitrogen outlet and the rich nitrogen inlet that are connected with the rich channel of nitrogen of ice chest; This richness nitrogen inlet is connected with the top exit of first separator; The tower bottom reboiler of low-pressure distillation tower comprises: a methane-rich liquid inlet, a methane-rich liquid outlet, a bottom liquefaction gas outlet
The overhead condenser of low-pressure distillation tower is connected with an inlet of first separator, and its top exit is connected with the gas nitrogen inlet of ice chest,
The tower still of high-pressure rectification tower has outlet at bottom, and this outlet at bottom is connected with the middle part of low-pressure distillation tower via the 6th throttling valve, and has an inlet, be connected with the mixed flow thigh outlet of ice chest,
The evaporator overhead condenser of high-pressure rectification tower is connected with an inlet of second separator, and its top exit is connected with the gas nitrogen inlet of ice chest,
The outlet at bottom of first separator is connected with low-pressure distillation tower, and its top exit is connected with the rich nitrogen inlet of ice chest,
The outlet at bottom of second separator is connected with the high-pressure rectification tower, and its top exit is connected with the hydrogen rich gas inlet of ice chest.
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| CN 201220294198 CN202626134U (en) | 2012-06-21 | 2012-06-21 | Process device for preparing liquefied natural gas (LNG) and hydrogen simultaneously through coke oven gas |
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| CN 201220294198 CN202626134U (en) | 2012-06-21 | 2012-06-21 | Process device for preparing liquefied natural gas (LNG) and hydrogen simultaneously through coke oven gas |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719289A (en) * | 2012-06-21 | 2012-10-10 | 新地能源工程技术有限公司 | Process for preparing liquefied natural gas (LNG) and hydrogen from coke oven gas |
| CN106039954A (en) * | 2016-07-25 | 2016-10-26 | 北京华福工程有限公司 | System and method for sulfurous gas desulfurization |
| CN106621692A (en) * | 2017-03-06 | 2017-05-10 | 成都赛普瑞兴科技有限公司 | Joint regeneration purifying system and purifying method |
| CN108179046A (en) * | 2018-01-17 | 2018-06-19 | 四川杰瑞恒日天然气工程有限公司 | A kind of method of coke-stove gas hydrogen making and LNG |
| CN109654807A (en) * | 2018-11-29 | 2019-04-19 | 山西易高煤层气有限公司 | A kind of Method and system for coalbed methane liquefaction |
| CN111170275A (en) * | 2020-02-25 | 2020-05-19 | 南京宝雅气体有限公司 | Hydrogen treatment purification process and device thereof |
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2012
- 2012-06-21 CN CN 201220294198 patent/CN202626134U/en not_active Withdrawn - After Issue
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719289A (en) * | 2012-06-21 | 2012-10-10 | 新地能源工程技术有限公司 | Process for preparing liquefied natural gas (LNG) and hydrogen from coke oven gas |
| CN102719289B (en) * | 2012-06-21 | 2014-05-07 | 新地能源工程技术有限公司 | Process for preparing liquefied natural gas (LNG) and hydrogen from coke oven gas |
| CN106039954A (en) * | 2016-07-25 | 2016-10-26 | 北京华福工程有限公司 | System and method for sulfurous gas desulfurization |
| CN106621692A (en) * | 2017-03-06 | 2017-05-10 | 成都赛普瑞兴科技有限公司 | Joint regeneration purifying system and purifying method |
| CN108179046A (en) * | 2018-01-17 | 2018-06-19 | 四川杰瑞恒日天然气工程有限公司 | A kind of method of coke-stove gas hydrogen making and LNG |
| CN109654807A (en) * | 2018-11-29 | 2019-04-19 | 山西易高煤层气有限公司 | A kind of Method and system for coalbed methane liquefaction |
| CN111170275A (en) * | 2020-02-25 | 2020-05-19 | 南京宝雅气体有限公司 | Hydrogen treatment purification process and device thereof |
| CN111170275B (en) * | 2020-02-25 | 2021-06-01 | 南京宝雅气体有限公司 | Purification device for hydrogen treatment and purification process |
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