CN108341398B - A kind of hydrogen purification system and method that the deoxidation of bright annealing furnace deep dehydration is energy-efficient - Google Patents

A kind of hydrogen purification system and method that the deoxidation of bright annealing furnace deep dehydration is energy-efficient Download PDF

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CN108341398B
CN108341398B CN201810124001.5A CN201810124001A CN108341398B CN 108341398 B CN108341398 B CN 108341398B CN 201810124001 A CN201810124001 A CN 201810124001A CN 108341398 B CN108341398 B CN 108341398B
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deoxidation
hydrogen
bright annealing
drier
annealing furnace
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CN108341398A (en
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陈�光
徐驰
卜春成
冯亚亚
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8671Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/16Hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00Purification or separation of specific gases
    • C01B2210/0043Impurity removed
    • C01B2210/0045Oxygen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00Purification or separation of specific gases
    • C01B2210/0043Impurity removed
    • C01B2210/0062Water
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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Abstract

The invention discloses a kind of hydrogen purification systems and method that the deoxidation of bright annealing furnace deep dehydration is energy-efficient, deep dehydration and deoxidation is carried out to hydrogen in bright annealing furnace using catalytic deoxidation system and adsorption and purification system, for raw hydrogen after oxygen-eliminating device catalytic deoxidation, cooling simultaneously enters adsorbent equipment water removal;Adsorbent equipment is made of double driers, one is in working condition, it is dehumidified by molecular sieve, another is reproduced state, introduce the water of dry hydrogen removing molecular sieve absorption, the work of two driers, the continuous cyclic switching of reproduced state, switching cycle are adjusted by monitoring the automatic control system of device on-line equipped with steam partial pressure.The present invention solves conventional method and improves the total purity of hydrogen merely, the problem of ignoring significant impact of the water vapour content to bright annealing effect, and it reduces operating conditions and regenerates the switching frequency of state drier, to reduce a large amount of dry hydrogens being vented in handoff procedure and the abrasion to valve etc., heating time is also reduced simultaneously, reduces energy consumption.

Description

A kind of hydrogen purification system that the deoxidation of bright annealing furnace deep dehydration is energy-efficient with Method
Technical field
The present invention relates to the technical fields of hydrogen purification more particularly to a kind of bright annealing furnace deep dehydration deoxidation efficiently to save The hydrogen purification system and method for energy.
Background technique
Bright annealing is in H2Steel band is heat-treated under protective atmosphere.Reach the requirement of BA plate, it is necessary to very tight Protective atmosphere in furnace is controlled to lattice, avoids aoxidizing as far as possible.Hydrogen is purified with modern science and technology, can obtain it is high-purity, Even ultra-pure hydrogen, but to obtain absolutely pure hydrogen be still it is impossible, different degrees of impurity is always contained in atmosphere, Middle O2And H2O is the most harmful.Hydrogen purification technology, which is only conceived to, in traditional furnace improves the total purity of hydrogen, has ignored foreign gas Middle O2And H2Significant impact of the O content to bright annealing effect, wherein especially with the lesser H of molecular weight2O is most difficult to remove, and water steams Gas partial pressure can only usually be reduced to 7~10Pa.Make main alloy element in stainless steel compared with remaining under low temperature thermal oxidation Guarantee sufficiently reduction, steam partial pressure must be decreased to 1Pa hereinafter, therefore the deoxidation of bright annealing furnace deep dehydration it is energy-efficient Hydrogen purification system and method have major application prospect and meaning in stainless steel industry production.
The dehydration technique being widely used at present is molecular sieve dry technology, however when use molecular sieve drying, in molecular sieve Water can reach saturation state, dehydration is unable to further progress, it is necessary to after molecular sieve removal moisture drying, can continue work, I.e. drier need to constantly switch between working condition and reproduced state.Traditional technology is adsorbed by drying using bitubular suitching type, During this, work, reproduced state switching time need to set according to use experience usually, in most cases Drier cannot all be fully utilized.In order to guarantee that the quality of hydrogen, switching cycle parameter are set by maximum qi-regulating amount Meter, and certain design surplus is left, therefore switching cycle parameter setting is relatively short.The control model exists Deficiency mainly has: work and the setting of regeneration period lack stringent science, although the adjustable work of user and regeneration Period, but cannot in real time according to gas production difference switching cycle is automatically adjusted, exist do not need switching when just into The problem of row switching, causes a large amount of qualified hydrogen to be vented in vain, causes unnecessary energy waste.In addition, due to drier Duty cycle is shorter, and valve transfer is more frequent, also accordingly shortens the service life of drier and valve.Therefore, it is necessary to The effective use to drier is realized using advanced control model.
Summary of the invention
To solve the above problems, the present invention provides, a kind of structure is simple, safe and reliable, high degree of automation bright annealing The energy-efficient hydrogen purification system of furnace deep dehydration deoxidation and method.
It is that the present invention uses the specific technical proposal is:
A kind of hydrogen purification system that the deoxidation of bright annealing furnace deep dehydration is energy-efficient, hydrogen purification system include catalysis Deaerating type of cycles and adsorption and purification system composition;Freezing water- to-water heat exchanger is equipped between catalytic deoxidation system and adsorption and purification system; Catalytic deoxidation system include hydrogen delivery tube road and palladium chtalyst deoxidation tank, palladium chtalyst deoxidation tank be equipped with observation window, thermometer and Dehydrated tube;Adsorption and purification system is two driers, and the drier includes multilayer molecular sieve adsorption layer, heater, temperature Spend sensor and gas ventilator;It is cut equipped with control system for controlling two drier working conditions and reproduced state circulation It changes.
The energy-efficient hydrogen purification method of bright annealing furnace deep dehydration deoxidation takes out the hydrogen in bright annealing furnace Out, after catalytic deoxidation system deoxidation, enter adsorption and purification system after chilled water- to-water heat exchanger is cooling;
When into adsorption and purification system, drier A enters work in control system control two driers of adsorption and purification system Start to be dehydrated hydrogen as state;And it controls another drier B and enters reproduced state;
By switching cycle T, control drier B enters working condition and starts to be dehydrated hydrogen, and drier A enters again Raw state;
The working condition and reproduced state of cyclic switching drier A and drier B, switching cycle T is according to steam partial pressure Control model control;
Finally hydrogen after drying is passed through in bright annealing furnace.
Further, steam partial pressure control model specifically:
Pass through steam partial pressure p at on-line monitoring dryer exportaWith setting partial pressure value p0It is compared, if pa< p0, then Drier works on, if pa> p0, control drier working condition progress cyclic switching.
Further, p0Value is not more than 0.8Pa.
Further, switching cycle T is adjusted by monitoring the automatic control system of device on-line equipped with steam partial pressure.
Further, steam partial pressure is no more than 1.08Pa everywhere in bright annealing furnace.
The present invention is compared compared with the prior art with remarkable advantage are as follows: is targetedly greatly reduced in bright annealing furnace O in hydrogen impurity2And H2The content of O significantly improves bright annealing effect.In addition, reducing operating conditions and regenerating state drier Switching frequency to reduce a large amount of dry hydrogens being vented in handoff procedure and the abrasion to valve etc., while also reducing heating Time reduces energy consumption.
Detailed description of the invention
Fig. 1 hydrogen purification system structural schematic diagram of the present invention.
In figure, 1: catalytic deoxidation system, 2: freezing water installations, 3: heat exchanger, 4: drier, 5: valve.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and embodiments
As shown in Figure 1, the energy-efficient hydrogen purification system of deep dehydration deoxidation of the invention by catalytic deoxidation system and Adsorption and purification system composition;The deoxygenation by the way of palladium chtalyst of catalytic deoxidation system;Adsorbent equipment is identical double dry by structure Device composition, one are in working condition, are dehumidified by molecular sieve, another is reproduced state, introduce dry hydrogen and remove molecular sieve The water of absorption, the work of two driers, the continuous cyclic switching of reproduced state.
Catalytic deoxidation system include hydrogen delivery tube road and palladium chtalyst deoxidation tank, palladium chtalyst deoxidation tank be equipped with observation window, Thermometer and dehydrated tube.
Freezing water- to-water heat exchanger is equipped between catalytic deoxidation system and adsorption and purification system.
Drier includes multilayer molecular sieve adsorption layer, heater, temperature sensor and gas ventilator.
Double drier cyclic switching periods of adsorption and purification system are automatically controlled by steam partial pressure automatic control system.
Specific operation process of the invention is discussed in detail below as each function.
By the hydrogen extraction in bright annealing furnace, hydrogen enters palladium chtalyst deoxidation tank by conveyance conduit and is efficiently taken off Oxygen, deaeration time 24 hours, the deoxygenation carried out in palladium chtalyst deoxidation tank was as follows:
Deoxygenation is exothermic reaction, high temperature is generated in deoxidation tank, the water of production is gaseous state, by vaporous water by freezing Enter the drier A in adsorption and purification system from bottom after water- to-water heat exchanger is cooling.Drier A enters drying and dehydrating working condition, Certain temperature is heated to by electric heater, it is dry by molecular sieve dehydration.Monitor the steam partial pressure in the exit drier A on-line Value pa, feed back to automatic control system.Work as pa< p0When, drier A is continued working, and works as pa> p0When, drier A enters regeneration shape State is passed through dry hydrogen and sloughs the adsorbed moisture of molecular sieve, and drier B enters drying and dehydrating working condition.Control drying Device carries out state switching.After the completion of switching, it is still transformed into steam partial pressure control model, device B exporting hydrogen is dried Partial pressure value monitoring, switches until next time.Drier A and B constantly moves in circles switching as a result, switching cycle extend to 36h with On, average power consumption hourly, air consumption can be reduced to 4.44kWh and 26.7m respectively3.Hydrogen after drying is passed through light and moves back In stove.

Claims (6)

1. a kind of hydrogen purification system that the deoxidation of bright annealing furnace deep dehydration is energy-efficient, which is characterized in that hydrogen purification system System includes that catalytic deoxidation system and adsorption and purification system form;Freezing is equipped between catalytic deoxidation system and adsorption and purification system Water- to-water heat exchanger;Catalytic deoxidation system include hydrogen delivery tube road and palladium chtalyst deoxidation tank, palladium chtalyst deoxidation tank be equipped with observation window, Thermometer and dehydrated tube;Adsorption and purification system be two driers, the drier include multilayer molecular sieve adsorption layer, Heater, temperature sensor and gas ventilator;Equipped with control system for controlling two drier working conditions and regeneration Cycle of states switching.
2. a kind of hydrogen purification method that the deoxidation of bright annealing furnace deep dehydration is energy-efficient, which is characterized in that by bright annealing Hydrogen extraction in furnace enters adsorption and purification system after chilled water- to-water heat exchanger is cooling after catalytic deoxidation system deoxidation;
When into adsorption and purification system, drier A enters work shape in control system control two driers of adsorption and purification system State starts to be dehydrated hydrogen;And it controls another drier B and enters reproduced state;
By switching cycle T, control drier B enters working condition and starts to be dehydrated hydrogen, and drier A enters regeneration shape State;
The working condition and reproduced state of cyclic switching drier A and drier B, switching cycle T are controlled according to steam partial pressure Scheme control;
Finally hydrogen after drying is passed through in bright annealing furnace.
3. the energy-efficient hydrogen purification method of bright annealing furnace deep dehydration deoxidation according to claim 2, feature It is, steam partial pressure control model specifically:
Pass through steam partial pressure p at on-line monitoring dryer exportaWith setting partial pressure value p0It is compared, if pa< p0, then dry Device works on, if pa> p0, control drier working condition progress cyclic switching.
4. the energy-efficient hydrogen purification method of bright annealing furnace deep dehydration deoxidation according to claim 3, feature It is, the p0Value is not more than 0.8Pa.
5. the energy-efficient hydrogen purification method of bright annealing furnace deep dehydration deoxidation according to claim 2, feature It is, the switching cycle T is adjusted by monitoring the automatic control system of device on-line equipped with steam partial pressure.
6. the energy-efficient hydrogen purification method of bright annealing furnace deep dehydration deoxidation according to claim 2, feature It is, steam partial pressure is no more than 1.08Pa everywhere in the bright annealing furnace.
CN201810124001.5A 2018-02-07 2018-02-07 A kind of hydrogen purification system and method that the deoxidation of bright annealing furnace deep dehydration is energy-efficient Active CN108341398B (en)

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