CN209537405U - Cog joint blast furnace gas or/and coal gas of converter produce H2The device of/CO unstripped gas - Google Patents

Cog joint blast furnace gas or/and coal gas of converter produce H2The device of/CO unstripped gas Download PDF

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CN209537405U
CN209537405U CN201821746643.0U CN201821746643U CN209537405U CN 209537405 U CN209537405 U CN 209537405U CN 201821746643 U CN201821746643 U CN 201821746643U CN 209537405 U CN209537405 U CN 209537405U
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gas
pressure
swing absorption
tower
blast furnace
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赵春风
丁艳宾
赵猛
马正飞
杨东昊
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Suzhou Gai Wo That Purification Technology Co Ltd
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Suzhou Gai Wo That Purification Technology Co Ltd
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Abstract

The utility model discloses a kind of cog joint blast furnace gases or/and coal gas of converter to produce H2The device of/CO unstripped gas.Device includes: the first pressure-swing absorption apparatus, for the first gas mainly containing blast furnace gas or/and coal gas of converter to be separated CO and N by pressure swing absorption process2, obtain CO；Second pressure-swing absorption apparatus, for the second gas mainly containing coke-stove gas to be gone out to the H in gas by pressure swing absorption process separating-purifying2；The device for producing alcohol is connected to the H of the CO outlet and the second pressure-swing absorption apparatus of the first pressure-swing absorption apparatus2Outlet is used for CO obtained and H2React the alcohol of obtained carbon atom number >=2.The present invention for blast furnace gas and or coal gas of converter provide a technical strategies with the comprehensive utilization of coke-stove gas, provide corresponding device, further improve blast furnace gas and or coal gas of converter with coke-stove gas economic value.

Description

Cog joint blast furnace gas or/and coal gas of converter produce H2/ CO unstripped gas Device
Technical field
The invention belongs to chemical technology field more particularly to a kind of cog joint blast furnace gases or/and coal gas of converter Produce H2The method and device of/CO unstripped gas.
Background technique
In industrial processes, a large amount of coke-stove gas (coking), blast furnace gas (ironmaking) and converter coal can be supervened Gas (steel-making), referred to as " three gas ".Meanwhile blast furnace coal can be also generated in the smelting process of other ferrous metal and non-ferrous metal Gas, coal gas of converter and gas component are similar to the tail gas of blast furnace gas, coal gas of converter.
In steel mill " three gas ", although blast furnace gas available gas content is minimum, its discharge amount is maximum.Blast furnace gas master Want ingredient are as follows: CO, CO2, N2, H2, CH4Deng wherein CO content accounts for about 25% or so, CO2And N2Content account for 15% respectively, 55%, H2、CH4Content it is seldom.Blast furnace gas calorific value is low, only 3300~3800kJ/Nm3.Due to the CO in blast furnace gas2, N2Both it is not involved in burning and generates heat, can not be combustion-supporting, on the contrary, also absorbing the heat generated in a large amount of combustion process, cause The theoretical temperature combustion of blast furnace gas is relatively low, only 1300 DEG C or so in addition some there was only 900 DEG C or so.Blast furnace gas room temperature Lower combustion instability, general industry furnace cannot be single using blast furnace gas as fuel, need to be with the high fevers such as coke-stove gas or coal gas of converter It is worth that coal gas ginseng is mixed to be used, but blast furnace gas and coke-stove gas or to be used in mixed way hot-restriking die with coal gas of converter big, not only to combustion It burns device and proposes requirements at the higher level, and also have different degrees of influence to product quality.Due to most of enterprise's blast furnace gas More than needed, high heating value gas is in short supply, therefore the blast furnace gas diffusing phenomenon of various degrees, this not only pollutes environment, but also Waste of energy.How these calorific values low, impurity content high, yield huge, purification difficult, environmental pollution is serious height is efficiently used Producer gas is the problem for requiring to solve both at home and abroad.Present blast furnace gas generally is used to burn, but since its calorific value is low, no Fire that constituent content is high, and efficiency of combustion and utilization rate are poor, and waste containing it is a large amount of it is valuable can be used to do it is high additional The CO of the industrial chemicals of value.Present coal gas of converter is generally to be used to burn or generate electricity, but since its calorific value is low, efficiency of combustion and Utilization rate is poor, and the generated income that generates electricity will be far below the change after using it to handle as industrial chemicals production high additive value The income of chemical product.The universal processing method of coke-stove gas is CO contained in coke-stove gas2Also be used as raw material, even CH contained in coke-stove gas4And CmHnCO, CO are generated also by reaction2And H2, but it needs to increase additional reaction step, needs Increase investment and operating cost, can also consume existing high heating value component and can also consume and waste more useful group Point.
In addition, the basic principle of pressure-variable adsorption (Pressure Swing Adsorption, PSA) is to utilize gas composition The difference of characterization of adsorption on solid material realizes the separation or purification of gas by periodic pressure alteration process.Appoint How a kind of absorption is for same adsorbate (adsorbate), and in adsorption equilibrium, temperature is lower, and pressure is higher, Adsorbance is bigger.Conversely, temperature is higher, pressure is lower, then adsorbance is smaller.If temperature is basically unchanged, the case where pressurizeing Lower absorption, with decompression (vacuumizing), the method desorbed with weakly stable gas purging or low pressure, referred to as pressure-variable adsorption.Pressure-variable adsorption Adsorption and desorption (vacuumize, purge or vacuumize plus purging) and pressure that may be present are generally comprised, pressurising, suitable put, is inverse It puts, replace.As it can be seen that pressure-variable adsorption is adsorbed and is desorbed by changing pressure.There is pressure change to there is energy Loss, and the method for present pressure-variable adsorption is not recycled to the energy of this part, causes the damage in vain of energy Lose, reduce the economic benefit of pressure-variable adsorption, thus cause in the case where hypertonia should pressure swing absorption process, cost Excessively high situation.With the development of industry, there is the case where gas separation under many condition of high voltage, operating pressure is higher, More lead to excessively high operation energy consumption.On the other hand, due to during the industrial operation of pressure-variable adsorption, it is between numerous equipment plus Transformation between pressure, decompression is very frequent, results in and is difficult preferably to recycle its energy.
Summary of the invention
That the object of the present invention is to provide process flows is simple, equipment investment is few and small power consumption by blast furnace gas and or turn Producer gas meets the technique of the unstripped gas of the synthol especially ethylene glycol of high standards, the work with cog joint preparation Skill, which is not only able to alleviate domestic energy shortage and blast furnace gas, wastes serious status, and can further increase blast furnace gas or Economy and environmental benefit of the coal gas of converter with coke-stove gas.It is a further object of the present invention to provide its devices.
Technical solution:
A kind of cog joint blast furnace gas or/and coal gas of converter produce H2The method of/CO unstripped gas, including walk as follows It is rapid:
Step 1, by the first gas mainly containing blast furnace gas or/and coal gas of converter by pressure swing absorption process separate CO and N2, obtain CO；
Step 2 goes out the second gas mainly containing coke-stove gas in second gas by pressure swing absorption process separating-purifying H2；
Step 3, by resulting CO and H2As H2/ CO unstripped gas.
The H2/ CO unstripped gas is used to produce the alcohol of carbon atom number >=2.
In step 2, the H in second gas is purified out2When, by a step pressure swing absorption process by H2With CO and N2Separation, mentions Pure H out2, or pressure swing absorption process is first passed through by CO and H2And N2Separation must contain H after purifying CO2And N2Gaseous mixture, then pass through transformation Adsorption method is by H2And N2Separation, purifies out H2。
In step 1, displacement gas when separating CO and nitrogen by pressure swing absorption process is purified in second gas CO out or/and from the CO for itself purifying out；In step 2, by pressure swing absorption process by CO and H2And N2Point From the displacement gas for purifying CO derives from the CO for purifying out in first gas；By a step pressure swing absorption process by H2With CO And N2Separation, purifies out H2It is suitable in pressure swing absorption process separation CO and nitrogen in the tail gas and first gas treatment process of process It deflates, displacement tail gas is mixed into step 1.
In step 1, first gas separates CO and N by pressure swing absorption process after the first removal of impurities pretreatment2；Step 2 In, second gas goes out the H in gas after the second removal of impurities pretreatment by pressure swing absorption process separating-purifying2。
Suitable deflation that step 2 or/and step 1 generate in the pressure-swing absorption process, reverse gas, in displacement tail gas extremely A kind of few gas is back to step 2, and the gas mixing in link is mixed or pre-processed with the second removal of impurities with second gas supplied materials gas.
The first removal of impurities pretreatment includes dedusting, dephosphorization, arsenic removal, dehydration, dehydrogenation deoxidation, desulfurization, de- CO2Or it removes CH4In a step or a few steps combination；The second removal of impurities pretreatment includes dedusting, tar removing, removes heavy constituent, dehydration, takes off Sulphur, deoxidation, de- CO2Or remove CH4Except CmHnIn a step or a few steps combination.
The first removal of impurities pretreatment or the second removal of impurities pretreatment includes desulfurization and de- CO2, take off CO2With the same stepping of desulfurization Capable or de- CO2After desulfurized step.
The first removal of impurities pretreatment further includes except CH4Or/and dehydrogenation deoxidation, remove CH4After desulfurized step, take off Hydrogen deoxidation, which is in, removes CH4After step；The second removal of impurities pretreatment further includes except CH4Except CmHn, remove CH4Except CmHnIn de- Sulphur and de- CO2After step.
De- CO in first removal of impurities pretreatment and the second removal of impurities pretreatment2By variable-pressure adsorption separating method or absorption process, When using absorption process, the absorbent in the first removal of impurities pretreatment takes off CO2Afterwards for the CO in the second removal of impurities pretreatment2Removing or the Absorbent in two removal of impurities pretreatments takes off CO2Afterwards for the CO in the first removal of impurities pretreatment2Removing.
In first removal of impurities pretreatment, CH is removed4It is that CH is removed by catalyst combustion reaction4；Dehydrogenation deoxidation is reacted by catalysis Method is removed；In second removal of impurities pretreatment, CH is removed4Except CmHnIt is outer defeated by variable-pressure adsorption separating method removing.
A kind of cog joint blast furnace gas or/and coal gas of converter produce H2The device of/CO unstripped gas, comprising:
First pressure-swing absorption apparatus, for the first gas mainly containing blast furnace gas or/and coal gas of converter to be passed through transformation Adsorption method separates CO and N2, obtain CO；
Second pressure-swing absorption apparatus, for proposing the second gas mainly containing coke-stove gas by pressure swing absorption process separation H in pure gas out2；
The device for producing alcohol is connected to the H of the CO outlet and the second pressure-swing absorption apparatus of the first pressure-swing absorption apparatus2Out Mouthful, it is used for CO obtained and H2React the alcohol of obtained carbon atom number >=2.
The cog joint blast furnace gas or/and coal gas of converter produce H2The device of/CO unstripped gas, further includes:
The first removal of impurities pretreatment unit being connect with the first pressure-swing absorption apparatus, for being pre-processed to first gas；
The second removal of impurities pretreatment unit being connect with the second pressure-swing absorption apparatus, for being pre-processed to second gas.
The first removal of impurities pretreatment unit includes dust-extraction unit, dephosphorization apparatus, arsenic removing apparatus, dehydration device, dehydrogenation Device for deoxidizing, desulfurizer, de- CO2Device removes CH4One or several combinations in device；Second removal of impurities is pre- Processing unit includes dust-extraction unit, coke removing appts, except recombination separating device, dehydration device, desulfurizer, device for deoxidizing, de- CO2Dress It sets or except CH4Except CmHnOne or several combinations in device.The function that the first removal of impurities pretreatment unit is accordingly realized It can include dedusting, dephosphorization, arsenic removal, dehydration, dehydrogenation deoxidation, desulfurization, de- CO2Or remove CH4In one or several combinations；The The function that two removal of impurities pretreatment units are accordingly realized includes dedusting, tar removing, except heavy constituent, dehydration, desulfurization, deoxidation, de- CO2Or Person removes CH4Except CmHnIn one or several combinations.
For different combinations, it is clear that, the first pressure-swing absorption apparatus is connected to the tail portion of the first removal of impurities pretreatment unit, Second pressure-swing absorption apparatus is connected to tail portion (the last one of i.e. last first pretreatment unit of the second removal of impurities pretreatment unit After unit).
The first removal of impurities pretreatment unit and the second removal of impurities pretreatment unit includes desulfurizer and de- CO2Device, De- CO2Device and desulfurizer integrate or de- CO2Device is in desulfurizer downstream side.
Further, the first removal of impurities pretreatment unit further includes except CH4Device or/and dehydrogenation device for deoxidizing remove CH4 Device is in desulfurizer downstream side, and dehydrogenation device for deoxidizing, which is in, removes CH4Device downstream side；The second removal of impurities pretreatment dress Set further includes except CH4Except CmHnDevice, CH4Except CmHnDevice is in desulfurization and de- CO2Device downstream side.For locating at first in advance Device is managed, i.e., ought be contained except CH4When device, CH is removed4Device is in desulfurizer downstream side, desulfurizer and de- CO2Device separates When, remove CH4Device is in desulfurizer downstream side, takes off CO2Upstream side；When device for deoxidizing containing dehydrogenation, dehydrogenation device for deoxidizing In desulfurizer downstream side, desulfurizer and de- CO2When device separates, dehydrogenation device for deoxidizing is in desulfurizer downstream side, De- CO2Upstream side, if also containing except CH4Device, dehydrogenation device for deoxidizing, which is in, removes CH4Device downstream.
De- CO in first removal of impurities pretreatment unit and the second removal of impurities pretreatment unit2Device is that pressure swing adsorption method takes off CO2Dress It sets or absorption process takes off CO2Device takes off CO using absorption process2When device, the absorption process in the first removal of impurities pretreatment unit takes off CO2Dress The absorbing liquid outlet or import set are connected to the absorption process of the second removal of impurities pretreatment unit except CO2The import or export of device.
The suitable deflation of first pressure-swing absorption apparatus or/and the second pressure-swing absorption apparatus, is replaced in offgas outlet at reverse gas At least one connect with second gas raw material gas inlet or the second removal of impurities pretreatment unit.
A kind of embodiment, second pressure-swing absorption apparatus pass through a step pressure swing absorption process for H2With CO and N2Point From purifying out H2, the suitable deflation of offgas outlet and the first pressure-swing absorption apparatus or/and displacement offgas outlet are connected by pipeline It connects, which connect with the gas feed of the first removal of impurities pretreatment unit or the first pressure-swing absorption apparatus.
Another embodiment, second pressure-swing absorption apparatus include concatenated third pressure-swing absorption apparatus and the 4th Pressure-swing absorption apparatus, wherein third pressure-swing absorption apparatus is used to pass through pressure swing absorption process for the CO and H in second gas2And N2 Separation must contain H after purifying CO2And N2Gaseous mixture, the 4th pressure-swing absorption apparatus are used to pass through pressure swing absorption process for the gaseous mixture In H2And N2Separation, purifies out H2；4th pressure-swing absorption apparatus is connect with the device of production alcohol.
The displacement gas entrance of first pressure-swing absorption apparatus by the outlet the CO connection of pipeline and third pressure-swing absorption apparatus or It exports and connects with the CO of its own；The displacement gas entrance of third pressure-swing absorption apparatus and the CO of the first pressure-swing absorption apparatus are exported and are connected It connects.
Above-mentioned first~the 4th pressure-swing absorption apparatus is only that name is numbered to device in sake of clarity, is had no in structure Be particularly limited to, in addition to this, the present invention in the pressure-swing absorption apparatus being related to name there are also some names functionally such as Pressure-variable adsorption mentions hydrogen production device, pressure-variable adsorption separation CO and N2Device, pressure-changeable adsorption decarbonization device etc. are for clear statement originally Invention, rather than structure is mainly limited.
In addition, needing the unit for having used more pressure-variable adsorption to clean to operate in above-mentioned separation process, transformation is inhaled Energy consumption is high, the operational transformation of buck is frequent caused by operating pressure is high during attached, when pressure-difference fluctuation and energy fluctuation all very Greatly, when shock loading is very big, it has been more than the fluctuation range of the permission of conventional apparatus for energy recovery, has will lead to the machinery equipment service life Shorten, can cause safely etc. a variety of hidden danger even machinery equipment can not work normally so that caused energy is difficult to recycle The problem of utilization.The present invention is normal adsorption separation process and energy recovery process and certain gas or liquid pressing process Be coupled, recycled energy, capacity usage ratio is high, and technical process is simple, reduce the operation cost of pressure-variable adsorption, from This angle has expanded the living space of pressure-variable adsorption.Mainly by by expanding machine, motor, compressor or pump group at coaxial The energy recycling system of driving carries out energy regenerating operation, which also has compact-sized, and overall efficiency is high, whole set equipment takes With and operating cost it is all relatively low, have preferable economic benefit.
In above-mentioned pressure-swing absorption process, method as follows can also be used:
A kind of energy reclaiming method with pressure-variable adsorption includes the following steps: the pressure reduction in working pressure-variable adsorption Gas in the process recycles its energy using expanding machine；It is slow by fluid in the gas access of expanding machine and/or gas outlet Flushing device stabilizes the fluctuation of air pressure；Alternatively, inhibiting the fluctuation of its revolving speed by the rotary resistance device in expanding machine shaft.
The fluid cushion device is selected from one of regulating valve or surge tank or several combinations；Described turns Dynamic resistance device refers to flywheel.
The pressure reduction process refer to pressure, pressurising, displacement, it is with pressure rinse, along put or inverse put etc. there are pressure changes The process of change.
In one embodiment, expanding machine drives electrical power generators, and electric energy caused by generator needs electricity for other Electric energy caused by the equipment or generator of power is by compressor to the gas or liquid for needing to boost in pressure-swing absorption process It is compressed.
By controlling the input current for the motor being connected with compressor to supplement the electric energy of its needs；Battery can be passed through Group or capacitance group stabilize the fluctuation of the electric energy for being input to motor.
In one embodiment, electric energy caused by generator is connected to the grid, and the effect of power grid is flat using carrying capacity Press down the fluctuation of electric energy caused by expanding machine；Electric energy obtained in power grid is used for other equipment for needing electric power, or passes through Compressor compresses the gas for needing to boost in pressure-swing absorption process.
In one embodiment, the shaft of expanding machine and the shaft of motor are coaxially connected, by expanding machine and motor It is common to drive compressor operating.
Based on above-mentioned method, following device can also be used:
A kind of pressure-swing absorption apparatus includes:
1), at least one High Pressure Absorption tower；
2), at least one energy recycle device includes expanding machine in the energy recycle device, for recycling high pressure The energy for the high pressure gas being discharged in adsorption tower；
The gas access of expanding machine and/or gas outlet are connected with fluid cushion device；
Alternatively, rotary resistance device is arranged in the shaft of expanding machine.
The fluid cushion device is selected from one of regulating valve or surge tank or several combinations；Described turns Dynamic resistance device refers to flywheel.
In one embodiment, High Pressure Absorption tower between energy recycle device and low pressure adsorbent tower by connecting.
It in one embodiment, further include having generator in pressure-swing absorption apparatus, expanding machine is connect with generator.
Generator with it is other need to connect using the equipment of electric power or generator drive compressor to pressure-swing absorption process It is middle that the gas to boost or liquid is needed to be compressed.
Generator is connect with power grid, and the effect of power grid is the wave that electric energy caused by generator is stabilized using carrying capacity It is dynamic.
It in one embodiment, further include having compressor and motor in pressure-swing absorption apparatus, and the shaft of expanding machine Be with the shaft of motor it is coaxially connected, compressor operating is driven by expanding machine and motor jointly.
Battery pack or capacitance group are also installed on motor.
Surge tank is additionally provided in the gas access of compressor and/or gas vent.
Compared with general pressure swing absorption process, methods and apparatus of the present invention pressure swing absorption process increase energy The process of recycling exists normal adsorption separation process and energy recovery process and certain gas or liquid pressing PROCESS COUPLING Together, energy has been recycled, the capacity usage ratio of system is improved, has reduced the operation cost of pressure-variable adsorption, from the angle of cost The living space of pressure-variable adsorption has been expanded, technical process is simple, and safety coefficient is high, and unit automation degree is high, and it is easy to operate, if Standby occupied area is few, ensure that product purity, ensure that the rate of recovery, flexible operation reduce tower quantity and size.
The utility model has the advantages that
Compared with prior art, the present invention having substantive distinguishing features and marked improvement to be: the invention proposes one kind by Blast furnace gas and or coal gas of converter prepared with a variety of processing units of cog joint synthol such as ethylene glycol unstripped gas work The thinking of the technique of process, not only for blast furnace gas and or coal gas of converter provide one with the comprehensive utilization of coke-stove gas Technical strategies, and further improve blast furnace gas and or coal gas of converter with coke-stove gas economic value；Utilize this The device of invention, by blast furnace gas and or coal gas of converter with coke-stove gas prepare H2The technique of/CO unstripped gas can also coproduction height Combustion value fuel gas and industrial nitrogen, nitrogen gas concn require up to technical grade and being capable of recycling and reusings；Monoblock type work of the present invention Skill by many experiments, simulation calculate, steel mill investigate on the spot and the experience in design of many years obtains, material match and energy Using considering from whole technique, process flow is optimized.
Detailed description of the invention
Fig. 1 is to prepare H2The process method flow chart of/CO unstripped gas；
Fig. 2 is H in embodiment 12/ CO unstripped gas preparation method process flow chart；
Fig. 3 is H in embodiment 22/ CO unstripped gas preparation method process flow chart；
Fig. 4 is H in embodiment 32/ CO unstripped gas preparation method process flow chart；
Fig. 5 is to prepare H2The structure drawing of device of/CO unstripped gas；
Fig. 6 is a kind of structure chart of energy recycle device applied to pressure-swing absorption process；
Fig. 7 is the structure chart that another is applied to the energy recycle device of pressure-swing absorption process；
Fig. 8 is to be integrated with two tower pressure swing adsorption purge H of energy recycle device2Device；
Fig. 9 is to be integrated with three tower pressure swing adsorption purge H of energy recycle device2Device；
Wherein 1 is adsorption tower, and 2 be the level-one of turbo-expander, and 3 be compressor, and 4 be motor, and 5 be to take out air cushion Tank, 6 be vacuum pump, and 7 be reverse gas surge tank, and 8 be inverse put air compressor, and 9 be flywheel, and 10 be capacitance group, and 11 be by compressed gas Body import surge tank, 12 be that surge tank is exported by compressed gas, and 13 be turbine import high-pressure buffering pot, and 14 be turbine outlet high pressure Surge tank, 15 be turbine import low pressure buffer tank, and 16 be turbine outlet low pressure buffer tank, and 17 be the second level of turbo-expander, 18 It is supplied materials gas surge tank, 19 be overhead product gas surge tank, and 20 be level-one turbine outlet heat exchanger, and 21 be that the outlet of second level turbine is changed Hot device.
Specific embodiment
H provided by the present invention2The production method of/CO unstripped gas, is mainly utilized blast furnace gas, coal gas of converter and coke Producer gas is as raw material.
It mainly include N in the gas composition of above-mentioned coal gas2、H2、CO、CO2、O2、CH4、H2S, COS etc., in some allusion quotations In the blast furnace gas of type, composition includes by volume percentage: N240~65%, H20.5~5%, O20.2~ 5%, CO210~30%, CO 10~30%, CH40.1~2.0%, H25~400ppm of S, 0.1~100ppm of COS.It is some In typical coal gas of converter, composition includes the N by volume percentage210~30%, H20~2%, O20~2%, CO215~25%, CO 50~80%, CH40.1~2.0% and micro sulphur.In some typical coke-stove gas, group At including N by volume percentage23~8%, H250~60%, O20.1~0.8%, CO21~4%, CO 4~ 8%, CH420~30%, CmHn2~4%, H25~400ppm of S and also containing micro impurity include coal tar, benzene, Naphthalene, SO2, organic sulfur, ammonia, thiophene, HCN etc..
Above raw material such as coal gas can also pass through conventional method before the technique and equipment entered in this patent Carry out the preprocessing process such as corresponding removal of impurities；These pre-treatments are not particularly limited.
Heretofore described " H2/ CO unstripped gas " is primarily referred to as CO and H2, they are individualism, H2/ CO unstripped gas Purposes can be used for synthesizing different industrial chemicals on different catalyst.In the present invention, obtaining containing H2With CO's H2After/CO unstripped gas, mainly it is applied to produce ethylene glycol.Since H is made in this method2The high quality of/CO unstripped gas, also The processes such as alcohol for making other carbon atom number >=2 can be used, such as by methanol ethyl alcohol and other are anti-by the way that CO realization chain is added One or more carbon atoms (carbonylation) should be increased to realize, needing to adjust product category later can when needed again It carries out adding hydrogen H2Obtained from product.
Cog joint blast furnace gas or/and coal gas of converter produce H2The method of/CO unstripped gas, includes the following steps:
Step 1, by the first gas mainly containing blast furnace gas or/and coal gas of converter by pressure swing absorption process separate CO and N2, obtain CO；
Second gas mainly containing coke-stove gas is gone out by pressure swing absorption process separating-purifying the H in gas by step 22；
Step 3, by resulting CO and H2As H2/ CO unstripped gas.
First gas in the present invention mainly containing blast furnace gas or/and coal gas of converter or mainly second containing coke-stove gas In gas, predominant gas is to account for exhausted big ingredient, such as more than 85%, 90%, 95% volume fraction, can contain other some tails Gas, periodic off-gases etc..
In step 1, by using pressure-variable adsorption partition method (or pressure swing absorption process) separation first gas in CO and The adsorbent of this field routine can be used in nitrogen, is such as inhaled using the adsorbent or metal organic framework type of copper-loaded base or load silver-based Attached dose (MOFs, ZIFs), metal-organic polyhedra (MOPs)；The carrier of adsorbent can be active carbon, aluminium oxide, silica gel, divide Sub- sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, corrugated plating, fiber (cloth) material and structure, braiding Object, metal foam, ceramic foam, graphite-based foaming body etc..CO and nitrogen are separated using pressure-variable adsorption partition method, transformation is inhaled Attached adsorptive pressure is 0.02~10MPa or so, 0~150 DEG C of operation temperature, in some embodiments, the suction of pressure-variable adsorption Enclosure pressure is 0.2~4MPa, and operation temperature is 20~80 DEG C, the volume fraction through pressure-variable adsorption extraction technical grade nitrogen >= 99.2%, it can carry out using or sell directly as product.When separating CO and nitrogen using pressure-variable adsorption partition method, need becoming It presses and temp.-changing adsorption method is added before the unit of absorption, water and heavy constituent are removed, because moisture and heavy constituent will affect subsequent change The effect for pressing adsorption step, can have adverse effect on adsorbent, can reduce the separating capacity of the pressure-variable adsorption of adsorbent, very Irreversible damage can be extremely caused to adsorbent, makes adsorbent degradation, even caused its inactivation, shortened its service life, especially Be for CO and nitrogen separation adsorbent damage it is even more serious, make rapidly adsorbent degradation, cause its inactivation, be not available. When using the series connection of a set of pressure-swing absorption apparatus is greater than, temp.-changing adsorption separative unit is added in the separation list of first set pressure swing adsorption method Before member, CO and nitrogen are separated in pressure-variable adsorption partition method, the nitrogen for being unsatisfactory for industrial standard is obtained, when nitrogen pressure is greater than Hydraulic recovery system can then be entered when 0.15MPa, recycle the had pressure energy of nitrogen.When using pressure swing adsorption method, Ke Yi Energy recycle device is added in pressure-swing absorption apparatus, recycles wave in pressure-swing absorption process simultaneously completing pressure-variable adsorption separation process The pressure energy taken.
In step 2, the H in second gas is purified2When, by a step pressure swing absorption process by H2With CO and N2Separation, purification H out2(i.e. one-step method), or pressure swing absorption process is first passed through by CO and H2And N2Separation must contain H after purifying CO2And N2Gaseous mixture, Pass through pressure swing absorption process again for H2And N2Separation, purifies out H2(i.e. two-step method).When wherein, using one-step method, adsorbent can be adopted With the adsorbent such as active carbon, activated alumina, molecular sieve, silica gel etc. of this field routine, the adsorptive pressure of pressure-variable adsorption is 0.3 ~20MPa, adsorption temp be 20~80 DEG C, in some embodiments, adsorptive pressure be 2~4MPa, adsorption temp be 20~ 40 DEG C, when using two-step method, adsorbent can using this field routine adsorbent for example active carbon, activated alumina, molecular sieve, Silica gel etc., the adsorptive pressure of pressure-variable adsorption are 0.3~20MPa, and temperature is 20~80 DEG C, in some embodiments, adsorption pressure Power is 2~4MPa, and adsorption temp is 20~40 DEG C.
In step 1, separates in CO and nitrogen in first gas pressure-variable adsorption due to the CO gas for needing to obtain high-purity, need Use displacement step, the supplied materials of displacement gas arise primarily at the high-purity for purifying out in second gas CO or/and From the CO for the high-purity for itself purifying out, second gas need to pass through catalytic dehydrogenation there are also the CO of high-purity more than needed It can just be incorporated to first gas after deoxidation, the high-purity CO for meeting the requirements preset requirement is made, as unstripped gas；In step 2 In, for two-step method, by pressure swing absorption process by CO and H2And N2Separation, purification CO need to obtain the CO gas of high-purity, need Displacement step is used, the supplied materials of displacement gas arises primarily at the CO for the high-purity for purifying out in first gas；For One-step method, by a step pressure swing absorption process by H2With CO and N2Separation, purifies out H2Contain a large amount of CO gas in the tail gas of process Body, by its first gas treatment process in pressure-variable adsorption CO and nitrogen separation suitable deflation or/and displacement tail gas mix it is laggard Enter step 1, such as enters first step pressure-variable adsorption and separate CO and N2Or the first removal of impurities preprocessing process before it, recycling the Two variable pressure gas adsorb in purifying hydrogen of hydrogen tail gas containing suitable in a large amount of CO gas and first gas CO and nitrogen separation It deflates, contain a large amount of CO gas in displacement tail gas, make the original of satisfactory synthesizing glycol after treatment Expect gas.This method reduces the devices of Pressure Swing Adsorption CO in processing coke-stove gas, reduce investment, and are utilized main The device that CO is purified in first gas containing blast furnace gas and/or coal gas of converter, has recycled mainly the second gas containing coke-stove gas CO in body improves the utilization rate of device, and valuable gases is made to be fully utilized while be good for the environment.But it needs to meeting The gases such as purifying hydrogen of hydrogen device exhaust are pressurized, the operating cost of slightly increased a part.
In one embodiment, in step 1, first gas passes through pressure swing absorption process after the first removal of impurities pretreatment Separate CO and N2；In step 2, second gas passes through pressure swing absorption process separating-purifying outlet after the second removal of impurities pretreatment H in body2。
In one embodiment, step 2 or/and step 1 generate in the pressure-swing absorption process suitable deflation, inverse put At least one of gas, displacement tail gas gas is back to step 2, mixes with second gas supplied materials gas or pre-processes with the second removal of impurities Gas mixing in link.Coke-stove gas supplied materials atmospheric pressure it is lower (be in some embodiments 0.02~0.1MPa of gauge pressure), With generated in pressure-variable adsorption step in first gas treatment process suitable deflation, reverse gas, the displacement processes atmospheric pressure phase such as tail gas Closely, it avoids and increases the expense of compressor, shortens process and reduce operating cost；Transformation is both recycled so after mixing CO and H in adsorption step in Process Gas2Etc. useful gas, avoids waste simultaneously and improve CO and H in coke-stove gas2 Concentration so that absorption when gas partial pressure increase, increase separation, be conducive to the CO for obtaining high-purity and H2.Gained Gas is pressurized (to be in some embodiments 0.3~4MPa), is conducive to the pressure-variable adsorption of gas in this way for 0.2~20MPa Separation the volume for reducing equipment, reduces investment outlay, saves occupied area, and pressurization can make the oil droplet in gas poly- simultaneously, increase oil droplet Diameter.It is specific to need to enter which link of step 2 be back to, it is determined by the impurity composition that the needs in gas to be mixed remove 's.For example, sulfur content is excessively high in gas to be mixed needs desulfurization, then gas to be mixed enters before desulfurized step.It is similar De- CH4Before step, before deoxygenation step, before dehydration, de- CO2Before step.
In one embodiment, the first removal of impurities pretreatment is de- including dedusting, dephosphorization, arsenic removal, dehydration, dehydrogenation Oxygen, desulfurization, de- CO2Or remove CH4In a step or a few steps combination；First gas has through the first removal of impurities pretreatment is purified Evil impurity content control is in sulfide≤1.15ppm, NH3≤ 200ppm, H2≤ 1000ppm, O2≤ 1000ppm, H2O≤ 100ppm, Cl+≤ 0.03ppm, arsenide≤0.1ppm, tar+dirt≤1mg/Nm3, naphthalene≤1mg/Nm3.It is further harmful miscellaneous Matter content is controlled in sulfide≤0.1ppm, Cl+≤ 0.01ppm, H2≤100ppm。
In one embodiment, the first removal of impurities pretreatment includes desulfurization and de- CO2, take off CO2With the same stepping of desulfurization Capable or de- CO2After desulfurized step.Due to the first gas mainly containing blast furnace gas and/or coal gas of converter contain it is micro Sulphur to the multiple catalysts (dehydrogenation deoxidation, product gas requirement, even demethanation catalyst) in subsequent step and can adsorb Agent (CO and nitrogen separation) has adverse effect on, and even causes its inactivation, shortens its service life, and its content sulphur is again Lower than sulfur content minimum required by some sulfur resistant catalysts, so to be removed at first to it.And due to the blast furnace of supplied materials Coal gas and/or coal gas of converter can be higher in start temperature, this is conducive to the reaction speed of the desulfurizing agent using metal oxide-type And desulfurization effect.Remove sulphur or the sulphur contained various impurity can using method commonly used in the art for example absorption method, membrane separating method, Oxide or hydroxide containing iron or manganese or zinc or copper or nickel or calcium or tin or the composition metal formed between them oxidation Solid desulfurating agent, the low-temp methanol of object are washed method, propylene carbonate ester process, N methylpyrrolidone process, polyglycol dimethyl ether process, are gathered Ethylene Glycol Methyl propyl ether method, tributyl phosphate method, hot potash method, activation hot potash method, MEA process, DEA process, MDEA method, DIPA Method, propylene carbonate ester process+DIPA, propylene carbonate ester process+glycol amine, sulfolane process, sulfolane+DIPA method, sulfolane+MDEA Method, methanol+secondary amine method, alkyl alcoholamine solwution method and MEA process, DEA process, MDEA method, ammonia scrubbing method, burning that activating agent is added Alkaline process, ADA method (stretford method), tannin process, LO-CAT method, Sulferox method, Sulfint method, Konox method, Bio-SR Method, naphthoquinones method (Takahax method), metal phthalocyanine method (PDS method), G-V (Giammarco-Vetrocoke process), arsenic alkaline process, MSQ method, Sulfolin Method, EDTA method, wet oxidation process, alkali absorption method, limestone-gypsum method, ammonia process, magnesium processes, phospho-ammonium fertilizer method, organic acid sodium-stone Cream method, lime-magnesium processes, calcium method, dry-type circulating fluidized bed method, zinc oxide method, urea method, Absorption via Chemical Complexation, charged Dry absorption Agent gunite, plasma method, electronic beam method, Dual alkali, vulcanization alkaline process and their combination.It is preferably de- using solid Sulphur agent, active absorption liquid such as DEA/MDEA absorption process, desulfurization effect is good and at low cost.The sulphur wherein removed is sent to sulfur recovery system System, sulphur of the unstripped gas after desulfurization in gas are removed to 0.01~0.1ppm.When using absorption process, absorbent such as DEA/MDEA There is absorbability to sulphur and carbon dioxide simultaneously, then can remove sulphur and carbon dioxide simultaneously.Desulfurization is in 0.2~10MPa, 20 ~700 DEG C, in some embodiments (0.2~4MPa, 20~400 DEG C, such as some metal oxides solid desulfurating agent 280 ~400 DEG C, 20~70 DEG C of absorbing liquid) under carry out.De- CO may be implemented using absorption process2It is synchronous with desulfurization to carry out, preferably set again Set the fine de-sulfur that a step uses solid desulfurating agent.
When supplied materials gas contains the too high levels of organic sulfur in sulphur, can by catalytic hydrogenation reaction or catalytic hydrolysis reaction, Make organic sulfur conversion H2S, then desulfurization is carried out, so that the sulfur content of gas after treatment can satisfy requirement, work as supplied materials It is mainly SO in sulphur that gas, which contains,2And too high levels, SO can be made by catalytic hydrogenation reaction2It is converted into H2S, then desulfurization is carried out, make The sulfur content for obtaining gas after treatment can satisfy requirement.Here iron of the catalyst of catalytic hydrogenation reaction to contain And/or copper and/or cobalt and/or manganese and/or molybdenum and/or zinc and/or aluminium and/or nickel and/or titanium and/or zirconium and/or tungsten and/or cerium Metal and/or their oxide and/or their sulfide and/or their soluble-salt and/or they between formed Metal composite oxide be active component, with titanium, zirconium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten, zinc, cobalt, cerium metal and/or it Oxide and silicon, rare earth, alkali metal, alkaline-earth metal, the oxide of transition metal and/or in their sulfide one Kind is several for auxiliary agent.Carrier be active carbon, aluminium oxide, silica, magnesia, titanium oxide, silica gel, molecular sieve, ceramic honey comb, Monazite, honeycomb, metal plate, ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, Ceramic foam, graphite-based foaming body etc..Here magnesium and/or lanthanum and/or barium of the catalyst of catalytic hydrolysis reaction to contain And/or aluminium and/or titanium and/or zirconium and/or cerium and/or potassium and/or calcium and/or cobalt and/or molybdenum and/or iron and/or copper and/or manganese And/or zinc and/or nickel and/or tungsten metal and/or their oxide and/or their sulfide and/or shape between them At metal composite oxide be active component, with titanium, zirconium, nickel, cobalt, molybdenum, cobalt, the metal of cerium and/or their oxide with And the oxide and/or one or more of their sulfide of silicon, rare earth, alkali metal, alkaline-earth metal, transition metal is help Agent.Carrier is active carbon, aluminium oxide, silica, magnesia, titanium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb Metal, metal plate, ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, Graphite-based foaming body etc..
CO2The separating effect that will affect pressure-variable adsorption separation CO and nitrogen steps, due to CO2In CO and nitrogen separation step There is certain adsorbance on adsorbent used, leads to CO2With CO, CO2Not high, the CO with nitrogen separation coefficient2Presence can lead It causes CO and nitrogen separation step that cannot access the CO and nitrogen of high-purity, the CO isolated can be made and contained in nitrogen gas More CO2, so to remove CO in advance2, remove CO2The step of need before CO and nitrogen separation step, remove CO2 The step of be the CO and nitrogen that CO and nitrogen can be made to respectively obtain high-purity for CO and nitrogen separation step, while it is this Sequencing also complies with the principle step by step of adsorption capacity and adsorbs low content component as far as possible, reduces desorption energy consumption principle, reduces The loss of adsorptive pressure, intergrade pressurization steps and desorption.To being carried out in coal gas except CO2The step of, it can use Pressure swing adsorption method, absorption process and their combination.Wherein absorption process includes: that WATER-WASHING METHOD, low-temp methanol wash method, propene carbonate Method, N methylpyrrolidone process, polyglycol dimethyl ether process, polyethylene glycol methyl propyl ether method, Catacarb method (catalysis thermokalite Method), hot potash method, activation hot potash method, improvement thermokalite method, hot carbonate method, amino-acid salt, ammonia scrubbing method, connection urine (alkali) method, G-V (Giammarco-Vetrocoke process), MEA process, DEA process, MDEA method, DIPA method, TEA method, sulfolane process, sulfolane+DIPA Method, sulfolane+MDEA method, methanol+secondary amine method, alkyl alcoholamine solwution method and MEA process, DEA process, MDEA that activating agent is added Method, TEA method etc., the CO after decarburization in unstripped gas2It is removed to 0.01~0.8Vol%, the carbon dioxide of removing can be used as Carbon dioxide product sale is vented as the unstripped gas of other processes or after reaching emptying standard, removes CO20.2~ 20MPa, it carries out under the conditions of 20~150 DEG C, in some embodiments (0.2~4MPa, 20~80 DEG C), when using absorption process When isolated unit as decarburization, it will usually take micro absorbing liquid out of in gas, need to be added behind its unit Temp.-changing adsorption separative unit is to remove the ingredients such as the heavy constituent contained in water and some gases.Temp.-change adsorptive process removes moisture and again The ingredients such as component；Adsorbent is molecular sieve, active carbon, aluminium oxide, silica gel or their composite bed, wherein containing for removing is a large amount of Carbon dioxide tail gas can recover energy when pressure is greater than 0.15MPa into residual pressure recovering equipment.
In one embodiment, in addition to including above-mentioned desulfurization and de- CO2Afterwards, the first removal of impurities pretreatment is also wrapped It includes except CH4Or/and dehydrogenation deoxidation；By removing CH4It can get industrial nitrogen (GB3864-2008 and its more new edition for meeting standard This) it is utilized.Through taking off CH4CO in unstripped gas afterwards2It is removed to≤0.2Vol%.Due to removing CH4Reaction needed for temperature compared with Height makes except CH4After desulfurized step, remove in advance, if desulfurization and de- CO2Step separates, and makes except CH4After desulfurization De- CO2Before, be conducive to save energy and heat exchange equipment, reduce equipment investment and operating cost.In one embodiment, it removes CH4Methane mainly is removed by carrying out the catalyst combustion reaction of methane under certain temperature and pressure, controls reaction temperature And pressure be respectively 200~1000 DEG C (may further be 250~350 DEG C) and 0.1~10MPa (may further be 0.2~ 1.6MPa), prevent catalyst from losing activity.Used catalyst can be this field conventional catalyst, for example, containing iron and/or Copper and/or cobalt and/or manganese and/or molybdenum and/or zinc and/or aluminium and/or nickel and/or chromium and/or bismuth and/or magnesium and/or titanium and/ Or the metal of barium and/or ruthenium and/or zirconium and/or cerium and/or group of the lanthanides and/or platinum and/or palladium and/or gold and/or rhodium and/or calcium And/or their oxide and/or their soluble-salt and/or the metal composite oxide formed between them is active group Point.With titanium, zirconium, manganese, iron, nickel, cobalt, copper, molybdenum, tungsten, zinc, cobalt, cerium, aluminium, chromium, bismuth, magnesium, titanium, barium, ruthenium, zirconium, cerium, lanthanum, platinum, palladium, Gold, rhodium, the metal of calcium and/or their oxide and/or their soluble-salt and/or the composition metal formed between them One or more of oxide and silicon, rare earth, alkali metal, alkaline-earth metal, the oxide of transition metal are auxiliary agent.Carrier is Active carbon, aluminium oxide, silica, magnesia, titanium oxide, silica gel, molecular sieve, ceramic honey comb, monazite, honeycomb, metal Plate, ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, metal foam, ceramic foam, graphite-based foaming Body etc..Except CH4Content≤0.5% in unstripped gas afterwards, further CH4≤ 0.1%.If you do not need to meeting the Industrial Nitrogen of standard Gas can not then use the step of removing methane.
If the content of the oxygen contained in first gas is higher (about > 0.1%, being all larger than the numerical value in representative gases) When, subsequent CO and nitrogen separation adsorbent can be had adverse effect on, even cause its inactivation, shorten its service life, Leading deoxidation is needed, and product gas requires lower hydrogen content and oxygen content；Due to carrying out being catalyzed de- H in pure CO later2 And O2, more CO and O can be made2Reaction causes the waste of CO, and since the reaction product after dehydrogenation deoxidation is reacted in catalysis It needs to remove again as impurity, simultaneously because H can be generated after reaction2O and CO2, as impurity in order to not influence subsequent reaction Catalyst need to remove, need the step of increasing corresponding removal of impurities and device remove by catalysis react caused by impurity.And And due to oxygen content excessively high so that adsorbent degradation, and over time through the requirement of separation is not achieved, and Due to the impurity that reaction generates, the purity of CO can not meet preset requirement, can not be as the unstripped gas of synthesizing glycol It is used for next step synthesizing glycol device.In addition to this, it is needed in required high concentration CO gas in the unstripped gas of synthesizing glycol Meet H2≤ 1000ppm and O2The concentration necessary of≤1000ppm.So primary in advance after desulfurization in the first removal of impurities pretreatment Dehydrogenation deoxidation (removing hydrogen when deoxidation simultaneously) fills into micro amount of oxygen, adjusts hydrogen-oxygen ratio, is in 0.1~20MPa pressure (in some implementations Be 0.2~4MPa in mode) and 50~1000 DEG C of (being in some embodiments 80~250 DEG C) temperature under the conditions of using selection Property dehydrogenation dehydrogenation catalyst removing coal gas in H2And O2).If desulfurization and de- CO2Step separates, and dehydrogenation deoxidation is made to be in desulfurization CO is taken off afterwards2Before, if containing CH is removed4Step is in dehydrogenation deoxidation except CH4Afterwards, so that a step reaches target, protection is had Adsorbent, the catalyst of subsequent step reduce CO waste, reduce the removal step of produced impurity after catalytic dehydrogenation deoxidation, contracting Short process reduces investment and operating cost, simultaneously because the temperature of gas is higher in front can satisfy catalytic dehydrogenation deoxidation Reaction temperature, so as to avoid put behind need heat up and caused by need heat exchange equipment needed for investment and running cost With, while this sequencing also complies with the principle step by step of reaction temperature height, reduces investment and the running cost of heat exchange equipment With dehydrogenation deoxidation is also beneficial to increase the purity of nitrogen, obtains the industrial nitrogen for meeting standard.If oxygen-containing in certain supplied materials gas Catalytic dehydrogenation deoxygenation step can also be put without dehydrogenation deoxidation if measuring lower (≤0.1%) in the first removal of impurities pretreatment CO and N is separated to pressure-variable adsorption2It below, in this way will not be to causing adsorbent, rapid catalyst deactivation, quickly shorten it using the longevity Life, but it will cause CO waste, increase impurity removing equipment and heat exchange equipment, increase process, increase investment and operating cost.Dehydrogenation Deoxidation is preferably at de- CO2Before.Palladium and/or platinum and/or cobalt and/or manganese and/or copper of the catalyst of dehydrogenation deoxidation to contain Metal and/or their oxide and/or sulfide be active component, with sodium, potassium, magnesium, titanium, zirconium, vanadium, manganese, iron, nickel, cobalt, Copper, molybdenum, tungsten, lanthanum, zinc, silver, palladium, the metal of cobalt or cerium and/or their oxide and/or sulfide and/or they formed One or more of complex compound is auxiliary agent.Carrier is active carbon, aluminium oxide, silica, magnesia, titanium oxide, silica gel, molecule Sieve, ceramic honey comb, monazite, honeycomb, metal plate, ripple packing, corrugated plating, fiber (cloth) material and structure, braided fabric, Metal foam, ceramic foam, graphite-based foaming body etc..
The second removal of impurities pretreatment includes dedusting, tar removing, except heavy constituent, dehydration, desulfurization, deoxidation, de- CO2Or Except CH4Except CmHnIn a step or a few steps combination；When using one-step method, coke-stove gas is purified through the second removal of impurities pretreatment The control of objectionable impurities content exists: sulfide≤1.15ppm, H2O≤100ppm, Cl+≤ 0.03ppm, arsenide≤0.1ppm, burnt Oil+dirt≤1mg/Nm3, naphthalene≤1mg/Nm3, further, sulfide≤0.1ppm, Cl+≤ 0.01ppm, when using two-step method, Coke-stove gas pre-processes purified objectionable impurities content control through the second removal of impurities and exists: sulfide≤1.15ppm, H2O≤ 100ppm, O2≤ 1%, NH3≤ 200ppm, Cl+≤ 0.03ppm, arsenide≤0.1ppm, tar+dirt≤1mg/Nm3, naphthalene≤ 1mg/Nm3, further, sulfide≤0.1ppm, Cl+≤ 0.01ppm, O2≤ 0.2%.
In one embodiment, the second removal of impurities pretreatment includes desulfurization and de- CO2, take off CO2With the same stepping of desulfurization Capable or de- CO2After desulfurized step.Sulphur can be to the multiple catalysts (dehydrogenation deoxidation, product gas requirement) in subsequent step It is had adverse effect on adsorbent (especially CO and nitrogen separation), influences its adsorption capacity, even caused its inactivation, shorten Its service life, so to be removed at first to it.Gas needs to remove the CO contained in gas later2, because of CO2It will affect change Pressure absorption purification CO and pressure swing adsorption method remove CH4、CmHnThe separating effect of exotic fuels gas is made, due to CO2It is purifying CO step and removing CH4、CmHnBeing made on the rapid adsorbent used of exotic fuels jia bombardier has certain adsorbance, leads to CO2With CO、CO2With nitrogen, CO2And CH4、CO2And CmHnSeparation is not high, CO2Presence will lead to purification CO step can not obtain To the CO of high-purity, can to contain more CO in the CO gas isolated2, can also to isolate by CH4、CmHn It is made in exotic fuels gas and contains more CO2, so to remove CO in advance2, work as CO2, concentration it is lower when, to CH4、 CmHnWhen the influence of exotic fuels gas is made in allowed limits, CO2Can and CH4、CmHnOne reinstates a step pressure-variable adsorption Method removing.If removing CO using absorption process2And thick desulfurization, then it needs to remove and takes micro absorbing liquid in gas out of, generally Moisture and heavy constituent micro contained by gas are removed by temperature swing absorption unit, because moisture and heavy constituent will affect subsequent change The effect for pressing adsorption step, can have adverse effect on adsorbent, can reduce the separating capacity of the pressure-variable adsorption of adsorbent, very Irreversible damage can be extremely caused to adsorbent, makes adsorbent degradation, even caused its inactivation, shortened its service life, especially Be for purify CO step adsorbent damage it is even more serious, make rapidly adsorbent degradation, cause its inactivation, be not available；Institute To need preferential removing removing moisture and heavy constituent.The sulphur of removing is sent to sulfur recovery system, and unstripped gas is after desulfurization in gas Sulphur is removed to no more than 1.15ppm, in some embodiments up to 0.1ppm or less.Desulfurization is in 0.2~20MPa, 20~700 DEG C, in some embodiments (0.2~4MPa, 20~400 DEG C).CO after decarburization in unstripped gas2It is removed to 0.01~ 0.8Vol%, the carbon dioxide of removing can be used as carbon dioxide product sale or the unstripped gas or reach as other processes is put It is vented after empty standard, removes CO2It is carried out under conditions of 0.2~20MPa, 20~150 DEG C, in some embodiments (0.2~ 4MPa, 20~80 DEG C).When the isolated unit using absorption process as decarburization, it will usually take micro suction out of in gas Liquid is received, needs to be added temp.-changing adsorption separative unit behind its unit to remove the heavy constituent etc. contained in water and some gases Ingredient.When using absorption process, absorbent has absorbability to sulphur and carbon dioxide simultaneously, then can remove at the same time sulphur and Then carbon dioxide completes desulfurization again using the fine de-sulfur unit of the compositions such as metal oxide and adsorbent again, advantageous in this way In saving cost.
In one embodiment, the second pre- removal of impurities processing, is first caught using using electrical tar precipitator, oil suction slot before sulphur removal Collect tar, carries out removing benzene, naphthalene, tar, ammonia, thiophene, HCN, most oxygen etc. except impurity, deoxygenation using temp.-changing adsorption Impurity.By the detar of front and except various impurity are the adsorbent or absorption process in order to protect pressure-variable adsorption step below Absorbing liquid makes it lack the harm by impurity, prolong the service life.
In one embodiment, the second removal of impurities pretreatment further includes except CH4Except CmHn, remove CH4In desulfurization and De- CO2After step.Using absorption process desulfurization, de- CO2When, remove CH4Except CmHnIt is carried out after temp.-changing adsorption or/and fine de-sulfur.It removes CH4Except CmHnIt is carried out using pressure swing absorption process.Exotic fuels gas is made externally to supply, this avoid in step below The pressure process that separation needs to carry out is carried out again, so that it is few that energy loss in exotic fuels gas is made；Simultaneously in order to avoid right It purifies adsorbent detrimental effect in CO step, influence its adsorption capacity, it is also desirable to remove CH in advance4、CmHnHigh heating value combustion is made Expect gas.Repressurization, component useful in gas is more at this time, and gas volume is minimum, and cost is relatively low for pressurization, and improves pressure at this time Power is conducive to the partial pressure of CO, and the adsorption capacity for being conducive to CO tends towards stability, to reach the separating effect, CO for being conducive to CO Purity, the energy consumption of CO and loss；In addition coke-stove gas is by the removal of impurities and processing step of front by directly purifying out CH4、 CmHnExotic fuels gas is made externally to supply, it is this uneconomic using the method for cryogenic separation that avoiding problems conventional methods Method purifies them, to save cost of investment and use cost.Except CH4Except CmHnIn 0.3~20MPa, 20~120 DEG C Under the conditions of carry out, in some embodiments (0.3~4MPa, 20~40 DEG C), through remove CH4Except CmHnRemoving in unstripped gas afterwards CH4Except CmHnIt is removed to CH4≤ 0.5%, CmHn≤ 0.1%, further, CH4≤ 0.1%, CmHn≤ 0.02%.Fig. 1 is shown A kind of preferable process flow, first gas such as blast furnace gas successively through desulfurization, remove CH4, dehydrogenation deoxidation, de- CO2Pass through again afterwards Pressure swing absorption process separates CO and N2, obtain CO；Second gas such as coke-stove gas is successively through temp.-changing adsorption removal of impurities, de- CO2(simultaneously Thick desulfurization), fine de-sulfur, remove CH4Except CmHnPass through a step pressure swing absorption process afterwards for H2With CO and N2Separation, purifies out H2, the change Tail gas in pressure absorption purifying hydrogen of hydrogen separates CO and N with first gas pressure swing absorption process2In suitable deflation, displacement tail gas mixing Flow direction removes CH afterwards4After step, by resulting CO and H2As H2/ CO unstripped gas is for producing ethylene glycol.
The production H accordingly provided2The device of/CO unstripped gas, such as Fig. 5, comprising:
First removal of impurities pretreatment unit, for pre-processing to first gas, which includes The desulfurizer that is sequentially connected, except CH4Device, dehydrogenation device for deoxidizing and de- CO2Device；
First pressure-swing absorption apparatus, with de- CO2Device is connected, for will treated the through the first removal of impurities pretreatment unit One gas separates CO and N by pressure swing absorption process2, obtain CO；De- CO2Pipeline between device and the first pressure-swing absorption apparatus Preferably it also is provided with a temperature swing absorption unit (not shown).
Second removal of impurities pretreatment unit, for pre-processing to second gas, which includes Temp.-changing adsorption exclusion device, the de- CO being sequentially connected2Device, removes CH at desulfurizer4Except CmHnDevice；
Second pressure-swing absorption apparatus, with remove CH4Except CmHnDevice be connected, for will through second removal of impurities pretreatment unit after Second gas goes out the H in gas by pressure swing absorption process separating-purifying2；Except CH4Except CmHnDevice and the second pressure-swing absorption apparatus Between pipeline also preferably be provided with a temperature swing absorption unit (not shown).The offgas outlet of second pressure-swing absorption apparatus with The suitable deflation of first pressure-swing absorption apparatus and displacement offgas outlet pass through piping connection, the pipeline and the first removal of impurities pretreatment unit The gas feed of middle dehydrogenation device for deoxidizing connects.
The device for producing ethylene glycol is connected to the H of the CO outlet and the second pressure-swing absorption apparatus of the first pressure-swing absorption apparatus2 Outlet is used for CO obtained and H2It carries out reacting obtained alcohol.
Based on above technique, present invention cog joint blast furnace gas or/and coal gas of converter produce H2/ CO raw material The device of gas, structure are as previously described.
In the methods described above, it is needed in some separating steps using to pressure-variable adsorption lock out operation；The purpose of the present invention It is relatively high for supplied materials gas pressure or needs to be pressurized to relatively high situation and be just able to achieve the separating effect for meeting demand Room temperature pressure-variable adsorption and non-room temperature pressure-variable adsorption field present in bigger pressure change process, grasped in frequent buck During work, by had higher pressure energy in the high pressure gas of equipment discharge, there are a large amount of energy losses for this process, so Energy recycle device is added during these pressure changes are bigger, recovers energy, the energy of recycling for providing machinery Can, for providing pressure to gas or liquid.
The equipment of discharge high pressure gas referred herein in industrialized variable-pressure adsorption equipment there are many, it is most commonly seen Be adsorption tower, be also possible to other vacuum tanks, surge tank, in these equipment have high pressure gas, pressure reduction may be and Another adsorption tower or vacuum tank, surge tank in low-pressure state pressed, pressurising, it is suitable put or the processes such as inverse put, at this During a little, the gas energy that the high pressure gas in adsorption saturation adsorption tower can be recycled through energy recycle device recycling is again Flow to adsorption tower or vacuum tank, surge tank in low-pressure state, be completed at the same time energy recycling and normal pressure-variable adsorption Pressure reduction, energy recycle device here can be converted pressure energy possessed by high pressure gas to when using expanding machine Mechanical energy, these mechanical energy can be applied to drive compressor rotation, engine power generation, supplement motor rotation power output etc. a variety of Purposes.It is all unstable for the decompression gas flow, pressure and the pressure drop that access energy recycle device in pressure-variable adsorption process, With periodical and bigger fluctuation, it will usually cause energy recycle device almost can not normal table work, therefore need Energy recycle device is correspondingly improved.
Major design design of the invention is: the periodic rapid fluctuations by stabilizing the gas by high-pressure installation discharge It can work normally expanding machine, mainly by slow by fluid in the gas access of expanding machine and/or gas outlet Flushing device stabilizes the fluctuation of air pressure；Another resolving ideas is: by inhibiting fluctuation of the shaft of expanding machine on revolving speed, It may be implemented to make its even running, can be realized by installing rotary resistance device in its shaft.
Based on above-mentioned design, there are several embodiments below:
The gas for needing energy regenerating enter energy recycle device in turbo-expander before or leave energy return The surge tank of a constant volume is added after receiving apparatus, surge tank can be used to stabilize the pressure of pressurized gas and the wave of flow It is dynamic, keep its basicly stable, the energy for first recycling the middle gas of pressure-variable adsorption by expanding machine may be implemented, be converted into the machinery of axis Energy.
In another embodiment, regulating valve is installed on the gas piping in energy recycle device, by pressing During power changes, according to Pressure change frequencies and size, correspondingly the aperture of regulating valve is adjusted, is expanded to entering The pressure of the high pressure gas of machine and flowed fluctuation are inhibited.
For needing to increase the design of the shaft rotary resistance of expanding machine, in another embodiment, in expanding machine The flywheel of certain size and certain mass distribution is installed to increase the rotary inertia of axis in shaft, the installation site of flywheel can be On the upstream side of expanding machine or the shaft in downstream side.
Above as can be seen that after having used buffer unit or resistance device, when expanding machine switchs to gas pressure energy During mechanical energy, the variation fluctuation of pressure energy can be preferably stabilized, allows the normal smooth working of expanding machine, is also suitable for In mechanical energy is applied to it is other it is each require the expenditure of energy during.
In order to preferably utilize mechanical energy caused by expanding machine, mechanical energy can be driven to other equipment rotation works Make, is recycled after mechanical energy can also being converted to electric energy.
In one embodiment, motor is driven to generate electricity in expanding machine, since the rotation of expanding machine has centainly Cyclic fluctuation variation, therefore the electric energy of generation is connected to the grid, power grid needs to have biggish electric loading capacity, utilizes Big power grid to the carrying capacity of periodically fast-changing electric current, can by with the electric energy that cyclic fluctuation changes stabilize with It realizes and utilizes；Electric energy in power grid can be delivered to other electrical equipments, can also drive the pressure in pressure-swing absorption apparatus again Contracting machine and then the gas or liquid compressed, make electric energy obtain reuse.
In pressure-swing absorption process, there is the processes periodically pressurizeed to gas.Therefore, in another implementation In mode, expanding machine drives electric energy caused by motor compressor can be driven to work by motor, completes to gas The pressurized operation of body or liquid, so that electric energy can recycle.
Due to the motor being connected with compressor operation when, overload can be to the appropriate rate of equipment, stability, service life, peace Full property adversely affects, and therefore, in one embodiment, motor can be connected with capacitance group or battery pack, work as electricity When stream fluctuates bigger, capacitance group or battery pack can quickly stabilize electric current and quickly change, and can reinforce motor system The response united to rotation energy needed for quick variation shaft.
The above description is that the embodiments that the mechanical energy generated using expanding machine is converted into electric energy, can also directly utilize Mechanical energy caused by expanding machine.In this embodiment, expanding machine, motor, compressor or pump group are filled at energy regenerating Coaxial drive system or not coaxial drive system can be formed by setting.Composition coaxial drive system is exactly to turn expanding machine Change the mechanical energy to come directly to replenish in the shafting of compressor or pump, while insufficient part provides energy by motor and carries out Supplement, such as motor is connected in biggish power grid, on the one hand by electric energy drive motor running, while motor Shaft is also interlocked with the shaft of expanding machine, realizes that mechanical energy is replenished the effect on motor, this mode simultaneously by expanding machine The mechanical energy that can be directly obtained using expanding machine, also can make the wave of mechanical energy by the collective effect of expanding machine and motor It is dynamic to be stabilized.Coaxial drive system has compact-sized, and overall efficiency is high, whole set equipment expense and operating cost are all relatively low, With preferable economic benefit.
For the process of pressure-variable adsorption, generally can there is high-pressure installation (such as: the adsorption tower of elevated pressures) to Low-voltage device (such as: the adsorption tower of lower pressure) conveying high-pressure gas, so that the pressure reduction of high-pressure tower, and the pressure of lower pressure column Power increases, and is also possible to that the pressure between two gas buffer tanks mutually changes or pressure between adsorption tower and surge tank is mutual Variation.When the energy recycle device using the fluid cushion device and expanding machine in the present invention as main body, gas may be implemented There is the phenomenon that gas temperature decline from when being flowed by high side to low side after expanding machine in body, this is because energy returns Receipts process is to be depressured the expansion process of external output work, and the temperature of the gas of expander outlet can decline, when cryogenic gas enters When in the tower to pressurize to other needs, adsorption temp can be reduced, and the adsorption temp of adsorption tower can be made lower than desorption and regeneration Temperature, the low adsorbance for being conducive to increase unit adsorbent of temperature when absorption, temperature height when desorption and regeneration advantageously allow The desorption of adsorbent more thoroughly, increase the dynamic adsorbance of adsorbent.It can also be using the gas of expander outlet through changing The cooling capacity that hot device externally exports certain temperature is used for other devices.
In addition, gas pressure quickly can also be effectively prevented by adding fluid cushion device before and after expanding machine Power periodicity quick shift；Since excessive and frequent impact load can make the easy dusting of adsorbent, adsorbent is reduced Service life, while also having an adverse effect to the safety of adsorption tower, tired service life, so having used in pressure-swing absorption apparatus It is middle to have used the rapid fluctuations that inhibit high pressure gas with equipment such as control valve, surge tanks, enable to making for adsorbent Extended with the service life, while being also beneficial to the safety and tired service life of adsorption tower.
Based on the operation of above-mentioned energy recycle device, a typical pressure-swing absorption process is as follows in the present invention:
One relatively common pressure-variable adsorption industrial process is as described below:
Step 1 is entered the adsorption tower in absorption phase, most of easily absorbed component quilt by the gaseous mixture of upstream supplied materials Adsorbent adsorbs in adsorption tower, and it is absorption phase that most of unsuitable easily absorbed component, which passes through adsorption tower bed,.
Step 2 is depressured what step 1 obtained in the adsorption tower of adsorption saturation, pressure reduction may be with it is another Platform is in the adsorption tower of low-pressure state or vacuum tank, surge tank are pressed, along putting or the processes such as inverse put.During these, The energy that high pressure gas in adsorption saturation adsorption tower can be recycled through energy recycle device recycling is then flowed into low pressure Adsorption tower or vacuum tank, the surge tank of state.It has been completed at the same time recycling and the pressure reduction of normal pressure-variable adsorption of energy.
Step 3, there may be need will be after the resulting decompression in the adsorption tower or vacuum tank, surge tank etc. of step 2 Gas be depressured again or by the gas after decompression by it is certain processing (such as: displacement or again absorption, it is with pressure rinse, Pressurising etc.) after be depressured again.This same process may be to need to take the processing method similar with step 2.This Process may be to be pressed, suitable put or inverse put was waited with another adsorption tower or vacuum tank, surge tank in low-pressure state Journey.During these, the high pressure gas in adsorption saturation adsorption tower recycles the energy that can be recycled through energy recycle device Amount then flows into adsorption tower or vacuum tank, surge tank in low-pressure state.It has been completed at the same time the recycling and normal transformation of energy The pressure reduction of absorption.
Step 4, there may be the similar procedure of step 2 or step 3 is repeated up to adsorption tower drop to it is sufficiently low Pressure.
The adsorption tower that low-pressure state is dropped in step 4 is carried out desorption and regeneration process in a low voltage state by step 5, It may take to vacuumize, purge or vacuumize during this and add the methods of purging or low pressure desorption.
Step 6, there may be need the adsorption tower by low pressure desorption by other adsorption towers in step 3 or steady It presses tank, surge tank to carry out boost pressure process, the process energy regenerating in step 2 or step 3 may be accepted in this process The high pressure gas being depressured afterwards.
Step 7, there may be need will be after the resulting boosting in the adsorption tower or vacuum tank, surge tank etc. of step 6 Gas boosted again or by the gas after boosting by it is certain processing (such as: displacement or again absorption, it is with pressure rinse, Pressurising etc.) after boosted again, may be accepted in these possible boost process in step 2 or step 3 and pass through energy The high pressure gas being depressured after amount recycling.
Step 8, there may be need by the adsorption tower unstripped gas passed through after boosting in step 7 or by adsorption tower Not adsorbed gas after absorption boosts to the pressure close to adsorption step again.
Step 9, preceding 8 processes carry out the continuous continuous operation that moves in circles for single column, for phase between tower and tower Mutually cooperate, alternately move in circles continuous continuous operation.
The processes such as its High Pressure Absorption, decompression energy regenerating, decompression, low pressure desorption move in circles for single column continuous Continuous operation, for cooperating between tower and tower, staggeredly carrying out the continuous continuous operation that moves in circles.
Periodically quickly variation pressure energy recycling during pressure-variable adsorption is separated, is converted to conventional available machinery It can supply to gas-pressurization, save to electric energy consumed by gas pressurized.In contrast to no addition energy recycle device Pressure swing adsorption system, can be recycled routine pressure swing adsorption system in the energy loss due to caused by pressure difference 50%.
In addition, the not adsorbed gas possible pressure in adsorption process after adsorption tower adsorbs is relatively high, or to drop a hint Or do not needed at demand end so high pressure gas can also the gas access amount of high pressure recycle and pressurize couple Device carry out energy regenerating, the gas of the pressure reduction after recovering energy access demand end or is vented again again.
In the present invention, adsorbent employed in adsorption process can be the adsorbent of any kind of suction-operated, It is not particularly limited, can be molecular sieve, active carbon, carbon molecular sieve, activated alumina, carbon fiber etc. and their mixing It loads and layering loads.
The present invention is further illustrated below with reference to specific embodiment, unless otherwise specified, side employed in embodiment This field conventional means can be used in method, adsorbent or catalyst etc..
Embodiment 1
After blast furnace gas supplied materials (380 DEG C, 0.36MPa) first passes through dedusting, then pass through iron, manganese at 380 DEG C, 0.36MPa Oxide and ZnO composition desulfurizing agent desulfurization after, with the reduction of temperature, then through methyl hydride catalyzed at 300 DEG C, 0.36MPa Combustion reaction after removing wherein micro methane, is further reduced to 200 DEG C in temperature and pressure remains unchanged and is still Catalysis reaction is carried out under conditions of 0.36MPa, removes hydrogen and oxygen micro in blast furnace gas.Gained gas is further existed Temperature is reduced to 32 DEG C and pressure is remained unchanged and still removed contained by gas to enter temperature swing absorption unit under conditions of 0.36MPa The ingredients such as micro moisture and heavy constituent after enter pressure-changeable adsorption decarbonization device carbon dioxide removal, the carbon dioxide of removing passes through It is vented after reaching discharge standard after processing.Gas component mainly contains CO and nitrogen at this time.This portion gas is sent into transformation to inhale The separation that CO and nitrogen are carried out in attached CO and nitrogen separation device is 0.35MPa in adsorptive pressure, and operation temperature is 32 DEG C Under the conditions of extract technical grade nitrogen (volume composition >=99.2%), and be sent to nitrogen recycling system as product.Transformation is inhaled The CO product that attached tower bottom vacuumizes the high-purity being desorbed out, which is sent into compressor set, to be pressurized, until 0.35MPa enters intermediate air accumulator Afterwards, it is used as the unstripped gas of synthesizing glycol for next step synthesizing glycol device.It is filled in pressure-variable adsorption CO and nitrogen separation Due to needing to obtain the CO gas of high-purity in setting, need to use displacement step, the supplied materials of displacement gas arises primarily at coke oven The CO for the high-purity for purifying out in coal gas.
By coke-oven plant by certain treated coke-stove gas supplied materials gas (40 DEG C, 0.02MPa) and blast furnace gas and coke oven After the Process Gas mixing such as the suitable deflation, reverse gas, the displacement tail gas that are generated in pressure-variable adsorption step in coal gas treatment process, so both The CO and H in pressure-variable adsorption step in Process Gas are recycled2Etc. useful gas, avoids waste simultaneously and improve coke-oven coal CO and H in gas2Concentration so that absorption when gas partial pressure increase, increase separation, be conducive to obtain high-purity CO and H2.Mixed gas boosting first passes through electrical tar precipitator, oil suction slot to 0.4MPa then at 0.4MPa, 40 DEG C in 40 DEG C Removal of impurities and deoxygenation are carried out by temperature swing absorption unit, removes the impurity such as benzene, naphthalene, tar, ammonia, thiophene, HCN, most oxygen. Then most H is removed by the thick desulfurization and decarburization of MDEA absorption process again2S and organic sulfur and CO2, gained gas adsorbing again Pressure is 0.3MPa, and operation temperature is molten in process activity MDEA by temperature swing absorption unit removing gas under conditions of being 32 DEG C Take moisture and heavy constituent micro contained in micro absorbing liquid when liquid desulfurization and decarburization in gas out of, then then at 0.3MPa, It is de- that 40 DEG C of fine de-sulfur units by the compositions such as iron, manganese, the metal oxide of zinc and active carbon, molecular sieve and aluminium oxide carry out essence Sulphur makes the sulfur content in gas phase lower than 0.1ppm.Then pass through pressure swing adsorption method one-step removal CH again4、CmHn, the gas of removing It is externally supplied as exotic fuels gas；Gas is after being pressurized 3.0MPa in 32 DEG C to the dress for entering Pressure Swing Adsorption CO later It sets, due to needing to obtain the CO gas of high-purity in the device of Pressure Swing Adsorption CO, needs to use displacement step, displacement gas Supplied materials arise primarily at the CO of the high-purity for purifying out in blast furnace gas, be in this way due in coke-stove gas CO it is dense Spend that low, purification difficulty is big, the purity after purification is relatively low, and the concentration of CO is higher in blast furnace gas, purification difficulty relatively It is small, purification after purity it is relatively high so that the step for purification process in using its be displacement gas, make it easier to from CO is purified in coke-stove gas and obtains the CO for meeting concentration requirement, and makes CO and H2The rate of recovery increase.High-purity after purification CO it is mainly supplied to blast furnace gas after catalytic dehydrogenation deoxidation as displacement gas, due to the CO after purifying in coke-stove gas It is narrow-minded, and the tolerance of blast furnace gas is very big so will not produce bigger effect to the purity after it is purified, to realize highly concentrated It spends the overall balance with low concentration and meets overall requirement.Simultaneously because the CO after purifying in coke-stove gas is narrow-minded then The demand pressure of continuous synthesizing glycol unstripped gas is higher, the investment cost and operating cost of required individual supercharging equipment all compared with It is high.And the pressure as displacement gas is lower, can subtract using the CO for the high-purity for purifying out in coke-stove gas as displacement gas Scalp expense and operating cost.And since the CO after purifying in coke-stove gas is narrow-minded, it is not used as blast furnace gas enough The tolerance for purifying the displacement gas of CO makes coke oven by adjusting the tolerance in blast furnace gas as the CO of the high-purity of displacement gas The tolerance based on CO after purifying in coal gas is used as the tolerance of the displacement gas of blast furnace gas purification CO enough.Finally have to purity The CO of the high-purity purified in higher blast furnace gas.The non-adsorbable gas warp of tower top in the device of Pressure Swing Adsorption CO later Purifying hydrogen of hydrogen device is crossed, the H of high-purity is obtained2Into after intermediate air accumulator, the unstripped gas as synthesizing glycol is in next step Synthesizing glycol device uses.
The unstripped gas that synthesizing glycol has not only been obtained under the technique of the present embodiment and reaction process, has also recycled industry Grade nitrogen, and CO a small amount of in coke-stove gas has been purified, accomplish to make the best use of everything, reduced waste and in blast furnace gas The a small amount of methane contained is carried out catalyst combustion reaction processing by high temperature workshop section, and environmental protection index is more secure.
1 concrete technology flow process of embodiment is detailed in Fig. 2, and the gas component in each step process is shown in Table 1.
Table 1
Embodiment 2
After coal gas of converter supplied materials (0.2MPa, 360 DEG C) first passes through dedusting, then through catalytic hydroconversion make the sulphur in gas turn The hydrogen sulfide (0.2MPa, 300 DEG C) easily removed is turned to, gas after processing enters gas compression unit and is pressurized to 0.4MPa, By gained gas further under conditions of temperature is reduced to 40 DEG C and pressure remains unchanged still as 0.4MPa through carbon dioxide Absorption tower, using MDEA absorption process carbon dioxide removal and extremely, Determination of Trace Sulfur, MDEA absorption process use this carbon dioxide absorption tower Absorbing liquid be generally be added sulfolane active MDEA solution, through absorption after active MDEA solution go out tower through pressurization go to The absorption tower for handling the decarbonization device of coke-stove gas, carries out absorption decarburization as absorbing liquid again.The carbon dioxide of removing is through locating It is used after reaching standard after reason for the recycling of other devices.Gas after carbon dioxide absorption tower desulfurization and decarburization is sent into alternating temperature It is 0.2MPa in adsorptive pressure, operation temperature carries out temp.-changing adsorption and separates and then remove under conditions of being 32 DEG C in adsorbent equipment After water and other heavy constituent ingredients, using passing through iron, manganese, the metal oxide of zinc and active carbon, molecular sieve and aluminium oxide etc. After the fine de-sulfur unit of composition carries out fine de-sulfur (0.2MPa, 32 DEG C), gas component mainly contains CO and nitrogen at this time.By this portion The displacement tail gas for mentioning hydrogen tail gas and pressure-variable adsorption CO and nitrogen separation of coke-stove gas after point gas and purified processing, along putting Pneumatic transmission enters to carry out the separation of CO and nitrogen in pressure-variable adsorption CO and nitrogen separation device (pressure-swing absorber), in similar adsorption pressure Under the conditions of power and adsorption temp (0.2MPa, 32 DEG C), (displacement gas is derived from it to the Methods For Purification CO gas separated by pressure-variable adsorption The CO itself extracted), purity >=99% of obtained CO gas contains a large amount of nitrogen what pressure-variable adsorption tower top was isolated Gas after the contained pressure energy of residual pressure recovering equipment recycling, be vented after reaching discharge standard after processing.Pressure-swing absorber Bottom vacuumizes to be pressurized in the gas feeding compressor set being desorbed out, until being urged under conditions of temperature is 140 DEG C after 0.35MPa Change reaction, after entering intermediate air accumulator after removing micro hydrogen and oxygen therein, the unstripped gas as synthesizing glycol is supplied Next step synthesizing glycol device uses.
It is processed by certain treated coke-stove gas supplied materials gas (0.02MPa, 40 DEG C) and coke-stove gas by coke-oven plant The mixing of the Process Gas such as suitable deflation, the reverse gas generated in pressure-variable adsorption step in journey, had both been recycled in pressure-variable adsorption step in this way CO and H in Process Gas2Etc. useful gas, avoids waste simultaneously and improve CO and H in coke-stove gas2Concentration so that The partial pressure of gas increases when absorption, increases separation, is conducive to the CO for obtaining high-purity and H2.Mixed gas boosting Electrical tar precipitator, oil suction slot is first passed through after being 40 DEG C to 3.2MPa, temperature to be removed using temp.-changing adsorption (3.2MPa, 40 DEG C) Miscellaneous and deoxygenation removes the impurity such as benzene, naphthalene, tar, ammonia, thiophene, HCN, most oxygen.Into carbon dioxide absorption tower, this Carbon dioxide absorption tower uses MDEA absorption process carbon dioxide removal and most sulphur, the absorbing liquid one that MDEA absorption process uses As for be added sulfolane active MDEA solution, this carbon dioxide absorption tower using activity MDEA solution mostly come from processing turn The carbon dioxide absorption tower of producer gas carries out absorption decarburization as absorbing liquid again, also partially absorbs liquid and comes from through overheating again Raw lean solution and process depressurizes regenerated semi lean solution.Active MDEA solution after absorbing saturation releases contained by decompression regeneration Partial CO 2, partially by decompression activating and regenerating active MDEA solution as semi lean solution go to absorption tower remove dioxy Change carbon；The active MDEA solution of remaining part ramp regeneration in hot recycling tower release contained remaining partial CO 2 and The regeneration of sulphur post activation, final activating and regenerating completely is lean solution；The carbon dioxide of removing is vented after reaching discharge standard after processing. Then the gas after active MDEA solution decarbonization, desulfuration is again 3MPa in adsorptive pressure, under conditions of operation temperature is 40 DEG C It is taken out of in gas when by activity MDEA solution by temperature swing absorption unit removing gas micro- contained in micro absorbing liquid The moisture and heavy constituent of amount, then heat to 280 DEG C, 3MPa pass through the gold of catalytic hydroconversion organic sulfur and iron, manganese, zinc again The thick desulfurization and fine de-sulfur unit (3MPa, 280 DEG C) for belonging to the compositions such as oxide make the sulfur content in gas phase lower than 0.1ppm.Then It is cooled to 32 DEG C again, passes through pressure swing adsorption method one-step removal CH4、CmHn, it is external that exotic fuels gas is made in the gas conduct of removing Gas supply；Gas enters Pressure Swing Adsorption hydrogen device under the conditions of 3MPa, 40 DEG C later, obtains the H of high-purity2Into centre After air accumulator, the unstripped gas as synthesizing glycol is used for next step synthesizing glycol device.Pressure Swing Adsorption hydrogen dress Contain a large amount of CO gas in the tower bottom gas set, by pressure-variable adsorption CO and nitrogen separation device in itself and coal gas of converter treatment process In suitable deflation, displacement tail gas pressurization after in coal gas of converter treatment process after the gas mixing of fine de-sulfur enter transformation inhale Attached CO and nitrogen separation device, recycle coke-stove gas Pressure Swing Adsorption hydrogen device tail gas in containing a large amount of CO gas with And suitable deflation in CO and nitrogen separation device, in displacement tail gas contain a large amount of CO gas, it makes after treatment The unstripped gas of satisfactory synthesizing glycol.
H is prepared under the technique of the present embodiment and reaction process2/ CO unstripped gas mainly considers with the MDEA that activator is added Absorption process removes CO under high and low two kinds of different pressures respectively in two times2, CO is removed twice2Method all use absorption process, and And CO is removed twice2Using same absorbent.Absorbent removes CO on the absorption tower of the decarbonization device of processing coal gas of converter2's Absorption tower at lower pressures absorbs a certain amount of CO in the process2Afterwards, processing coke-stove gas is entered after absorbing liquid is pressurized Decarbonization device absorption tower remove CO2During, absorption tower at a higher pressure continues to absorb CO2Afterwards, to be absorbed complete Cheng Hou enters back into regenerator and completes activating and regenerating process.Since the operation on the absorption tower of the decarbonization device of processing coal gas of converter exists The absorption carried out under lower pressure condition, saturation absorption is generally not implemented in absorbing liquid, and handles the decarbonization device of coke-stove gas Absorption tower absorption process pressure it is higher, above-mentioned absorbing liquid can be further to CO2It is absorbed, to reach full Be conducive to reduce the internal circulating load of absorbing liquid to reduce the internal circulating load of regenerated liquid, to be conducive to reduce recovery stream with, the method Journey.And the unstripped gas of synthesizing glycol has not only been obtained under the technique of the present embodiment and reaction process, while having been returned with overbottom pressure The contained pressure energy of gas recycling of the receipts system to emptying, and CO a small amount of in coke-stove gas has been recycled, obtain valuable gases To make full use of, reduce the waste of available gas, it is good for the environment simultaneously.
2 concrete technology flow process of embodiment is detailed in Fig. 3, and the gas component in each step process is shown in Table 2.
Table 2
Embodiment 3
After blast furnace gas supplied materials (0.2MPa, 350 DEG C) first passes through dedusting, then by manganese, zinc etc. at 350 DEG C, 0.2MPa After the desulfurizing agent desulfurization of the oxide composition of metal, reacts, remove wherein micro- through methane catalytic combustion at 290 DEG C, 0.2MPa After the methane of amount, with the reduction of temperature, gas after processing enters gas compression unit and is pressurized to 0.46MPa, then in temperature Degree is reduced to 200 DEG C and pressure remains unchanged still to carry out catalysis reaction under conditions of 0.46MPa, removes micro- in blast furnace gas The hydrogen and oxygen of amount.Gas after processing enters carbon dioxide absorption tower after 0.46MPa, temperature are reduced to 40 DEG C, this Carbon dioxide absorption tower uses DEA absorption process, this carbon dioxide absorption tower uses the DEA mixed solution that sulfolane is added to absorb Agent carbon dioxide removal in absorption tower, the DEA solution that this carbon dioxide absorption tower uses mostly come from processing coke-stove gas Decarbonization device absorption tower, carry out absorption decarburization again as absorbing liquid, carbon dioxide absorption tower also partially absorbs liquid From by regenerated absorbing liquid.Heating releases carbon dioxide and Determination of Trace Sulfur to DEA solution after absorbing saturation in regenerator again Activation and the regeneration of other impurity, the carbon dioxide of removing use after reaching standard after processing for the recycling of other devices.By Gas after carbon dioxide removal is 0.36MPa in adsorptive pressure, and operation temperature carries out temp.-changing adsorption point under conditions of being 32 DEG C After removing water and other heavy constituent ingredients in turn, adsorbed using the fine de-sulfur of the compositions such as active carbon, molecular sieve and aluminium oxide After tower carries out fine de-sulfur (0.36MPa, 32 DEG C), gas component mainly contains CO and nitrogen at this time.By this portion gas in The separation that CO and nitrogen are carried out in 0.35MPa, 32 DEG C of feeding pressure-variable adsorption CO and nitrogen separation device, in similar adsorptive pressure Under the conditions of adsorption temp, the Methods For Purification CO gas separated by pressure-variable adsorption, purity >=99% of obtained CO gas, and And the technical grade nitrogen (volume composition >=99.2%) of tower top is extracted, and be sent to nitrogen recycling system as product, remaining Tower overhead gas is vented after reaching discharge standard after processing after the contained pressure energy of residual pressure recovering equipment recycling.Pressure-swing absorber The CO product that bottom vacuumizes the high-purity being desorbed out, which is sent into compressor set, to be pressurized, until 0.35MPa, after 120 DEG C as synthesis second The unstripped gas of glycol is used for next step synthesizing glycol device.Due to needing in pressure-variable adsorption CO and nitrogen separation device To the CO gas of high-purity, need to use displacement step, the supplied materials of displacement gas arises primarily at the height for itself purifying out The CO of purity；And coke-stove gas purified in the step of high-purity CO gas, and the displacement gas of displacement step also derives from above The CO for the high-purity for purifying out in blast furnace gas.The source of displacement gas unified in this way can simplify step, simple flow.
By coke-oven plant by certain treated coke-stove gas supplied materials gas (0.02MPa, 40 DEG C) and blast furnace gas and coke oven The Process Gas mixing such as the suitable deflation, reverse gas, the displacement tail gas that generate in pressure-variable adsorption step in coal gas treatment process, are pressurized to 0.4MPa, 40 DEG C first pass through electrical tar precipitator, oil suction slot and carry out dedoping step and deoxygenation using temp.-changing adsorption, remove benzene, The impurity such as naphthalene, tar, ammonia, thiophene, HCN, most oxygen.Enter carbon dioxide absorption tower under the conditions of 0.4MPa, 40 DEG C again, This carbon dioxide absorption tower uses the thick desulfurization carbon dioxide removal of absorption process, and absorbent is the DEA solution that sulfolane is added, this dioxy The DEA solution that change carbon absorption tower uses mostlys come from the absorbing liquid in regenerator after regeneration, and the DEA after absorbing is molten Liquid goes out the absorption tower that tower goes to the decarbonization device of processing blast furnace gas through being pressurized, and carries out absorption decarburization again as absorbing liquid.It is de- The carbon dioxide removed is vented after reaching discharge standard after processing.Most H is removed by absorption tower2S and organic sulfur and CO2Gas, be then 0.3MPa in adsorptive pressure, operation temperature by temperature swing absorption unit removes gas under conditions of being 32 DEG C Body takes moisture and heavy constituent micro contained in micro absorbing liquid out of in gas when by DEA solution, then passes through again The fine de-sulfur unit that iron, manganese, the metal oxide of zinc and active carbon form makes the sulfur content in gas phase lower than 0.1ppm.Then again Pass through pressure swing adsorption method one-step removal CH4、CmHn, the gas of removing is made exotic fuels gas and externally supplies；Gas is through increasing later In 32 DEG C to the device for entering Pressure Swing Adsorption CO after pressure 3.0MPa, due to needing in the device of Pressure Swing Adsorption CO The CO gas of high-purity is obtained, needs to use displacement step, the supplied materials of displacement gas, which arises primarily in blast furnace gas, to be purified The CO of high-purity out is since the concentration of CO in coke-stove gas is low, purifies the purity of difficulty greatly, after purification relatively in this way It is low, and the concentration of CO is higher in blast furnace gas, purification difficulty is relatively small, the purity after purification is relatively high, so that at this It is displacement gas that it is used in the purification process of step, makes it easier to the purification CO from coke-stove gas and obtains meeting concentration requirement CO, and make CO and H2The rate of recovery increase.The CO of high-purity after purification is pressurized to 0.35MPa under conditions of 120 DEG C After catalytic dehydrogenation deoxidation, with the high-purity purified out by blast furnace gas CO together as synthesizing glycol unstripped gas for next Synthesizing glycol device is walked to use.Due to the raw material of the synthesizing glycol of the operation temperature and subsequent needs of catalytic dehydrogenation deoxidation CO is high temperature, and temperature close, and the principle step by step of reaction temperature height is also complied with by the arrangement of such technical process, Reduce the investment and operating cost of heat exchange equipment.Later in the device of Pressure Swing Adsorption CO the non-adsorbable gas of tower top in 3MPa, 32 DEG C of process purifying hydrogen of hydrogen devices, obtain the H of high-purity2Raw material into after intermediate air accumulator, as synthesizing glycol Gas is used for next step synthesizing glycol device.
H is prepared under the technique of the present embodiment and reaction process2/ CO unstripped gas mainly considers to be absorbed with DEA mixed solution Method is in two times respectively in high and low two different CO2Concentration under remove CO2, CO is removed twice2Method all use absorption process, And CO is removed twice2Using same absorbent.Removing of the absorbent on the absorption tower of the decarbonization device of processing coke-stove gas CO2During in lower CO2Absorption tower under concentration absorbs a certain amount of CO2Afterwards, pressurized rear into processing blast furnace gas Decarbonization device absorption tower removing CO2During in higher CO2Continue to absorb CO in absorption tower under concentration2Afterwards, wait inhale After the completion of receipts, enters back into regenerator and complete activating and regenerating process.Due to the absorption tower removing of the decarbonization device of processing coke-stove gas CO2Operation in lower CO2The absorption of absorbing liquid is carried out under concentration conditions, saturated absorption is generally not implemented in absorbing liquid, and handles The CO on the absorption tower of the decarbonization device of blast furnace gas2Concentration is higher, and above-mentioned absorbing liquid can be further to CO2It is absorbed, To reach saturation, the method is conducive to reduce the internal circulating load of absorbing liquid to reduce the internal circulating load of regenerated liquid, to be conducive to Reduce regeneration process.
3 concrete technology flow process of embodiment is detailed in Fig. 4, and the gas component in each step process is shown in Table 3.
Table 3
Comparative example 1
Difference with embodiment 1 is: the catalysis of front takes off H in blast furnace gas purification process in embodiment 12And O2Step is moved CO and N is separated to pressure-variable adsorption2After step, carry out being catalyzed again taking off to by obtaining pure CO after pressure-variable adsorption separation CO and nitrogen H2And O2.Other parts are all same as Example 1.
The result is that: the separation of CO and nitrogen are carried out in pressure-variable adsorption CO and nitrogen separation device, are in adsorptive pressure 0.35MPa, the nitrogen volume composition≤99.2% that operation temperature is extracted under conditions of being 32 DEG C, is unable to satisfy technical grade nitrogen Demand can only be sent to energy recycling system, be vented after recycling nitrogen pressure energy.And the volume composition≤99% of CO, meets Not preset requirement, can not use as the unstripped gas of synthesizing glycol for next step synthesizing glycol device.And Over time, adsorbent starts to deteriorate, and by about one month time, the purity of the CO purified out was begun to decline；Through The about bimestrial time is spent, the comparison of the purity of CO decline is more (purity is lower than 90%), takes the method for improving displacement tolerance To improve the purity of CO as far as possible；By about four months time, CO can not be prevented using the method for improving displacement tolerance The requirement of separation has been not achieved in the decline of purity, adsorbent.Pressure-variable adsorption tower bottom vacuumizes the CO product being desorbed out and is sent into pressure It is pressurized in contracting unit, until after being then warming up to 140 DEG C again, pressure, which remains unchanged, is still after 0.35MPa enters intermediate air accumulator Catalysis reaction is carried out under conditions of 0.35MPa, removes hydrogen and oxygen micro contained in CO gas.It is de- by being catalyzed H2And O2Pure CO used as the unstripped gas of synthesizing glycol for next step synthesizing glycol device, due to being carried out in pure CO It is catalyzed de- H2, de- H is made since CO content is high2And O2To H2≤ 100ppm, O2≤ 1000ppm, can make more CO and O2Reaction, causes the waste of CO, simultaneously because can generate H after reaction2O and CO2, as impurity in order to not influence subsequent anti- The catalyst answered needs to remove, and need to separately increase a set of temp.-changing adsorption purification device and remove by being catalyzed de- H2And O2Produced by reaction Impurity.
Comparative example 2
Difference with embodiment 2 is: Pressure Swing Adsorption hydrogen device tower bottom in oven gas purification process in embodiment 2 Tail gas enters after the gas mixing of fine de-sulfur after no longer it is pressurized with coal gas of converter treatment process as exhaust-gas treatment Pressure-variable adsorption CO and nitrogen separation device.Other parts are all same as Example 2.
The result is that: it can not recycle in coke-stove gas Pressure Swing Adsorption hydrogen device tail gas and contain a large amount of CO gas, The waste of a large amount of CO gas is caused, so that the total recovery of CO gas reduces 22%.
Comparative example 3
Difference with embodiment 3 is: pressure-variable adsorption during blast furnace gas purification in embodiment 3 not being separated CO and nitrogen In obtain pure CO as displacement gas supply oven gas purification process in Pressure Swing Adsorption CO device.Its displacement gas is respectively by each From isolated CO supply.Other parts are all same as Example 3.
The result is that: displacement gas is supplied by respective isolated CO respectively, then needs at least to increase a set of displacement air pressure Contracting machine also increases the expense of operation and maintenance to increase equipment investment, while also increasing the leakage point of fuel gas, To increase security risk.It can be seen that the concentration of CO will be much higher than CO in coke-stove gas supplied materials in blast furnace gas supplied materials Concentration, the concentration of the CO purified by blast furnace gas are higher than the concentration of the CO purified by coke-stove gas, with comparative example 3 In comparison, embodiment 3 can more effectively to purify by the CO that the blast furnace gas of concentration more purifies as displacement gas The purity for the CO that CO is obtained is higher, while making the displacement tolerance needed smaller, and displacement gas compression energy consumption becomes smaller, CO gas Loss becomes smaller, and the yield of CO gas increases.Required displacement tolerance reduces 4%, small 5%, the CO gas of displacement gas compression energy depletion The yield that the loss of body reduces 2%, CO gas increases by 2% (increasing to 96.8% by 94.8%).
Comparative example 4
Difference with embodiment 1 is: not pressure-variable adsorption separates in CO and nitrogen in blast furnace gas purification process in embodiment 1 Pure CO is obtained as Pressure Swing Adsorption CO device in displacement gas supply oven gas purification process, equally also not embodiment 1 Obtained in Pressure Swing Adsorption CO in middle oven gas purification process pure CO as displacement gas supply blast furnace gas purification process in become Press adsorbing separation CO and nitrogen device.Its displacement gas is supplied by respective isolated CO respectively.Other parts all with implementation Example 1 is identical.
The result is that: displacement gas is supplied by respective isolated CO respectively, then needs at least to increase a set of by oven gas The CO purified out also increases the expense of operation and maintenance to increase equipment investment for the booster compressor of ethylene glycol unstripped gas With, while the leakage point of fuel gas is also increased, to increase security risk.Eventually respectively obtain two bursts of concentration differences CO gas (concentration is respectively 99% and 99.5%).It can be seen that the concentration of CO will be much higher than coke oven in blast furnace gas supplied materials The concentration of CO in gas supplied materials, the concentration of the CO purified by blast furnace gas are higher than the dense of the CO purified by coke-stove gas Degree, in comparison with comparative example 4, the CO that embodiment 1 is purified by the blast furnace gas of concentration more can more have as displacement gas The purity for purify the CO that CO is obtained of effect is higher；Since the CO after purifying in coke-stove gas is narrow-minded, and blast furnace gas Tolerance is very big so will not produce bigger effect to the purity after it is purified, to realize the overall balance of high concentration and low concentration And meet overall requirement.And since the CO after purifying in coke-stove gas is narrow-minded, it is not used as blast furnace coal air lift enough The tolerance of the displacement gas of pure CO makes coke-stove gas by adjusting the tolerance in blast furnace gas as the CO of the high-purity of displacement gas The tolerance based on CO after middle purification is used as the tolerance of the displacement gas of blast furnace gas purification CO enough.One is finally had to purity The CO gas (concentration 99.5%) of the high-purity purified in higher blast furnace gas.Make the displacement tolerance needed simultaneously more Small, displacement gas compression energy consumption becomes smaller, and the loss of CO gas becomes smaller, and the yield of CO gas increases.Required displacement tolerance reduces 2%, the yield that the loss of small 3%, the CO gas of displacement gas compression energy depletion reduces 2.2%, CO gas increase by 2.2% (by 97%) 94.8% increases to.
4 the present embodiment of embodiment is used to illustrate the energy recovery process in two tower pressure-variable adsorptions
Also contain micro N in certain exhaust gas2、CO、CO2、CH4, the impurity such as Ar, need to be arranged to reach product hydrogen demands Hydrogen separation unit carries out separating-purifying.Since the operating pressure of upstream device is higher, the pressure-variable adsorption separator of H2 is caused The raw gas pressure of entrance is higher, while needing to complete the H after separation2Need to be pressurized to 4.2MPa (G).
Unstripped gas condition:
Component (butt) CO H2 CO2 N2 Ar CH4 H2S+COS
Vol, % 11.179 68.28 10.004 10.227 0.003 0.308 0.1ppm
Flow: 2000Nm3/ h (butt)
Pressure: 2.2MPa (G)
Temperature: 32 DEG C of ≈
Total H2O、O2、NH3、CH3OH, chlorine, phosphorus, arsenic, fluorine, HCN :≤0.1ppm
Through being equipped with H2The Pressure Swing Adsorption device for separating Special adsorbent carries out isolation of purified, and separating step includes: to inhale Attached, drop pressure inversely bleeds off pressure, vacuumizes, boost pressure, final pressurising.In the step of including pressure change: pressing, is inverse The device that energy regenerating and pressurization coupling are used in bleeding off pressure, finally boost has recycled energy, has been completed at the same time H2Specially point From purification.
Energy regenerating and the device of pressurization coupling be screw expander, compressor, motor unit at system and its is auxiliary It helps the capacitance group of effect, adjust valve group, flywheel, multiple surge tanks, further include the complication systems such as gear and control system. In pressurized H2Before entering in energy recycle device and the surge tank that a constant volume is added after energy recycle device is left, is come Stabilize pressurized H2Pressure and flow fluctuation, keep its basicly stable.
The device provided in the present embodiment is as shown in Fig. 6 and Fig. 7, Fig. 8, wherein the exhaust pipe of adsorption tower 1A is connected to swollen The discharge directions of the level-one 2 of swollen machine, the level-one 2 of expanding machine are connected with adsorption tower 1B again, expanding machine level-one 2 import and On the pipeline of outlet side, it is connected separately with surge tank 13,14, the shaft of the level-one 2 of expanding machine is connected with motor 4 again, electricity Motivation 4 is connected with compressor 3 again, for being also equipped with respectively by compressed gas in the inlet and outlet of compressor 3 to gas pressurized Import surge tank 11 and by compressed gas export surge tank 12, capacitance group 10 is also connected on motor 2.
Operating process below in conjunction with the device runs it and is further described:
The process that adsorption tower 1A (hereinafter referred to as A tower) is adsorbed in the period of (0~3min), valve A5A1 are beaten It opens, unstripped gas enters the adsorption tower A tower of state to be adsorbed by unstripped gas vacuum tank (18) and regulating valve E4；Tower top is unadsorbed Gas is used as product gas for other devices by product gas vacuum tank (19) and regulating valve E3.Adsorption tower 1B (hereinafter referred to as B Tower) process that is vacuumized, valve B6 opens, vacuumized through taking out air surge tank (5) to B tower by reciprocating pump (6). Energy recycle device does not have gas to pass through, and does not recover energy and supplies compressor (3) progress gas compression.
The process that A tower and B tower are pressed is carried out in the period of (3~4min), valve A2B3E2 is opened, and utilizes A High pressure gas in tower boosts to B tower, firstly, pressure, expanding machine (3) in the moment that valve A2B3E2 is opened, pipeline The pressure difference of inlet and outlet, changes in flow rate are all very big, so will cause bigger shock loading, excessive shock loading, which will affect, to be set Standby steady, safe operation, the service life that will affect equipment.So being imported and exported by regulating valve E5E10 to adjust expanding machine 3 Pressure difference, flow, valve A2B3E2 open moment, reduce regulating valve E5E10 aperture, corresponding adsorption tower is suppressed Pressure, to reduce influence of the impact load to expanding machine.Also by expanding machine inlet/outlet pipeline be connected surge tank (13) (14) come It is buffered, when pressure is higher than the pressure of valve E6E7 setting in the pipeline being connected with surge tank, valve E6E7 is opened, and is delayed It rushes tank to be connected with pipeline, gas distribution is made to enter surge tank, reduce the amount reduction impact load for entering the gas of expanding machine It influences, strives for the required time for the movement of expanding machine regulating mechanism, so that the cunning of adjusting control mechanism movement screw expander Valve adjusts the outer pressure ratio and stream of the expanding machine inlet and outlet after can be adapted to valve opening by the flow, inner pressure ratio, interior volume specific ratio of expanding machine Amount.The pressure energy band moving axis acted on expanding machine simultaneously rotates, and the mechanical energy of axis is converted into, due to the impact lotus formed when valve opening Carrying easily makes axis revolving speed be more than the revolving speed that needs of setting, and the change of axis revolving speed is unfavorable for same motor and forms the common driving compressor of resultant force The compression process to another gas is completed, increases axis by increasing the flywheel of certain size and certain mass distribution in shaft Rotary inertia so that under identical torque, shaft says that the acceleration obtained reduces, and is conducive to the stabilization of the revolving speed of shaft fixed Need revolving speed.The shaft of expanding machine is connected with motor (4), can drive motor rotation, but by expanding machine institute The mechanical energy revolving speed of output can lead to cyclically-varying due to the frequent change procedure of pressure-variable adsorption, will lead to motor Fluctuation of service, therefore, electric current needed for motor need to access overall grid, using big power grid to periodically quickly variation Electric current carrying capacity, application control device smoothly drives to complete motor.Under Impact Load, power grid is to electricity The flow of the electric current of motivation input may quickly reduce, or even cause the change of the conveying direction of electric current, so passing through motor Connect with capacitance group (10), to stabilize the quick variation of the flow of caused electric current under Impact Load, electricity can be reinforced Motivation system reduces the impact to power grid to the responding ability of rotation energy needed for quick variation shaft.With adding for runing time Long, since the gas in A tower gradually flows to B tower, A pressure tower is gradually decreased, and B pressure tower gradually rises, the pressure difference between two towers It is gradually reduced, the pressure difference of gas is gradually reduced between expanding machine inlet and outlet, and flow is also gradually reduced, this process gradually changes 's.The aperture of regulating valve E5E10 is tuned up, the drag losses at valve are reduced.Gradually with expanding machine import and export line pressure Variation, gas taper to outflow surge tank by inflow surge tank, when pressure is lower than valve in the pipeline being connected with surge tank When the pressure of E6E7 setting, valve E6E7 is closed, and surge tank is no longer connected to pipeline.Since gas compressed needs are substantially steady Fixed pressure and flow, it means that the needs of shaft power needed for the gas of compression are basicly stable, so gas compressed exists Compressor inlet and outlet have all accessed surge tank to cope with the fluctuation of possible pressure and flow, with the variation of time, expanding machine The pressure difference of gas is gradually reduced between inlet and outlet, and flow is also gradually reduced, so the shaft power that expanding machine is exported is also gradually Become smaller, then the shaft power for needing motor to be exported becomes larger, then the electric current of power grid input needs to adjust by control system Become larger shaft power needed for carrying out completion gas compressed.Electric current needed for motor needs to access overall grid, utilizes Big power grid smoothly drives the carrying capacity of periodically fast-changing electric current, application control device to complete motor. The slide valve for passing through adjusting control mechanism adjusting screw rod expanding machine simultaneously, adjusts the flow, inner pressure ratio, interior volume specific ratio by expanding machine So that the higher efficiency of the holding of expanding machine.
Since energy recovery process is the expansion process for being depressured external output work, the temperature of the gas of expander outlet can under Drop, cooling extent are determined that the gas of expander outlet is externally exported through heat exchanger (20) (21) by the pressure difference of expanding machine import and export The cooling capacity of certain temperature is used for other devices.The gas of expander outlet enters B tower, and the process of boost pressure is carried out to B tower, Gas temperature after certain cooling capacity is recycled in heat exchange is lower than the gas temperature at expander inlet end, and the entrance of cryogenic gas is so that B The temperature of tower reduces.For B tower, equally existed in the Plenum Process of next step similar cryogenic gas entrance so that The process that the temperature of B tower reduces, can make B tower in the step of being adsorbed in next step, the adsorption temp of B tower can reduce, meeting So that the adsorption temp of adsorption tower is lower than the temperature of desorption and regeneration, the low suction for being conducive to increase unit adsorbent of temperature when absorption Attached amount, what temperature height when desorption and regeneration advantageously allowed the desorption of adsorbent more thoroughly increases the Dynamic Adsorption of adsorbent Amount.Simultaneously because gas has carried out energy regenerating by expanding machine, the boost or depressurization process of adsorption tower can be made to tend to slowly, Compared to the pressure-swing absorption apparatus for not using energy regenerating, reduce the gas in pressure equalizing to the impact lotus of adsorption tower It carries.Excessive and frequent impact load can make the easy dusting of adsorbent, reduce the service life of adsorbent, while also to adsorption tower Safety, tired service life has an adverse effect.Energy regenerating dress has been used in pressure-swing absorption apparatus so having used Meeting is set so that the service life of adsorbent extends, while being also beneficial to the safety and tired service life of adsorption tower.
A tower carries out inverse put in the period of (4~5min), and B tower carries out Plenum Process.Valve A4E13 is opened, in A tower High pressure gas after energy recycling system has recycled pressure energy and cooling capacity through reverse gas surge tank (7) and inverse put air compressor (8) other burners are gone to after.It is similar with the function situation of energy recycling system in pressure equalizing, in the moment shape of valve opening At impact load, by adjusting valve group E6E8E9, surge tank (13) (15) (16), flywheel, capacitance group (10) work as a buffer into Row alleviates and the access of big power grid, the adjusting of expanding machine slide valve can also play certain buffer function to impact load. It is same similar with the function situation of energy recycling system in pressure equalizing, with the lengthening of runing time, the pressure of gas in A tower It gradually decreases, the pressure difference of gas is gradually reduced between expanding machine inlet and outlet, and flow is also gradually reduced, so what expanding machine was exported Shaft power is also gradually becoming smaller, then the shaft power for needing motor to be exported becomes larger, then the electric current of power grid input needs logical Cross control system adjusting become larger carry out completion gas compressed needed for shaft power.Electric current needed for motor needs to access Overall grid, using big power grid to the carrying capacity of periodically fast-changing electric current, application control device is electronic to complete Machine smoothly drives, and capacitance group is output and input smoothly to drive motor and also contributed by electric current.Pass through tune simultaneously The slide valve of control mechanism adjusting screw rod expanding machine is saved, so that the flow of expanding machine, inner pressure ratio, interior volume specific ratio are enabled suitable for after valve opening Expanding machine inlet and outlet outer pressure ratio and flow, so that expanding machine is kept higher efficiency.Equally pass through changing at expander outlet The cooling capacity that hot device externally exports certain temperature is used for other devices.The running feelings of energy recycling system in same and pressure equalizing Condition is similar, because joined energy recycling system during pressure change is excessive, so that the service life of adsorbent extends, It is also beneficial to the safety and tired service life of adsorption tower simultaneously.Valve E1E2B3 is opened, in product gas vacuum tank (19) High pressure gas carries out pressurising to B tower after energy recycling system has recycled pressure energy and cooling capacity, is increased to B pressure tower close to suction The pressure of attached step.Energy recycling system is to inputting electricity in the coping style of the shock loading of valve opening, power grid in this course The variation of stream externally provides cooling capacity, slide valve to expanding machine flow, inner pressure ratio, interior volume specific ratio to stable driving, by heat exchanger Adjusting and A tower suitable to let off journey similar.Gas temperature after certain cooling capacity is recycled in heat exchange is lower than expander inlet end Gas temperature, the entrance of cryogenic gas is so that the temperature of B tower reduces.
The process that B tower is vacuumized in the period of (5~8min), valve A6 is opened, by reciprocating pump (6) to A tower It is vacuumized.B tower is in adsorbed state, and unstripped gas enters state to be adsorbed by unstripped gas vacuum tank (18) and regulating valve E4 Adsorption tower B tower；Tower top unabsorbed gases supply other dresses as product gas by product gas vacuum tank (19) and regulating valve E3 Set use.B tower is since in boost pressure and Plenum Process before, the temperature of the gas after energy regenerating of receiving is low Gas temperature in expander inlet end.Meeting so that the adsorption temp of B tower can reduce, the B absorption the step of in, can to adsorb The adsorption temp of tower, which is lower than, vacuumizes the temperature of desorption and regeneration, the low absorption for being conducive to increase unit adsorbent of temperature when absorption Amount, temperature height when desorption and regeneration advantageously allow the desorption of adsorbent more thoroughly, increase the dynamic adsorbance of adsorbent. Energy recycle device does not have gas to pass through in this period, does not recover energy and supplies compressor (3) progress gas compression.
The process that B tower and A tower are pressed is carried out in the period of (8~9min), valve B2A3 is opened, and utilizes B tower In high pressure gas boost to A tower.Its process is similar with the process pressed of (3~4min) section, between A tower and B tower It cooperates, alternately move in circles continuous continuous operation.
A tower carries out Plenum Process in the period of (9~10min), and B tower carries out inverse put process.Valve E1E2B3, product High pressure gas in gas vacuum tank (19) carries out pressurising to A tower after energy recycling system has recycled pressure energy and cooling capacity, makes A Pressure tower is increased to the pressure close to adsorption step.Valve B4E13 is opened, and the high pressure gas in A tower passes through energy recycling system Other burners are gone to after reverse gas surge tank (7) and inverse put air compressor (8) after having recycled pressure energy and cooling capacity.Its process A tower carries out inverse put in (4~5min) section, and B tower progress Plenum Process is similar, cooperates, replaces between A tower and B tower Carry out the continuous continuous operation that moves in circles.
So far, adsorption tower completes a complete adsorption-regeneration cycles process, and carries out for next cyclic process Prepare.The operating process of B tower is identical with tower A, the operation of the alternately each step of each adsorption tower, and single column is carried out Move in circles continuous continuous operation, and for cooperating between tower and tower, alternately move in circles continuous continuous operation.
Pressure-variable adsorption is separated into H by pressure-variable adsorption2During periodically quickly variation pressure energy recycling, be converted to often Available mechanical energy supply is advised to H2Pressure process and the cooling capacity externally exported, save to H2Electric energy consumed by pressurizeing.It is right Than can be recycled in routine pressure swing adsorption system since pressure difference causes in no pressure swing adsorption system that energy recycle device is added Energy loss 46%.
4 liang of tower pressure swing adsorption purge H of table2Circulate operation step time-scale
5 the present embodiment of embodiment is used to illustrate the energy recovery process in three tower pressure-variable adsorptions
Also contain micro N in certain exhaust gas2、CO、CO2、CH4, the impurity such as Ar, need to be arranged to reach product hydrogen demands Hydrogen separation unit carries out separating-purifying.Since the operating pressure of upstream device is higher, the pressure-variable adsorption separator of H2 is caused The raw gas pressure of entrance is higher, while needing to complete the H after separation2Need to be pressurized to 4.2MPa (G).
Unstripped gas condition:
Component (butt) CO H2 CO2 N2 Ar CH4 H2S+COS
Vol, % 11.179 68.28 10.004 10.227 0.003 0.308 0.1ppm
Flow: 2000Nm3/ h (butt)
Pressure: 2.2MPa (G)
Temperature: 32 DEG C of ≈
Total H2O、O2、NH3、CH3OH, chlorine, phosphorus, arsenic, fluorine, HCN :≤0.1ppm
Through being equipped with H2The Pressure Swing Adsorption device for separating Special adsorbent carries out isolation of purified, and separating step includes: to inhale Attached, drop pressure inversely bleeds off pressure, vacuumizes, boost pressure, final boosting.In the step of including pressure change: pressing, is inverse The device that energy regenerating and pressurization coupling are used in bleeding off pressure, finally boost has recycled energy, has been completed at the same time H2Specially point From purification.Energy regenerating and the device of pressurization coupling are the system of turbo-expander, compressor, motor compressor composition, and The capacitance group of its booster action adjusts valve group, flywheel, multiple surge tanks, further includes the complicated system such as gearbox and control system System.In pressurized H2A constant volume is added in entering energy recycle device before compressor and after leaving energy recycle device Long-pending surge tank, to stabilize pressurized H2Pressure and flow fluctuation, keep its basicly stable.
As shown in Figure 9.
Energy regenerating mistake in each operating procedure of this pressure-variable adsorption and energy regenerating and the device of pressurization coupling Journey has similar process.For pressure, adjusting are swollen in the moment pipeline of valve opening in operating procedure conversion process in operating process All very greatly, so will cause bigger shock loading, excessive shock loading be will affect for the pressure difference variation of swollen machine entrance end Steady, the safe operation of equipment, the service life that will affect equipment.So by regulating valve E2E5, to adjust expanding machine inlet and outlet Pressure difference, flow, valve open moment, reduce regulating valve E2E5 aperture, build the pressure to corresponding adsorption tower, to subtract Few influence of the impact load to expanding machine.Also by expanding machine inlet/outlet pipeline be connected surge tank (13) (14) (15) (16) come It is buffered, when pressure is higher than the pressure of valve E6E7E8E9 setting in the pipeline being connected with surge tank, valve E6E7E8E9 It opens, surge tank is connected with pipeline, and gas distribution is made to enter surge tank, reduces the amount reduction impact for entering the gas of expanding machine The influence of load strives for the required time for the movement of expanding machine regulating mechanism, so that adjusting control mechanism acts turbine expansion The deflection angle of the inlet vanes of machine or the aperture of adjustable nozzle adjust and can be adapted to valve opening by flow, the pressure difference of expanding machine The pressure difference and flow of expanding machine import and export afterwards.The pressure energy band moving axis acted on expanding machine simultaneously rotates, and is converted into axis Mechanical energy, since the impact load easily band moving axis revolving speed formed when valve opening accelerates, the change of axis revolving speed is unfavorable for same motor and is formed The common driving compressor of resultant force completes the compression process of another gas, by increasing certain size and certain mass point in shaft The flywheel of cloth increases the rotary inertia of axis, so that shaft says that the acceleration obtained reduces under identical torque.Needed for motor Electric current need to access overall grid, using big power grid to the carrying capacity of periodically fast-changing electric current, application control Device smoothly drives to complete motor.Under Impact Load, power grid may to the flow for the electric current that motor inputs Quickly reduce, or even cause the change of the conveying direction of electric current, so being connected by motor and capacitance group, is being impacted to stabilize The quick variation of the flow of caused electric current under load action can reinforce electric motor system to rotation needed for quick variation shaft The responding ability of energy reduces the impact to power grid.With the lengthening of runing time, due to the gas in high-pressure tower gradually flow to it is low Pressure tower or vacuum tank, high pressure pressure tower gradually decrease, and low pressure pressure tower gradually rises, and the pressure difference between two towers is gradually reduced, swollen The pressure difference of gas is gradually reduced between swollen machine inlet and outlet, and flow is also gradually reduced, what this process gradually changed.Tune up regulating valve The aperture of E2E5 reduces the drag losses at valve.As expanding machine import and export line pressure gradually changes, gas is by flowing into Surge tank tapers to outflow surge tank, when pressure is lower than set by valve E6E7E8E9 in the pipeline being connected with surge tank When pressure, valve E6E7E8E9 is closed, and surge tank is no longer connected to pipeline.Due to gas compressed need it is basicly stable Pressure and flow, it means that the needs of shaft power needed for the gas of compression are basicly stable, so gas compressed is being compressed Machine inlet and outlet have all accessed surge tank to cope with the fluctuation of possible pressure and flow, with the variation of time, expanding machine disengaging The pressure difference of gas is gradually reduced between mouthful, and flow is also gradually reduced, so the shaft power that expanding machine is exported also is gradually becoming smaller, The shaft power for then needing motor to be exported becomes larger, then the electric current of power grid input needs to adjust by control system and gradually become Shaft power needed for carrying out completion gas compressed greatly.Electric current needed for motor needs to access overall grid, utilizes big electricity Net smoothly drives the carrying capacity of periodically fast-changing electric current, application control device to complete motor.Lead to simultaneously The deflection angle of the inlet vanes of control mechanism adjusting turbo-expander or the aperture of adjustable nozzle are overregulated, is adjusted by swollen Flow, the pressure difference of swollen machine make the higher efficiency of the holding of expanding machine.Since energy recovery process is the external output work of decompression The temperature of expansion process, the gas of expander outlet can decline, and cooling extent is determined by the pressure difference that expanding machine is imported and exported, expanding machine The cooling capacity that the gas of outlet externally exports certain temperature through heat exchanger is used for other devices.The gas of expander outlet enters low Tower is pressed, to the process that lower pressure column boosts, the gas temperature after certain cooling capacity is recycled in heat exchange is lower than expander inlet end Gas temperature, the entrance of cryogenic gas is so that the temperature of lower pressure column reduces.Boosting for lower pressure column, in following step Process equally exists the entrance of similar cryogenic gas so that the process that the temperature of lower pressure column reduces, can make lower pressure column rise In the step of being adsorbed after pressure, the adsorption temp of lower pressure column can be reduced, and the adsorption temp of adsorption tower can be made lower than de- Attached regenerated temperature, the low adsorbance for being conducive to increase unit adsorbent of temperature when absorption, temperature height when desorption and regeneration have Conducive to so that the desorption of adsorbent more thoroughly increases the dynamic adsorbance of adsorbent.Simultaneously because gas by expanding machine into It has gone energy regenerating, the boost or depressurization process of adsorption tower can have been made to tend to slowly, compared to the change for not using energy regenerating Adsorbent equipment is pressed, reduces the gas in pressure equalizing to the impact load of adsorption tower.Excessive and frequent impact load meeting The easy dusting for making adsorbent, reduces the service life of adsorbent, while also generating not to the safety of adsorption tower, tired service life Benefit influences.So the service life for having used energy recycle device that can make adsorbent in pressure-swing absorption apparatus has been used to prolong It is long, while being also beneficial to the safety and tired service life of adsorption tower.
In simple terms, by the way that the buffering of a constant volume is added in pressure-variable adsorption and energy regenerating and the device of pressurization coupling Tank stabilizes the pressure of gas in pipelines or the fluctuation of flow with valve group is adjusted, and first recycles pressure-variable adsorption by turbo-expander The energy of middle gas is converted into the mechanical energy of axis.What addition certain size and certain mass were distributed in energy recycle device flies It takes turns to increase the rotary inertia of axis, to stabilize the rotation energy for periodically quickly changing shaft.Then again control system according to system The gross energy needed determines the power output needed by motor compressor, control motor power output, then is mentioned by motor compressor or electrodynamic pump Required remaining energy is supplemented for energy to H2Complete pressurization.Being connected with capacitance group for motor, works as current wave When moving bigger, battery pack can quickly stabilize electric current and quickly change, and can reinforce electric motor system and turn to quick variation The response of rotation energy needed for axis.Electric current needed for motor needs to access overall grid, using big power grid to periodically quick The carrying capacity of the electric current of variation, application control device smoothly drive to complete motor.To which pressure-variable adsorption is separated H2 During periodically quickly variation pressure energy recycling, be converted to conventional available mechanical energy supply to H2Pressure process, section It has saved to H2Electric energy consumed by pressurizeing.In contrast to no pressure swing adsorption system that energy recycle device is added, can be recycled normal Advise 46% of the energy loss due to caused by pressure difference in pressure swing adsorption system.And for pressure-swing absorption process, according to three tower transformations Adsorption cleaning H2 circulate operation step time-scale (table 5), the operation of the alternately above each step of each adsorption tower, for Single column carries out the continuous continuous operation that moves in circles, continuous for cooperating between tower and tower, alternately moving in circles Continuous operation.
Reverse gas and pumping air lead to the exhaust gas torch pipe network of plant area as exhaust gas, pass through H2Adsorption separation device obtains pure The H2 of degree >=99.9% is 1300Nm3/ h, remaining CO be about 0.03%, CO2About 0.03%, N2About 0.03%, Ar+ CH4About 0.01%；Reverse gas and pumping air 700Nm3/ h, wherein CO be about 31.94%, CO2About 28.59%, N2About 29.22%, H2About 9.37%, CH4About 0.88%.
Pressure-variable adsorption separates H2Process, this pressure-variable adsorption process is illustrated by taking A tower as an example:
(a) adsorb (0~2min): under 2.2MPa pressure, valve A4 opening unstripped gas enters fixed bed and is adsorbed, Absorption forward position just stops absorption before not reaching bed exit end, makes to retain a Duan Xinxian between absorption forward position and bed outlet Bed, the resulting H of tower top2It is discharged as product gas by the valve A1 of the opening of tower top.Adsorptive pressure comes close to unstripped gas Expect pressure.
(b) adsorb (2~3min): the outlet of A column overhead is connected by A tower while absorption with the B tower after rising, and uses The part H that tower top obtains2Pressurising step is carried out to B tower, this step need to recycle energy by the device of energy regenerating and pressurization coupling Amount, valve A1A4 are opened, and A column overhead valve A2, B tower tower bottom valve B3, E3E6E7 valve is opened, when gas in the connected tank of E6 E6 is closed when pressure is lower than 1.9MPa, and when the pressure of gas in the connected tank of E7 is lower than 1.4MPa, E7 is closed.Adjust valve group E2, E5 It is that can reduce to adjust pressure in pipeline and gas flow becomes larger or becomes smaller so that turbo-expander (2) is run Fluctuation.The connected surge tank of E6E7 valve and adjusting valve group E2, E5 can buffer saturating by turbine in the moment that valve has just been opened The flow and pressure difference of the gas of flat expanding machine, can reduce the momentary output of turbo-expander.
(c) drop (3~4min): by A tower in vacuum state C tower be connected progress pressure step, this walk need through The device for crossing energy regenerating and pressurization coupling has recycled energy, and A column overhead valve A2, C tower tower bottom valve C3, E3E6E9 valve is beaten It opens, when the pressure of gas in the connected tank of E6 is lower than 1.9MPa, E6 is closed, when the pressure of gas in the connected tank of E9 is lower than 0.4MPa When E7 close.It adjusts valve group E2, E5 and is to adjust pressure in pipeline and gas flow becomes larger or becomes smaller, can reduce So that the fluctuation of turbo-expander operation.The moment that the connected surge tank of E6E9 valve and adjusting valve group E2, E5 have just been opened in valve The flow and pressure difference that the gas by turbine turbo-expander can be buffered, can reduce the momentary output of turbo-expander.It is right It is one section of pressure reduction for tower A, is one section of boost process for tower C.The pressure of A tower is slightly above reset pressure after pressing The purity of half (1.1MPa), the purity for body of calming the anger and the product gas flowed out from tower top is essentially identical.
(d) inverse put (4~5min): by A tower in close to normal pressure state reverse gas surge tank be connected progress inverse put step Suddenly, inverse put circuit is walked at this simultaneously need to recycle energy by the device of energy regenerating and pressurization coupling, A tower tower bottom valve A3, E1E4E8E9 valve is opened, and when the pressure of gas in the connected tank of E8 is lower than 0.9MPa, E8 is closed, when gas in the connected tank of E9 E9 is closed when pressure is lower than 0.4MPa.Adjusting valve group E2, E5 is to adjust pressure in pipeline and gas flow and become larger Or become smaller, the fluctuation so that turbo-expander operation can be reduced.The connected surge tank of E8E9 valve and adjusting valve group E2, E5 are in valve The moment that door has just been opened can buffer the flow and pressure difference of the gas by turbine turbo-expander, can reduce turbo-expander Momentary output.After drop pressure process, the impurity forward position in adsorbent bed has reached the outlet port of adsorption tower.This When, adsorption column pressure is down to close to normal pressure (0.11MPa) against absorption direction.In the process, it is adsorbed in adsorption tower Impurity starts largely to desorb from adsorbent.Inversely gas is bled off pressure after reverse gas surge tank (7) and inverse put air compressor (8) Go to other burners.
(e) it vacuumizes (5~6min): after inverse put step, to make adsorbent obtain more thoroughly regenerating, to absorption Tower evacuates, and desorbs adsorbent thoroughly.The A5 valve for opening A tower bottom, inversely vacuumizes bed with vacuum pump (6), tower Interior pressure extremely -0.09MPa.
(f) it rises (6~7min): the A tower in vacuum state is connected progress with the B tower terminated in adsorbed state Press step.It is one section of Plenum Process for tower A, is one section of pressure reduction for tower B.A tower tower bottom valve A3, B column overhead Valve B2, E3E6E9 valve is opened, this step need to recycle energy by the device of energy regenerating and pressurization coupling, and process is similar In the process that (c) drops, only A tower becomes the lower pressure column by boost pressure for receiving gas.The pressure of A tower is omited after pressing Lower than the purity base of the half (0.9MPa) of adsorption step pressure, the purity for body of calming the anger and the product gas flowed out from B column overhead This is identical.
(g) vacant (7~8min): A column overhead, tower bottom valve are all closed, and do not have gas disengaging in A tower, and A tower, which is in, to be waited State.
(h) pressurising (8~9min): by A tower and the C column overhead after rising export be mutually used in conjunction part H2 to A tower into Row pressurising step increases A tower internal pressure, close to adsorptive pressure (2.1MPa).A tower tower bottom valve A3, C column overhead valve C2, E3E6E7 valve are opened, this step need to be analogous to (b) by the process that the device of energy regenerating and pressurization coupling has recycled energy The process of absorption, only A tower becomes the lower pressure column being pressurized for receiving gas.
So far, adsorption tower completes a complete adsorption-regeneration cycles process, and carries out for next cyclic process Prepare.The operating process of other three towers is identical with tower A, the operation of the alternately above each step of each adsorption tower, right The continuous continuous operation that moves in circles is carried out in single column, for cooperating, alternately being moved in circles constantly between tower and tower Continuous operation.
Its specific ring operating procedure and operating time and timing are referring to table 5, the therebetween control of each valve opening state of each tower System and operation are referring to table 6.According to time-scale (table 5) and valve opening control table (table 6) it is known that energy recycling system is in Continuous duty is alternately present for pressure, inverse put, Plenum Process, and alternately move in circles continuous continuous operation, energy Recovery system is continuously run, and recycles the energy in this 3 operating procedures, so that energy recycling system avoids zero load, Be conducive to machine to safely and steadily run, avoid the loss of the adverse effect and energy to machine.
5 three tower pressure swing adsorption purge H of table2Circulate operation step time-scale
Each tower valve opening control table of table 6

Claims (10)

1. a kind of cog joint blast furnace gas or/and coal gas of converter produce H2The device of/CO unstripped gas, which is characterized in that packet It includes:
First pressure-swing absorption apparatus, for the first gas mainly containing blast furnace gas or/and coal gas of converter to be passed through pressure-variable adsorption Method separates CO and N2, obtain CO；
Second pressure-swing absorption apparatus, for going out the second gas mainly containing coke-stove gas by pressure swing absorption process separating-purifying H in gas2；
The device for producing alcohol is connected to the H of the CO outlet and the second pressure-swing absorption apparatus of the first pressure-swing absorption apparatus2Outlet, is used for By CO obtained and H2React the alcohol of obtained carbon atom number >=2.
2. cog joint blast furnace gas according to claim 1 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that further include:
The first removal of impurities pretreatment unit being connect with the first pressure-swing absorption apparatus, for being pre-processed to first gas；
The second removal of impurities pretreatment unit being connect with the second pressure-swing absorption apparatus, for being pre-processed to second gas.
3. cog joint blast furnace gas according to claim 2 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that the first removal of impurities pretreatment unit includes dust-extraction unit, dephosphorization apparatus, arsenic removing apparatus, dehydration dress It sets, dehydrogenation device for deoxidizing, desulfurizer, de- CO2Device removes CH4One or several combinations in device；Described second Removal of impurities pretreatment unit includes dust-extraction unit, tar-removing device, except recombination separating device, dehydration device, desulfurizer, deoxidation dress It sets, de- CO2Device removes CH4Except CmHnOne or several combinations in device.
4. cog joint blast furnace gas according to claim 3 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that the first removal of impurities pretreatment unit and the second removal of impurities pretreatment unit includes desulfurizer and de- CO2 Device takes off CO2Device and desulfurizer integrate or de- CO2Device is in desulfurizer downstream side.
5. cog joint blast furnace gas according to claim 4 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that the first removal of impurities pretreatment unit further includes except CH4Device or/and dehydrogenation device for deoxidizing remove CH4Dress It sets in desulfurizer downstream side, dehydrogenation device for deoxidizing, which is in, removes CH4Device downstream side；The second removal of impurities pretreatment unit It further include except CH4Except CmHnDevice removes CH4Except CmHnDevice is in desulfurization and de- CO2Device downstream side.
6. cog joint blast furnace gas according to claim 4 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that the de- CO in the first removal of impurities pretreatment unit and the second removal of impurities pretreatment unit2Device is pressure swing adsorption method De- CO2Device or absorption process take off CO2Device takes off CO using absorption process2Absorption process when device, in the first removal of impurities pretreatment unit De- CO2The absorbing liquid of device exports or import is correspondingly connected to the absorption process of the second removal of impurities pretreatment unit except CO2The import of device Or outlet.
7. cog joint blast furnace gas according to claim 2 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that the suitable deflation of the first pressure-swing absorption apparatus or/and the second pressure-swing absorption apparatus, reverse gas, displacement tail gas go out At least one of mouth is connect with second gas raw material gas inlet or the second removal of impurities pretreatment unit.
8. cog joint blast furnace gas according to claim 1 or 2 or/and coal gas of converter produce H2/ CO unstripped gas Device, which is characterized in that second pressure-swing absorption apparatus passes through a step pressure swing absorption process for H2With CO and N2Separation, mentions Pure H out2, the suitable deflation of offgas outlet and the first pressure-swing absorption apparatus or/and displacement offgas outlet pass through piping connection, the pipe Road is connect with the gas feed of the first removal of impurities pretreatment unit or the first pressure-swing absorption apparatus.
9. cog joint blast furnace gas according to claim 1 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that second pressure-swing absorption apparatus includes concatenated third pressure-swing absorption apparatus and the 4th pressure-variable adsorption Device, wherein third pressure-swing absorption apparatus is used to pass through pressure swing absorption process for the CO and H in second gas2And N2Separation, mentions H must be contained after pure CO2And N2Gaseous mixture, the 4th pressure-swing absorption apparatus are used to pass through pressure swing absorption process for the H in the gaseous mixture2 And N2Separation, purifies out H2；4th pressure-swing absorption apparatus is connect with the device of production alcohol.
10. cog joint blast furnace gas according to claim 9 or/and coal gas of converter produce H2The dress of/CO unstripped gas It sets, which is characterized in that the displacement gas entrance of the first pressure-swing absorption apparatus is exported by the CO of pipeline and third pressure-swing absorption apparatus Connection exports connection with the CO of its own；The displacement gas entrance of third pressure-swing absorption apparatus and the CO of the first pressure-swing absorption apparatus Outlet connection.
CN201821746643.0U 2018-10-26 2018-10-26 Cog joint blast furnace gas or/and coal gas of converter produce H2The device of/CO unstripped gas Active CN209537405U (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100714A (en) * 2018-10-26 2020-05-05 苏州盖沃净化科技有限公司 Production of H by combining coke oven gas with blast furnace gas or/and converter gas2Method and device for preparing/CO raw material gas
CN111320528A (en) * 2020-03-24 2020-06-23 北京石油化工工程有限公司 Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas
CN111732975A (en) * 2020-05-19 2020-10-02 福州大学 Blast furnace gas partial deoxidation and desulfurization method and system

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100714A (en) * 2018-10-26 2020-05-05 苏州盖沃净化科技有限公司 Production of H by combining coke oven gas with blast furnace gas or/and converter gas2Method and device for preparing/CO raw material gas
CN111320528A (en) * 2020-03-24 2020-06-23 北京石油化工工程有限公司 Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas
CN111732975A (en) * 2020-05-19 2020-10-02 福州大学 Blast furnace gas partial deoxidation and desulfurization method and system

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