CN106039964A

CN106039964A - Method for desulfurization cogenerating of hydrogen and sulfuric acid

Info

Publication number: CN106039964A
Application number: CN201610529572.8A
Authority: CN
Inventors: 许文林; 王大为; 王雅琼; 张淮浩
Original assignee: Yangzhou University
Current assignee: Yangzhou University
Priority date: 2016-07-06
Filing date: 2016-07-06
Publication date: 2016-10-26
Anticipated expiration: 2036-07-06
Also published as: CN106039964B

Abstract

The invention discloses a method for desulfurization cogenerating of hydrogen and sulfuric acid. The method includes three main steps, namely SO2 absorption and conversion, Fe3+regeneration and H2 cogeneration and F2+removal and H2 cogeneration. In the method, a Fe3+/F2+ electrochemical pair is adopted as a process catalyst, indirect electrochemical oxidation is realized, sulfur dioxide in a gas phase is removed by using a sulfuric acid water solution wet method, and hydrogen and sulfuric acid can be cogenerated at the same time. The method is high in process efficiency and energy utilization rate, low in equipment investment and production cost, safe and reliable in process and conducive to large-scale industrialization, and is an environment-friendly technology for desulfurization, comprehensive utilization of sulfur dioxide and cogeneration of hydrogen and sulfuric acid.

Description

A kind of desulfurization co-producing hydrogen and the method for sulphuric acid

Technical field

The present invention relates to the process of a kind of method of desulfurization co-producing hydrogen and sulphuric acid, particularly relate to remove in gas phase Sulfur dioxide, simultaneously co-producing hydrogen and the method for sulphuric acid, belong to three-protection design and application technology as the second resource field, especially remove Sulfur dioxide technical field of comprehensive utilization；Fall within the preparing technical field of hydrogen and sulphuric acid, especially hydrogen energy source technology of preparing Field；Fall within electrochemical reaction engineering and technical field of chemical separation.

Background technology

Sulfur dioxide (SO₂), also known as sulfurous anhydride, be modal oxysulfide, under room temperature for colourless, poisonous, have strong Strong irritating sour gas, density is bigger than air, easily liquefies, soluble in water.

Coal and oil generally all contain sulfide, SO during burning, can be generated₂；Sulfur, hydrogen sulfide, troilite and sphalerite Also SO can be generated Deng sulfur compound when burning₂.Chemical equation is as follows:

SO₂It is the important source material producing sulphuric acid, is also one of Air Pollutant Discharge.In an atmosphere, SO₂Can aoxidize and give birth to Become sulfuric acid mist or sulfate aerosol, be the main predecessor of environmental acidification.

Therefore, research and develop the new technology of efficient desulfurization and recycling, at removing SO₂While realize SO₂Resource Change to utilize and protection environment, raising resource utilization are not only with a wide range of applications and learning value, it may have be notable Social benefit and economic benefit.

Current existing sulfur removal technology predominantly absorbs and dissolves removing SO₂Technique, is summarized as follows.

1. alkalescent menstruum dissolves removing SO₂Technology

Remove SO at present₂Topmost Technology is to use the SO in alkalescent menstruum gas phase₂Gas.Mainly have wet Method, dry method and semidry method, its ultimate principle is with the aqueous solution containing basic anhydride or hydroxide as absorbent, alkalescence oxygen Compound or hydroxide and SO₂React generation sulphite, and sulphite prepares sulfate through oxidation further.

Although this technique can effectively remove SO₂But, this technique basic anhydride to be consumed or hydroxide, simultaneously The economy of a large amount of sulphite of by-product or the utilization of sulfate, sulphite or sulfate, raising process is that restriction should The principal element of process industrialization application.

2. remove SO based on S-I circulation theory₂Technology

Removing SO is dissolved in order to solve conventional suction₂The problem that Technology exists, especially at removing SO₂Same Time can comprehensively utilize, have developed according to S-I circulation (Sulphur-Iodine Cycle) technological principle sulfur removal technology Technology.

(1) S-I circulation principle and essence

S-I circulation (Sulphur-Iodine Cycle) is that AM General Atomic Energy corporation (General Atomics) exists The seventies in last century invention, its purpose is to research and development thermal decomposition water hydrogen producing technology S-I circulation dominant response and purpose such as Under:

1. oxidizing sulfur dioxide conversion reaction

2H₂O+SO₂+I₂→H₂SO₄+2HI

Utilize the I in aqueous solution₂Can be by SO₂Oxidation generation sulphuric acid, and I₂Self it is reduced to the principle of HI, by SO₂Turn While turning to sulphuric acid, obtain preparing the raw material HI of hydrogen；

2. sulphuric acid pyrolysis

H₂SO₄→H₂O+SO₂+0.5O₂

Sulphuric acid obtains SO through pyrolysis₂, SO can be realized₂Recycling；

3. hydroiodic acid pyrolysis

2HI→H₂+I₂

HI obtains I through pyrolysis₂And H₂, prepare target product H₂While get back I₂, it is achieved that I₂Circulation make With.

The essence of this process is hydrothermal cracking H₂, by-product O simultaneously₂.In theory, SO₂And I₂Only play the effect of catalyst, Do not consume.

The technology of S-I circulation is to use atomic energy or the radiation such as solar energy can prepare H₂Technology, substantially with de- The techniques such as sulfur are unrelated.The oxidizing sulfur dioxide conversion reaction of this process is applied to sweetening process, it is simply that Wet Flue Gas Desulfurization Technique Principle.

(2) desulfurization based on S-I circulation theory and process for making hydrogen technology

If only utilizing oxidizing sulfur dioxide conversion reaction in S-I cyclic process, then this process is typical wet desulphurization Technology, can be by the SO in gas phase₂Removing, by-product sulphuric acid simultaneously；During the HI that generates by the available H of thermal decomposition₂And I₂, Its essence is that iodine circulates (Iodine Cycle) Technology.This technique there is problems in that

①H₂SO₄Separation problem with HI: after oxidizing sulfur dioxide converts, SO₂By I₂Oxidation generates sulphuric acid, I₂It is reduced For HI.The raw material HI of sulphuric acid to be respectively obtained and hydrogen manufacturing, is necessary for solving H₂SO₄With the separation problem of HI, use conventional separation Technology is difficult to isolated and meets the H using requirement₂SO₄And HI.

2. HI thermal decomposition process operating difficulties: HI is through the available I of thermal decompositionization reaction₂And H₂, at prepared target product H₂'s Meanwhile, the I obtained₂Can recycle.But, this course of reaction easily distils due to iodine, during the loss amount of iodine big, Operating difficulties.

3. response system seriously corroded: hydriodic acid aqueous solution corrosivity is strong, particularly when coexisting with sulphuric acid, and at high temperature bar Time under part, corrosivity is extremely strong, is difficult to the requirement finding suitable material to meet process.

(3) iodine circulation-electrochemical redox coupling technique technology

In order to solve problem present in above-mentioned technique, by H₂SO₄Separation with HI and HI electrochemistry prepare I₂And H₂Mistake Journey couples, and by electrochemical oxidation, reduction, makes H₂SO₄With the I in HI mixed liquor^-I is obtained at anode electrochemical oxidation regeneration₂, H⁺ H is obtained in electrochemical cathode reduction₂, thus by HI from H₂SO₄Remove with in HI mixed liquor, while realizing desulfurization, be prepared into To H₂And H₂SO₄。

The advantage of this Technology is:

1. can effective scrubbing CO_2: use I₂Aqueous solution absorbs SO₂MODEL OF CHEMICAL ABSORPTION PROCESS, have absorption rate fast, Removal efficiency high.

2. separation-regenerative coupling: by H₂SO₄The electrochemical process with HI that separates of-HI mixed liquor prepares H₂And I₂It is coupled, Not only solve H₂SO₄With the separation problem of HI mixed liquor, and simplify technique, improve production efficiency.

3. desulfurization and coproduction H₂SO₄And H₂PROCESS COUPLING: while realizing desulfurization, coproduction obtains H₂SO₄And H₂。

But, this Technology yet suffers from problems with:

1. HI prepares I₂There is problem: the I such as electrode inactivation and operating difficulties in process₂Fusing point be 119 DEG C, be solid under room temperature State, uses electrochemical techniques by I^-I is obtained at anode electrochemical oxidation regeneration₂During, operation temperature is generally at I₂Fusing point Hereinafter, therefore I₂Deposit at anode surface, cause electrode to inactivate, operating difficulties, it is also difficult to realize continuous operation.

2. the problem that oxidizing sulfur dioxide conversion reaction process exists: because I₂Dissolubility in aqueous is little, in order to Make SO₂Oxidation conversion reaction generates the process of sulphuric acid and can be smoothed out, generally use improve absorption process operation temperature or The method using organic solvent.

Improve the operation temperature of absorption process: in order to make I₂Being in a liquid state, operation temperature need to reach I₂Fusing point more than.But, Carry High Operating Temperature and can cause SO₂Dissolubility decline.Obviously, SO is certainly existed₂Dissolubility and I₂Contradiction between dissolubility.

Use organic solvent: in order to improve I₂Dissolubility, can be selected for the organic solvent such as benzene, toluene, but use organic molten Agent can cause SO₂The process absorbing dissolving-oxidation conversion reaction generation sulphuric acid becomes liquid-liquid inhomogeneous reaction process, not only deposits In the liquid-liquid dispersion mixed problem of course of reaction, but also deposit the separation problem of liquid-liquid heterogeneous system after the reaction, simultaneously Due to the introducing of organic solvent, necessarily bring the problems, particularly organic solvent such as the recovery of solvent, loss and systemic contamination Exist and subsequent electrochemical regenerative process can be brought Organic substance adverse influence such as absorption on electrode, make regenerative process be difficult to suitable Profit is carried out.

3. hydroiodic acid corrosivity is strong: hydriodic acid aqueous solution corrosivity is strong, particularly when coexisting with sulphuric acid, and in hot conditions Time lower, corrosivity is extremely strong, is difficult to the requirement finding suitable material to meet process.Obviously, the above technology be all difficult to into Row industrializing implementation.Therefore, the research and development Technology that technique is simple, production cost is low, economic and environment-friendly, atom utilization is high, tool It is of great significance.

Summary of the invention

It is an object of the invention to provide the process of a kind of method of desulfurization co-producing hydrogen and sulphuric acid, particularly relate to take off Sulfur dioxide in degasification mutually, the Technology of the comprehensive utilization of resources of co-producing hydrogen and sulphuric acid simultaneously.

Desulfurization co-producing hydrogen of the present invention and the method for sulphuric acid, by " SO₂Sorption enhanced ", " Fe³⁺Regeneration and coproduction H₂”、“Fe²⁺Removing and coproduction H₂" three part compositions.Specifically:

(1) SO₂Sorption enhanced

With containing Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, Absorb the SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺, obtain containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂

In isolating membrane electrochemical reactor, with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Sulfuric acid solution be sun Pole liquid, Fe²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation reactions³⁺, obtain containing Fe³⁺Aqueous sulfuric acid as SO₂Inhale The absorbent receiving conversion process recycles；With aqueous sulfuric acid as catholyte, H⁺H is generated in negative electrode generation reduction reaction₂；Real Existing Fe³⁺Regeneration and coproduction H₂Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂

In isolating membrane electrochemical reactor, with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be Catholyte, Fe²⁺Fe, Fe in removing solution is separated out in negative electrode generation electrochemical reducting reaction deposition²⁺, this solution passes through further Absorb SO₃Or after dehydration by evaporation, prepare and meet the sulfuric acid product that user requires；Fe is removed in negative electrode electro-deposition²⁺Same Time, H⁺H is generated in cathodic reduction₂.With step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, Fe² ⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation reactions³⁺, obtain containing Fe³⁺Aqueous sulfuric acid as SO₂Sorption enhanced mistake The absorbent of journey recycles.Both Fe was achieved at negative electrode²⁺Removing and coproduction H₂, make Fe at anode again³⁺Regeneration.

Further, the specifically comprising the following steps that of step (one)

(1) absorbing liquid preparation: in absorbing liquid dosing apparatus, sulphuric acid and water are mixed to obtain aqueous sulfuric acid, ferric sulfate solution Solution is in aqueous sulfuric acid, and preparation obtains containing Fe³⁺Aqueous sulfuric acid as absorbent；

(2)SO₂Absorb-convert: at SO₂In absorption plant, with previous step prepare containing Fe³⁺Aqueous sulfuric acid make For absorbent, Fe³⁺For oxidant, SO₂Absorption is dissolved in aqueous sulfuric acid, the SO in removing gas phase₂, absorb the SO dissolved₂With Water reaction generates sulfurous acid (H₂SO₃), H₂SO₃By Fe³⁺Oxidation is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺, obtain containing Fe²⁺ Aqueous sulfuric acid；

(3) solid-liquid separation: in solid-liquid separation equipment, by the material after separation obtained in the previous step through solid-liquid separation Remove solid impurity, obtain containing Fe²⁺Aqueous sulfuric acid.

Further, the specifically comprising the following steps that of step (two)

(1) absorbent preparation: in absorbent dosing apparatus, sulphuric acid and water are mixed to prepare aqueous sulfuric acid, then by sulfur Acid ferrum is dissolved in this aqueous sulfuric acid, prepares containing Fe³⁺Aqueous sulfuric acid, this solution uses as absorbent.

(2)SO₂Sorption enhanced: at SO₂In sorption enhanced device, with previous step prepare containing Fe³⁺Aqueous sulfuric acid be Absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in solid-liquid separation equipment, carries out material obtained in the previous step solid-liquid separation and removes solid State impurity, obtains containing Fe²⁺Aqueous sulfuric acid.

Further, the specifically comprising the following steps that of step (two)

(1) anolyte preparation: step () is obtained containing Fe²⁺Aqueous sulfuric acid directly as anolyte；Or In anolyte dosing apparatus, sulphuric acid is mixed with water, then dissolve in ferrous sulfate, obtain containing Fe²⁺Aqueous sulfuric acid as sun Pole liquid.

(2) catholyte preparation: sulphuric acid and water mixed preparing are obtained aqueous sulfuric acid, or by step (three) (3rd) step Fe³⁺ Regeneration and removing Fe²⁺Co-production H₂In the removing Fe that obtains²⁺Aqueous sulfuric acid as catholyte.

(3)Fe³⁺Regeneration and coproduction H₂: in isolating membrane electrochemical reactor, with sulphuric acid as supporting electrolyte, sulphuric acid is water-soluble Fe in liquid²⁺Fe is generated at anode generation electrochemical oxidation reactions³⁺, containing Fe³⁺Aqueous sulfuric acid can be as SO₂Absorb and turn The absorbent of change process recycles；H with aqueous sulfuric acid as catholyte, in solution⁺Anti-at negative electrode generation electrochemical reduction H should be obtained₂；Realize Fe³⁺Regeneration and coproduction H₂Paired electrochemical synthesis.

Further, the specifically comprising the following steps that of step (three)

(2) catholyte preparation: step () is obtained containing Fe²⁺Aqueous sulfuric acid directly as catholyte；Or In catholyte dosing apparatus, sulphuric acid is mixed with water, make aqueous sulfuric acid as catholyte.

(3)Fe³⁺Regeneration and removing Fe²⁺Co-production H₂: in isolating membrane electrochemical reactor, with sulphuric acid for supporting electrolysis Matter, the Fe in aqueous sulfuric acid in anode chamber²⁺Fe is generated at anode generation electrochemical oxidation reactions³⁺, obtain containing Fe³⁺Sulfur Aqueous acid enters step () as SO₂The absorbent of sorption enhanced process recycles；In cathode chamber in aqueous sulfuric acid Fe²⁺Fe, the Fe in removing solution is generated in negative electrode generation reduction reaction electro-deposition²⁺, H simultaneously⁺Reduction obtains H₂, remove Fe²⁺ Aqueous sulfuric acid enter next step；Described removing Fe²⁺Aqueous sulfuric acid can be also used for step (two) (2nd) step；

(4) aqueous sulfuric acid concentration: previous step is removed Fe²⁺Aqueous sulfuric acid through absorption SO₃Or dehydration by evaporation After, prepare and meet the aqueous sulfuric acid product that user requires.

Further, in aqueous sulfuric acid described in step () (1st) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe³⁺Concentration is 0.2mol/L-2.0mol/L, Fe³⁺Concentration≤0.2mol/L, operation temperature is 20 DEG C-60 DEG C.

Further, the SO described in step () (2nd) step₂Absorption plant be spray tower, spray column, packed tower, tubulent contact tower, Any one of sieve-plate tower and Venturi absorber, operation temperature is 20 DEG C-60 DEG C.

Further, step () (3rd) step solid-liquid separation equipment is piping filter, filter press, centrifuge, turns Cylinder filter, disk type filter, leaf filter any one.

Further, in aqueous sulfuric acid described in step (two) (1st) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration is 0.2mol/L-2.0mol/L, and operation temperature is 20 DEG C-60 DEG C.

Further, in aqueous sulfuric acid described in step (two) (2nd) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration≤0.2mol/L, operation temperature is 20 DEG C-60 DEG C.

Further, the isolating membrane described in step (two) (3rd) step is acidproof cation exchange membrane.

Further, the anode described in step (two) (3rd) step is PbO₂Electrode, graphite electrode, the geometric shape of anode can Be flat board, netted and three-dimension fixed-bed electrode or porous electrode any one.

Further, the negative electrode described in step (two) (3rd) step is ferrum, the geometric shape of negative electrode can be flat board, netted and Any one of three-dimension fixed-bed electrode or porous electrode.

Further, step (two) (3rd) step Fe³⁺Regeneration and coproduction H₂During, anode operation electric current density is 10mA/ cm²-300mA/cm², operation temperature is 20 DEG C-80 DEG C.

Further, step (two) (3rd) step Fe³⁺Regeneration and coproduction H₂During, cathode operation electric current density is 10mA/ cm²-600mA/cm², operation temperature is 20 DEG C-80 DEG C.

Further, in aqueous sulfuric acid described in step (three) (1st) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration is 0.2mol/L-2.0mol/L, and operation temperature is 20 DEG C-60 DEG C.

Further, in aqueous sulfuric acid described in step (three) (2nd) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration is 0.2mol/L-2.0mol/L, and operation temperature is 20 DEG C-60 DEG C.

Further, the isolating membrane described in step (three) (3rd) step is acidproof cation exchange membrane.

Further, the anode described in step (three) (3rd) step is PbO₂Electrode, graphite electrode, the geometric shape of anode can Be flat board, netted and three-dimension fixed-bed electrode or porous electrode any one.

Further, the negative electrode described in step (three) (3rd) step is ferrum, the geometric shape of negative electrode can be flat board, netted and Any one of three-dimension fixed-bed electrode or porous electrode.

Further, step (three) (3rd) step Fe³⁺Regeneration and removing Fe²⁺Co-production H₂During, anode operation electric current density For 10mA/cm²-300mA/cm², operation temperature is 20 DEG C-80 DEG C.

Further, step (three) (3rd) step Fe³⁺Regeneration and removing Fe²⁺Co-production H₂During, cathode operation is further, Electric current density is 10mA/cm²-600mA/cm², operation temperature is 20 DEG C-80 DEG C.

Further, the method for step (three) (4th) step aqueous sulfuric acid concentration is for absorbing SO₃Or dehydration by evaporation technology Combination in any.

The know-why that the present invention uses:

(1) SO₂Sorption enhanced process

SO₂Soluble in water, can be by the Fe in solution³⁺Oxidation is converted into H₂SO₄。SO₂The chemical equation of sorption enhanced process As follows:

SO₂+2H₂O+Fe³⁺→H₂SO₄+Fe²⁺+2H⁺

Principle involved by this process is as follows:

(1) SO is utilized₂The characteristic of solution soluble in water: SO₂Soluble in water, dissolubility in aqueous is along with temperature Raising and decline, the dissolubility in aqueous sulfuric acid declines along with the rising of sulfuric acid concentration.Under experimental conditions, SO₂Tool There is bigger dissolubility.

(2) SO is utilized₂The most oxidized characteristic: the SO being absorbed in water₂There is reproducibility, be oxidized easily agent and be oxidized to Sulphuric acid.

(3) Fe in aqueous sulfuric acid is utilized³⁺There is the characteristic of certain oxidability: the Fe in aqueous sulfuric acid³⁺For having The oxidant of medium oxidability, can be by SO₂Oxidation is converted into sulphuric acid, Fe simultaneously³⁺It is reduced to Fe²⁺.At aqueous sulfuric acid In, SO₂There is bigger dissolubility, Fe³⁺And Fe²⁺The most all there is certain dissolubility, and stable in properties, therefore can realize SO₂Chemical absorbing and oxidation convert.

(2) Fe³⁺Regeneration and coproduction H₂Process

Fe in aqueous sulfuric acid²⁺Fe is generated in anode electrochemical oxidation³⁺, H simultaneously⁺Obtain in negative electrode generation reduction reaction H₂。Fe³⁺Electrochemical regeneration coproduction H simultaneously₂The reaction equation of process is as follows:

Anode: 2Fe²⁺→2Fe³⁺+2e^-

Negative electrode: 2H⁺+2e^-→H₂

Overall reaction: 2Fe²⁺+2H⁺→2Fe³⁺+H₂

(1) Fe is utilized²⁺Easily obtain Fe in the regeneration of anode generation electrochemical oxidation reactions³⁺Characteristic

At Fe³⁺In regenerative process, use electrochemical oxidation technology, with PbO₂For anode, the Fe in anode chamber²⁺Send out at anode Raw electrochemical oxidation reactions generates Fe³⁺, it is achieved Fe³⁺/Fe²⁺Electricity to recycling.

2Fe²⁺→2Fe³⁺+2e

The standard electrode potential of this reaction

In aqueous sulfuric acid, the reaction equation of oxygen evolution reaction is:

2H₂O→O₂+4H⁺+4e^-

The standard electrode potential of this reaction is

Obviously, before Oxygen anodic evolution, first there is Fe²⁺To Fe³⁺The reaction converted.

(2) H in aqueous sulfuric acid is utilized⁺Easily generate H at negative electrode generation electrochemical reducting reaction₂Characteristic

H in cathode chamber⁺Iron electrode occur reduction reaction generate H₂, realizing Fe²⁺Anodic oxidation generates Fe³⁺Same Time, there is H at negative electrode⁺Electrochemical reducting reaction obtain H₂。

2H⁺+2e^-→H₂

The standard electrode potential of this reaction is

Obviously, aqueous sulfuric acid is susceptible to evolving hydrogen reaction on negative electrode.

(3) characteristic of paired electrochemical reaction on negative electrode and anode is utilized

In isolating membrane electrochemical reactor, with sulphuric acid as supporting electrolyte, the Fe in aqueous sulfuric acid in anode chamber²⁺? Anode generation oxidation reaction generates Fe³⁺；H in aqueous sulfuric acid in cathode chamber⁺H is generated in negative electrode generation reduction reaction₂, it is achieved Negative electrode and anode paired electrosynthesis.

(3) Fe²⁺Removing and coproduction H₂Process

(1) Fe on negative electrode is utilized²⁺Electrochemical reduction coproduction H simultaneously₂Characteristic

Fe in sulfuric acid solution²⁺Through electrochemical reduction deposition removing Fe on negative electrode²⁺, H simultaneously⁺Reduction generates H₂.Anode and The reaction of negative electrode is as follows:

Anode reaction: 2Fe²⁺→2Fe³⁺+2e

Cathode reaction: Fe²⁺+2e→Fe；2H⁺+2e→H₂

(2) Fe is utilized²⁺The characteristic of ferrum is generated in negative electrode generation electrochemical reduction deposition

Fe²⁺The standard electrode potential of ferrum is generated in negative electrode generation electrochemical reduction depositionWork as Fe²⁺ Concentration is 1.0 × 10^-6During mol/L,Obviously, in order to by the Fe in aqueous sulfuric acid²⁺Drop to ratio relatively low Concentration, negative electrode certainly exists evolving hydrogen reaction.

(3) process coproduction H is utilized₂Particularity

Fe is removed in negative electrode electro-deposition²⁺During, as long as meeting removing Fe²⁺Concentration requirement, it is not necessary to consider process Current efficiency problem because the only parallel reaction of this process is evolving hydrogen reaction, and the technology of evolving hydrogen reaction not influence process And economic indicator.

(4) particularity of aqueous sulfuric acid is utilized

Sulphuric acid stable in properties, dilute sulfuric acid aqueous solution absorbs and dissolves SO₃Concentrated sulphuric acid can be prepared.Therefore, through containing Fe²⁺Sulfur Aqueous acid takes off Fe²⁺After, use and absorb SO₃Or after dehydration by evaporation concentration, can prepare and meet the sulfuric acid product that user requires.

The main technique technology that the present invention uses:

(1) SO₂Sorption enhanced process

(1)Fe³⁺Oxidation SO₂H processed₂SO₄Technology: SO₂In aqueous be absorbed as MODEL OF CHEMICAL ABSORPTION PROCESS, with Fe³⁺For oxidation Agent, by SO₂Oxidation is converted into sulphuric acid, improves speed and the SO of absorption process₂Meltage in aqueous sulfuric acid.Meanwhile, Fe³⁺The Fe that reduction obtains²⁺Fe can be regenerated as by electrochemical techniques³⁺Recycle, when in aqueous sulfuric acid, sulphuric acid reaches certain After concentration, can be through removing Fe further²⁺And concentration operation prepares sulfuric acid product.

(2) aqueous sulfuric acid absorbs SO₂Technology: although SO₂Dissolubility in aqueous sulfuric acid along with temperature rising and Sulfuric acid concentration raises and declines, but in order to meet Fe³⁺SO in aqueous sulfuric acid will be absorbed in for oxidant₂It is oxidized to sulphuric acid Process, and Fe³⁺And Fe²⁺In aqueous sulfuric acid, it is respectively provided with the feature such as certain dissolubility and SOLUTION PROPERTIES stability, adopts It is absorbent with aqueous sulfuric acid.Use this Technology, be possible not only to realize SO₂Absorption, but also can be at oxidant Fe³⁺Oxidation under, by SO₂It is converted into sulphuric acid.

(3)SO₂Sorption enhanced coupling technique: by SO₂Absorbing dissolving and being converted into the process of sulphuric acid at aqueous sulfuric acid Coupling.Fe in aqueous sulfuric acid³⁺For having the oxidant of medium oxidability, can be with the SO in sulfur oxide aqueous acid₂ Obtain sulphuric acid, simultaneously Fe³⁺It is reduced to Fe²⁺。

(2) Fe³⁺Regeneration and coproduction H₂Process

(1)Fe²⁺Anodic oxidation and H⁺Cathodic reduction paired electrochemical synthesis technology: with cation exchange membrane as isolating membrane Electrochemical reactor in, anode occur Fe²⁺Electrochemical oxidation generates Fe³⁺Reaction, simultaneously negative electrode occur H⁺Electrochemistry also Former reaction obtains H₂, it is achieved effective utilization of dual chamber electrode.

(2) containing Fe²⁺Fe on aqueous sulfuric acid Anodic²⁺Electrochemical oxidation regeneration preparation Fe³⁺Technology: with PbO₂For sun Pole, with SO₂Obtain during sorption enhanced containing Fe²⁺Aqueous sulfuric acid be electrolyte, realize Fe at anode²⁺Electrochemical oxidation Regeneration obtains Fe³⁺, due to the analysis O of this electrode₂Overpotential is big, therefore Fe²⁺Oxidation generates Fe³⁺The current efficiency of process is high.

(3) H in iron electrode in aqueous sulfuric acid⁺Electrochemical reducting reaction is occurred to prepare H₂Technology: in isolating membrane electrochemistry In reactor, with sulphuric acid as supporting electrolyte, the H in aqueous sulfuric acid in cathode chamber⁺H is generated in negative electrode generation reduction reaction₂。 Owing to anode is Fe²⁺To Fe³⁺Convert, therefore can obtain target product at negative electrode and anode, it is achieved having of dual chamber electrode simultaneously Effect utilizes.

(3) Fe²⁺Removing and coproduction H₂Process

(1) anodic oxidation and cathodic reduction paired electrochemical synthesis technology: at the electricity with cation exchange membrane as isolating membrane In chemical reactor, Fe on anode²⁺Electrochemical oxidation is occurred to generate Fe³⁺, Fe on negative electrode simultaneously²⁺And H⁺There is electrochemical reduction Reaction generates Fe and H respectively₂, it is achieved effective utilization of dual chamber electrode.

(2)Fe²⁺Electrochemical deposition removing ferrum co-production H₂Technology: remove Fe in negative electrode electro-deposition²⁺During, if full Foot removing Fe²⁺Concentration requirement, it is not necessary to consider process current efficiency problem because the only parallel reaction of this process be analysis Hydrogen reacts, and the technical and economic requirements of evolving hydrogen reaction not influence process, at removing Fe²⁺While can be with coproduction H₂。

(3) aqueous sulfuric acid concentration technology: containing Fe²⁺Aqueous sulfuric acid take off Fe²⁺After, use and absorb SO₃Or evaporation is de- After water concentration, can prepare and meet the sulfuric acid product that user requires.

The innovative point of the present invention

(1)Fe³⁺/Fe²⁺For blood circulation: use Fe³⁺It is dissolved in SO in aqueous solution as absorption₂Wet oxidation prepares sulfur The oxidant of aqueous acid, meanwhile, Fe³⁺It is reduced to Fe²⁺。Fe²⁺Fe is obtained through the regeneration of electrochemical anodic oxidation method³⁺, it is achieved Fe³⁺/Fe²⁺Electricity is to the recycling during indirect electrochemical oxidation.

(2)Fe³⁺Regeneration and coproduction H₂PROCESS COUPLING: realize Fe using electrochemical anodic oxidation technology²⁺Electrochemical oxidation It is regenerated as Fe³⁺During, the H of cathode chamber⁺H is generated in cathodic reduction₂, it is achieved Fe³⁺Regeneration, coproduction H simultaneously₂。

(3)Fe²⁺Anode electrochemical regeneration Fe³⁺Fe is removed with negative electrode²⁺PROCESS COUPLING: use electrochemical techniques, Fe²⁺At sun Pole occurs oxidation reaction to generate Fe³⁺, it is achieved Fe³⁺/Fe²⁺Electricity to recycling；In order to meet aqueous sulfuric acid purity requirement, By the Fe in negative electrode electro-deposition techniques removing aqueous sulfuric acid²⁺Deng impurity metal ion, it is achieved Fe²⁺Anode electrochemical regenerates Fe³⁺Fe is removed with negative electrode²⁺PROCESS COUPLING.

(4) removing Fe²⁺With coproduction H₂PROCESS COUPLING: in using electrochemical cathode reduction technique removing aqueous sulfuric acid Fe²⁺During, the H in solution⁺H is generated at negative electrode generation electrochemical reducting reaction₂, it is achieved Fe²⁺While removing, coproduction obtains To H₂。

(5) aqueous sulfuric acid absorbs SO₂: employing aqueous sulfuric acid is absorbent, absorbs and dissolves SO₂, through peroxidating, remove impurity, The operation such as concentration can prepare aqueous sulfuric acid.Fundamentally change to use and traditional dissolve SO with alkali liquor absorption₂Drawback, solve Determine and consumed alkali and the critical defect of by-product sulfate.The most inherently solve and remove sulfur, coproduction hydrogen based on S-I circulation theory Gas, the critical defect of sulphuric acid.

Beneficial effects of the present invention is embodied in:

(1) wet desulphurization-oxidation converts: SO₂Dissolubility in aqueous declines along with the rising of temperature, SO₂At sulfur Dissolubility in aqueous acid also declines along with the rising of sulfuric acid concentration.Under experimental conditions, SO₂There is bigger dissolubility, Aqueous sulfuric acid can be used to absorb SO₂, absorb the SO dissolved₂With oxidant Fe³⁺Reaction generates sulphuric acid, makes SO₂Absorb and convert Carry out simultaneously.SO₂Removal efficiency high, convert thoroughly, mild condition, other no coupling product of process, it is achieved SO₂Wet method removing-oxygen Change and convert co-producing sulfuric acid aqueous solution simultaneously.

(2) by Fe³⁺/Fe²⁺It is applied to SO as blood circulation₂Wet oxidation converts: Fe³⁺And Fe²⁺In aqueous sulfuric acid Can stable existence, and there is bigger dissolubility.Fe in aqueous sulfuric acid³⁺For having the oxygen of medium oxidability Agent, Fe³⁺With the SO absorbed₂Reaction generates sulphuric acid, Fe³⁺It is reduced to Fe²⁺.In aqueous sulfuric acid, Fe³⁺And Fe²⁺It is respectively provided with one Fixed dissolubility, and stable in properties.Fe²⁺Fe can be obtained by electrochemical oxidation regeneration³⁺, it is possible to realize Fe³⁺/Fe²⁺Electricity to Recycling, the utilization ratio of material and energy is high.

(3)Fe²⁺Electrochemical oxidation regeneration obtains Fe³⁺: with SO₂Obtain during sorption enhanced containing Fe²⁺Sulphuric acid water-soluble Liquid is electrolyte, realizes Fe at anode²⁺Electrochemical oxidation regeneration obtains Fe³⁺, owing to the overpotential for oxygen evolution of this electrode is big, therefore Fe²⁺Oxidation generates Fe³⁺The current efficiency of process is high.

(4) electro-deposition removing Fe²⁺Co-production H₂Technology: remove Fe in negative electrode electro-deposition²⁺During, as long as meeting removing Fe²⁺Concentration requirement, it is not necessary to consider process current efficiency problem because the only parallel reaction of this process is that liberation of hydrogen is anti- Should, and the technical and economic requirements of evolving hydrogen reaction not influence process.

(5) H of coproduction₂Product purity is high, and energy consumption is low, and process safety is reliable: Fe³⁺Regeneration and Fe²⁺Subtractive process all and joins Produce H₂.With traditional electrolysis H₂O H₂Compare, owing to anode is without O₂Produce, the H obtained₂Purity is high, it is also possible to avoid O₂With H₂Mixed Close the danger that blast occurs.Due to Fe²⁺Electrochemical oxidation generates Fe³⁺Electrode potential compare H₂O decomposes generation O₂Electrode potential Low, therefore its tank voltage is also than electrolysis water H₂Low.The Technology of the present invention not only H₂The purity of product is high, and energy consumption is low, Process safety is reliable.

(6) desulfurization co-producing hydrogen and sulphuric acid coupling: the present invention is a kind of desulfurization co-producing hydrogen and the method for sulphuric acid, not only uses Aqueous sulfuric acid wet method is stripped of the sulfur dioxide in gas phase, simultaneously can be with co-producing hydrogen and sulphuric acid.The technical process of the present invention Efficiency and capacity usage ratio are high, and equipment investment and production cost are low, and process safety is reliable, and beneficially heavy industrialization, is one Plant desulfurization and the Technology of sulfur dioxide comprehensive utilization technique of environmental protection.

Accompanying drawing explanation

Fig. 1 is the inventive method step (one) SO₂Sorption enhanced process chart.

Fig. 2 is the inventive method step (two) Fe³⁺Regeneration and coproduction H₂Process chart.

Fig. 3 is the inventive method step (three) Fe²⁺Removing and coproduction H₂Process chart.

Fig. 4 is the Fe of the inventive method³⁺Regeneration and coproduction H₂Electrochemical reactor schematic diagram.

Fig. 5 is the Fe of the inventive method²⁺Removing and coproduction H₂Electrochemical reactor schematic diagram.

Detailed description of the invention

The present invention is further detailed explanation with embodiment below in conjunction with the accompanying drawings.

Embodiment one

As Figure 1-Figure 5, a kind of desulfurization co-producing hydrogen and the method for sulphuric acid, including " SO₂Sorption enhanced ", " Fe³⁺Regeneration And coproduction H₂”、“Fe²⁺Removing and coproduction H₂" three key steps:

Specifically comprise the following steps that

(1) SO₂Sorption enhanced process

As it is shown in figure 1, a kind of SO₂The process of sorption enhanced, particularly with containing Fe³⁺Aqueous sulfuric acid for absorb Agent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺；Obtain containing Fe²⁺Aqueous sulfuric acid can be further by Fe²⁺Oxidation regeneration is Fe³⁺Conduct afterwards Absorbent recycles, it is also possible to through removing Fe further²⁺And concentration operation prepares sulfuric acid product.Its concrete steps are such as Under:

(1) absorbent preparation: in absorbent dosing apparatus, sulphuric acid and water are mixed to prepare aqueous sulfuric acid, then by sulfur Acid ferrum is dissolved in this aqueous sulfuric acid, prepares the H Han 0.2mol/L₂SO₄And 0.2mol/L Fe³⁺Absorbent, temperature is 20 DEG C.

(2)SO₂Sorption enhanced: at spray tower SO₂In absorption plant, operation temperature is 20 DEG C, with containing that previous step prepares Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, with previous step prepare containing Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, simultaneously Fe³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in piping filter solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid It is separated off solid impurity, obtains containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂Process

As shown in Figure 2 and Figure 4, in isolating membrane electrochemical reactor, with containing Fe²⁺Aqueous sulfuric acid be anolyte, Fe² ⁺Fe is generated in anode generation oxidation reaction³⁺, containing Fe³⁺Aqueous sulfuric acid as SO₂Oxidant use；With aqueous sulfuric acid For catholyte, H⁺H is generated in negative electrode generation reduction reaction₂.Specifically comprise the following steps that

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consist of 0.2mol/LH₂SO₄And 0.2mol/L Fe²⁺, operation temperature is 20 DEG C.

(2) catholyte preparation: in catholyte dosing apparatus, sulphuric acid and water are mixed to prepare 0.2mol/L H₂SO₄As Catholyte, operation temperature is 20 DEG C.

(3)Fe³⁺Regeneration and coproduction H₂: in the electrochemical reactor with sulfonic acid type cation exchange membrane as isolating membrane, with Sulphuric acid is supporting electrolyte, with flat board PbO₂Electrode is anode, and operation electric current density is 10mA/cm², operation temperature is 20 DEG C, sun Fe in extremely indoor aqueous sulfuric acid²⁺Fe is obtained at anode generation electrochemical oxidation³⁺, reacted anolyte is as containing oxidation Agent Fe³⁺Aqueous sulfuric acid use.With flat board ferroelectricity extremely negative electrode, operation electric current density is 10mA/cm², operation temperature is 20 DEG C, the H in aqueous sulfuric acid in cathode chamber⁺H is generated at negative electrode generation electrochemical reducting reaction₂, it is achieved Fe³⁺Regeneration and coproduction H₂ Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂Process

As shown in Fig. 3 and 5 figures, in isolating membrane electrochemical reactor, negative electrode Fe²⁺Electro-deposition removes ferrum and coproduction H₂, anode Fe²⁺Oxidation regeneration obtains Fe³⁺.Specifically comprise the following steps that

(1) anolyte preparation: in anolyte dosing apparatus, sulphuric acid and water are mixed to obtain aqueous sulfuric acid, solution composition For 0.2mol/L H₂SO₄And 0.2mol/L Fe²⁺, operation temperature is 20 DEG C.

(2) catholyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be catholyte, molten Liquid consists of 8.0mol/L H₂SO₄、2.0mol/L Fe²⁺And 0.02mol/L Fe³⁺, operation temperature is 20 DEG C.

(3)Fe²⁺Removing and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with flat board ferroelectricity extremely negative electrode, operation electric current density is 10mA/cm², operation temperature is 20 DEG C, Fe²⁺? Negative electrode generation electro-deposition generates Fe, the Fe in removing aqueous sulfuric acid²⁺；H⁺H is generated at negative electrode generation electrochemical reducting reaction₂。 With flat board PbO₂Electrode is anode, and operation electric current density is 10mA/cm², operation temperature is 20 DEG C, Fe²⁺Electrification is there is at anode Learn oxidation regeneration and obtain Fe³⁺, reacted anolyte is as containing oxidant Fe³⁺Aqueous sulfuric acid uses.Fe is removed at negative electrode²⁺ And coproduction H₂While, obtain Fe in anode regeneration³⁺, dual chamber electrode is obtained for effectively utilization.

(4) aqueous sulfuric acid concentrates: when previous step is through removing Fe²⁺Aqueous sulfuric acid in Fe²⁺Concentration≤1.0 × 10^- ⁶During mol/L, aqueous sulfuric acid dehydration by evaporation is concentrated, prepare 9.0mol/L H₂SO₄As lead storage battery electrolytic solution preparation former Material uses.

Embodiment two

A kind of desulfurization co-producing hydrogen and the method for sulphuric acid, it is characterised in that the method includes " SO₂Sorption enhanced ", " Fe³⁺Again Life and coproduction H₂”、“Fe²⁺Removing and coproduction H₂" three key steps:

Specifically comprise the following steps that

(1) SO₂Sorption enhanced process

As it is shown in figure 1, a kind of SO₂The process of sorption enhanced, particularly with containing Fe³⁺Aqueous sulfuric acid for absorb Agent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺；Obtain containing Fe²⁺Aqueous sulfuric acid can be further by Fe²⁺Oxidation regeneration is Fe³⁺Conduct afterwards Absorbent recycles, it is also possible to through removing Fe further²⁺And concentration operation prepares sulfuric acid product.Specifically comprise the following steps that

(1) absorbent preparation: in absorbent dosing apparatus, Fe will be contained²⁺Aqueous sulfuric acid mix with water, then dissolve in sulfur Acid ferrum, prepares the H Han 0.2mol₂SO₄、2.0mol/L Fe³⁺With 0.2mol/L Fe²⁺Absorbent, temperature is 60 DEG C.

(2)SO₂Sorption enhanced: at spray column SO₂In absorption plant, operation temperature is 60 DEG C, with containing that previous step prepares Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂ With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in filter press solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid It is separated off solid impurity, obtains containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂Process

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consists of 8.0mol/L H₂SO₄、2.0mol/L Fe²⁺And Fe³⁺Concentration≤0.2mol/L, operation temperature is 60 DEG C.

(2) catholyte preparation: in catholyte dosing apparatus, prepares 0.6mol/L H₂SO₄、0.02mol/L Fe³⁺With 0.02mol/L Fe³⁺The catholyte of concentration, operation temperature is 60 DEG C.

(3)Fe³⁺Regeneration and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, with netted PbO₂Electrode is anode, and operation electric current density is 300mA/cm², operate temperature 80 DEG C, anode Fe in indoor aqueous sulfuric acid²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation³⁺, reacted anolyte is as oxygen-containing Agent Fe³⁺Aqueous sulfuric acid use.With netted ferroelectricity extremely negative electrode, operation electric current density is 600mA/cm², operation temperature is 80 DEG C, the H in aqueous sulfuric acid in cathode chamber⁺H is generated at negative electrode generation electrochemical reducting reaction₂, it is achieved Fe³⁺Regeneration and coproduction H₂Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂Process

(2) catholyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be catholyte, molten Liquid consists of 8.0mol/L H₂SO₄、2.0mol/L Fe²⁺And 0.02mol/L Fe³⁺, operation temperature is 60 DEG C.

(3)Fe²⁺Removing and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with netted ferroelectricity extremely negative electrode, operation electric current density is 600mA/cm², operation temperature is 80 DEG C, Fe²⁺ Fe, the Fe in removing aqueous sulfuric acid is generated in negative electrode generation electro-deposition²⁺；H⁺Generate at negative electrode generation electrochemical reducting reaction H₂.With netted PbO₂Electrode is anode, and operation electric current density is 300mA/cm², operation temperature is 80 DEG C, Fe²⁺Electricity is there is at anode Chemical oxidation regeneration obtains Fe³⁺, reacted anolyte is as containing oxidant Fe³⁺Aqueous sulfuric acid uses.Fe is removed at negative electrode² ⁺And coproduction H₂While, obtain Fe in anode regeneration³⁺, dual chamber electrode is obtained for effectively utilization.

Embodiment three

A kind of desulfurization co-producing hydrogen and the method for sulphuric acid, including " SO₂Sorption enhanced ", " Fe³⁺Regeneration and coproduction H₂”、“Fe²⁺ Removing and coproduction H₂" three key steps: specifically comprise the following steps that

(1) SO₂Sorption enhanced process

(1) absorbent preparation: with SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid mix with water, then dissolve in sulphuric acid Ferrum, prepares the H Han 2.0mol/L₂SO₄、0.6mol/L Fe³⁺With 0.1mol/L Fe²⁺Absorbent, temperature is 30 DEG C.

(2)SO₂Sorption enhanced: at packed tower SO₂In absorption plant, operation temperature is 30 DEG C, with containing that previous step prepares Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂ With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in centrifuge solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid separation Remove solid impurity, obtain containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂Process

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Sulfuric acid solution be anolyte, solution Consist of 3.0mol/L H₂SO₄、1.0mol/L Fe²⁺And 0.2mol/L Fe³⁺, operation temperature is 40 DEG C.

(2) catholyte preparation: by the aqueous sulfuric acid that obtains directly as catholyte, solution composition is 0.8mol/L H₂SO₄、0.02mol/L Fe³⁺And 0.01mol/L Fe³⁺, operation temperature is 40 DEG C.

(3)Fe³⁺Regeneration and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with graphite three-dimension fixed-bed electrode as anode, operation electric current density is 100mA/cm², operation temperature is 60 DEG C, the Fe in aqueous sulfuric acid in anode chamber²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation³⁺, reacted anolyte As containing oxidant Fe³⁺Aqueous sulfuric acid use.With three-dimension fixed-bed electrode ferroelectricity extremely negative electrode, operation electric current density is 600mA/cm², operation temperature is 60 DEG C, the H in aqueous sulfuric acid in cathode chamber⁺Generate at negative electrode generation electrochemical reducting reaction H₂, it is achieved Fe²⁺Oxidation preparation Fe³⁺And coproduction H₂Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂Process

(1) anolyte preparation: by step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consists of 3.0mol/L H₂SO₄、1.0mol/L Fe²⁺And 0.2mol/L Fe³⁺, operation temperature is 40 DEG C.

(2) catholyte preparation: by step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be catholyte, molten Liquid consists of 8.0mol/L H₂SO₄、1.0mol/L Fe²⁺And 0.02mol/L Fe³⁺, operation temperature is 40 DEG C.

(3)Fe²⁺Removing and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with three-dimensional fixed bed ferroelectricity extremely negative electrode, operation electric current density is 600mA/cm², operation temperature is 60 DEG C, Fe²⁺Fe, the Fe in removing aqueous sulfuric acid is generated in negative electrode generation electro-deposition²⁺；H⁺At negative electrode generation electrochemical reducting reaction Generate H₂.With graphite three-dimension fixed-bed electrode as anode, operation electric current density is 100mA/cm², operation temperature is 60 DEG C, Fe²⁺ Fe is obtained in the regeneration of anode generation electrochemical oxidation³⁺, reacted anolyte is as containing oxidant Fe³⁺Aqueous sulfuric acid uses. Fe is removed at negative electrode²⁺And coproduction H₂While, obtain Fe in anode regeneration³⁺, dual chamber electrode is obtained for effectively utilization.

(4) aqueous sulfuric acid concentrates: when previous step is through removing Fe²⁺Aqueous sulfuric acid in Fe²⁺Concentration≤1.0 × 10^- ⁵During mol/L, aqueous sulfuric acid dehydration by evaporation is concentrated, prepare 10.0mol/L H₂SO₄Join as metallic aluminium electrochemical corrosive liquid The sulphuric acid raw material of the purposes such as system uses.

Embodiment four

A kind of desulfurization co-producing hydrogen and the method for sulphuric acid, including " SO₂Sorption enhanced ", " Fe³⁺Regeneration and coproduction H₂”、“Fe²⁺ Removing and coproduction H₂" three key steps:

Specifically comprise the following steps that

(1) SO₂Sorption enhanced process

(1) absorbent preparation: in absorbent dosing apparatus, sulphuric acid and water are mixed to prepare aqueous sulfuric acid, then by sulfur Acid ferrum is dissolved in this aqueous sulfuric acid, prepares the H Han 4.0mol/L₂SO₄And 1.0mol/L Fe³⁺Absorbent, temperature is 60 DEG C.

(2)SO₂Sorption enhanced: at tubulent contact tower SO₂In absorption plant, operation temperature is 60 DEG C, with containing that previous step prepares Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂ With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in drum filtering-machine solid-liquid separation equipment, material obtained in the previous step is carried out solid-liquid It is separated off solid impurity, obtains containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂Process

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consists of 2.0mol/L H₂SO₄、2.0mol/L Fe²⁺And 0.1mol/L Fe³⁺, operation temperature is 60 DEG C.

(2) catholyte preparation: by the aqueous sulfuric acid that obtains directly as catholyte, solution composition is 4.0mol/L H₂SO₄、0.02mol/L Fe³⁺And 0.01mol/L Fe³⁺, operation temperature is 60 DEG C；

(3)Fe³⁺Regeneration and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with graphite three-dimension fixed-bed electrode as anode, operation electric current density is 200mA/cm², operation temperature is 80 DEG C, the Fe in aqueous sulfuric acid in anode chamber²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation³⁺, reacted anolyte As containing oxidant Fe³⁺Aqueous sulfuric acid use.With netted ferroelectricity extremely negative electrode, cathode operation electric current density is 400mA/ cm², operation temperature is 80 DEG C, the H in aqueous sulfuric acid in cathode chamber⁺H is generated at negative electrode generation electrochemical reducting reaction₂, it is achieved Fe²⁺Oxidation preparation Fe³⁺And coproduction H₂Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂Process

(1) anolyte preparation: by obtain containing Fe²⁺Aqueous sulfuric acid directly as anolyte, solution composition be 2.0mol/L H₂SO₄、2.0mol/L Fe²⁺And 0.1mol/L Fe³⁺, operation temperature is 60 DEG C.

(2) catholyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be catholyte, molten Liquid consists of 2.0mol/L H₂SO₄、1.6mol/L Fe²⁺And 0.2mol/L Fe³⁺, operation temperature is 60 DEG C.

(3)Fe²⁺Removing and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with netted ferroelectricity extremely negative electrode, operation electric current density is 400mA/cm², operation temperature is 80 DEG C, Fe²⁺ Fe, the Fe in removing aqueous sulfuric acid is generated in negative electrode generation electro-deposition²⁺；H⁺Generate at negative electrode generation electrochemical reducting reaction H₂.With graphite three-dimension fixed-bed electrode as anode, operation electric current density is 200mA/cm², operation temperature is 80 DEG C, Fe²⁺At sun Pole occurs electrochemical oxidation regeneration to obtain Fe³⁺, reacted anolyte is as containing oxidant Fe³⁺Aqueous sulfuric acid uses.At the moon Pole removing Fe²⁺And coproduction H₂While, obtain Fe in anode regeneration³⁺, dual chamber electrode is obtained for effectively utilization.

(4) aqueous sulfuric acid concentrates: by previous step through removing Fe²⁺Aqueous sulfuric acid prepare directly as pickle Sulphuric acid raw material uses.

Embodiment five

Specifically comprise the following steps that

(1) SO₂Sorption enhanced process

(1) absorbent preparation: in absorbent dosing apparatus, Fe will be contained²⁺Aqueous sulfuric acid mix with water, then dissolve in sulfur Acid ferrum, prepares the H Han 2.0mol/L₂SO₄、1.6mol/L Fe³⁺And 0.2mol/L Fe²⁺Absorbent, temperature is 50 DEG C.

(2)SO₂Sorption enhanced: at sieve-plate tower SO₂In absorption plant, operation temperature is 50 DEG C, with containing that previous step prepares Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂ With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in disk type filter solid-liquid separation equipment, material obtained in the previous step is carried out admittedly- Liquid is separated off solid impurity, obtains containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂Process

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consists of 4.0mol/L H₂SO₄、2.0mol/L Fe²⁺And Fe³⁺Concentration≤0.2mol/L, operation temperature is 20 DEG C-60 DEG C.

(2) catholyte preparation: by the aqueous sulfuric acid that obtains directly as catholyte, solution composition is 1.0mol/L H₂SO₄、Fe³⁺Concentration≤0.02mol/L, Fe³⁺Concentration≤0.02mol/L, operation temperature is 60 DEG C.

(3)Fe³⁺Regeneration and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, with netted PbO₂Electrode is anode, and operation electric current density is 100mA/cm², operation temperature is 60 DEG C, sun Fe in extremely indoor aqueous sulfuric acid²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation³⁺, reacted anolyte is as containing Oxidant Fe³⁺Aqueous sulfuric acid use.With three-dimensional porous ferroelectricity extremely negative electrode, operation electric current density is 500mA/cm², operation Temperature is 60 DEG C, the H in aqueous sulfuric acid in cathode chamber⁺H is generated at negative electrode generation electrochemical reducting reaction₂, it is achieved Fe²⁺Oxidation Preparation Fe³⁺And coproduction H₂Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂Process

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consists of 4.0mol/L H₂SO₄、2.0mol/L Fe²⁺And Fe³⁺Concentration≤0.2mol/L, operation temperature is 60 DEG C.

(2) catholyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be catholyte, Solution composition is 8.0mol/L H₂SO₄、0.2mol/L Fe²⁺And 0.02mol/L Fe³⁺, operation temperature is 60 DEG C.

(3)Fe²⁺Removing and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with three-dimensional porous ferroelectricity extremely negative electrode, operation electric current density is 500mA/cm², operation temperature is 60 DEG C, Fe²⁺Fe, the Fe in removing aqueous sulfuric acid is generated in negative electrode generation electro-deposition²⁺；H⁺Raw at negative electrode generation electrochemical reducting reaction Become H₂.With netted PbO₂Electrode is anode, and operation electric current density is 500mA/cm², operation temperature is 60 DEG C, Fe²⁺Occur at anode Electrochemical oxidation regeneration obtains Fe³⁺, reacted anolyte is as containing oxidant Fe³⁺Aqueous sulfuric acid uses.Remove at negative electrode Fe²⁺And coproduction H₂While, obtain Fe in anode regeneration³⁺, dual chamber electrode is obtained for effectively utilization.

(4) aqueous sulfuric acid concentrates: previous step is through removing Fe²⁺Aqueous sulfuric acid absorb SO₃Prepare 18.4mol/L H₂SO₄Raw material as pickle uses.

Embodiment six

Specifically comprise the following steps that

(1) SO₂Sorption enhanced process

(1) absorbent preparation: in absorbent dosing apparatus, Fe will be contained²⁺Aqueous sulfuric acid mix with water, then dissolve in sulfur Acid ferrum, prepares the H Han 6.0mol/L₂SO₄、1.8mol/L Fe³⁺And 0.2mol/L Fe²⁺Absorbent, temperature is 40 DEG C.

(2)SO₂Sorption enhanced: at venturi SO₂In absorption plant, operation temperature is 60 DEG C, with containing that previous step prepares Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂ With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺。

(3) solid-liquid separation: in leaf filter solid-liquid separation equipment, material obtained in the previous step is carried out admittedly- Liquid is separated off solid impurity, obtains containing Fe²⁺Aqueous sulfuric acid.

(2) Fe³⁺Regeneration and coproduction H₂Process

(1) anolyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, molten Liquid consists of 8.0mol/L H₂SO₄And 2.0mol/L Fe²⁺, operation temperature is 40 DEG C.

(2) catholyte preparation: in catholyte dosing apparatus, prepares 6.0mol/L H₂SO₄Catholyte, operation temperature be 40℃。

(3)Fe³⁺Regeneration and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, with PbO₂Three-dimension fixed-bed electrode is anode, and operation electric current density is 200mA/cm², operation temperature is 80 DEG C, the Fe in aqueous sulfuric acid in anode chamber²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation³⁺, reacted anolyte is made For containing oxidant Fe³⁺Aqueous sulfuric acid use.With netted ferroelectricity extremely negative electrode, operation electric current density is 400mA/cm², operation Temperature is 80 DEG C, the H in aqueous sulfuric acid in cathode chamber⁺H is generated at negative electrode generation electrochemical reducting reaction₂, it is achieved Fe²⁺Oxidation Preparation Fe³⁺And coproduction H₂Paired electrochemical synthesis.

(3) Fe²⁺Removing and coproduction H₂Process

(2) catholyte preparation: with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be catholyte, molten Liquid consists of 2.0mol/L H₂SO₄、1.6mol/L Fe²⁺And 0.1mol/L Fe³⁺, operation temperature is 40 DEG C.

(3)Fe²⁺Removing and coproduction H₂: in sulfonic acid type cation exchange membrane for isolating membrane electrochemical reactor, with sulfur Acid is supporting electrolyte, and with netted ferroelectricity extremely negative electrode, operation electric current density is 400mA/cm², operation temperature is 80 DEG C, Fe²⁺ Fe, the Fe in removing aqueous sulfuric acid is generated in negative electrode generation electro-deposition²⁺；H⁺Generate at negative electrode generation electrochemical reducting reaction H₂.With PbO₂Three-dimension fixed-bed electrode is anode, and operation electric current density is 200mA/cm², operation temperature is 80 DEG C, Fe²⁺At anode Electrochemical oxidation regeneration is occurred to obtain Fe³⁺, reacted anolyte is as containing oxidant Fe³⁺Aqueous sulfuric acid uses.At negative electrode Removing Fe²⁺And coproduction H₂While, obtain Fe in anode regeneration³⁺, dual chamber electrode is obtained for effectively utilization.

(4) aqueous sulfuric acid concentrates: by previous step through removing Fe²⁺Aqueous sulfuric acid absorb SO₃Prepare 18.4mol/L H₂SO₄Sulphuric acid raw material as metallic aluminium electrochemical corrosive liquid preparation etc. uses.

The invention is not restricted to above-described embodiment, the technical scheme of all employing equivalents or equivalence replacement formation belongs to this The scope that invention is claimed.Except the various embodiments described above, embodiment of the present invention also have a lot, and all employing equivalents or equivalence are replaced The technical scheme changed, all within protection scope of the present invention.

Claims

1. a desulfurization co-producing hydrogen and the method for sulphuric acid, it is characterised in that the method includes SO₂Sorption enhanced, Fe³⁺Regeneration and Coproduction H₂、Fe²⁺Removing and coproduction H₂Three key steps:

(1) SO₂Sorption enhanced

With containing Fe³⁺Aqueous sulfuric acid be absorbent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs The SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺, obtain containing Fe²⁺Aqueous sulfuric acid；

(2) Fe³⁺Regeneration and coproduction H₂

In isolating membrane electrochemical reactor, with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Sulfuric acid solution be anode Liquid, Fe²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation reactions³⁺, obtain containing Fe³⁺Aqueous sulfuric acid as SO₂Absorb The absorbent of conversion process recycles；With aqueous sulfuric acid as catholyte, H⁺H is generated in negative electrode generation reduction reaction₂；Realize Fe³⁺Regeneration and coproduction H₂Paired electrochemical synthesis；

(3) Fe²⁺Removing and coproduction H₂

In isolating membrane electrochemical reactor, with step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be negative electrode Liquid, Fe²⁺Fe, Fe in removing aqueous sulfuric acid is separated out in negative electrode generation electrochemical reducting reaction deposition²⁺, this solution leads to further Cross absorption SO₃Or after dehydration by evaporation, prepare and meet the sulfuric acid product that user requires；Fe is removed in negative electrode electro-deposition²⁺'s Meanwhile, H⁺H is generated in cathodic reduction₂；With step (one) SO₂Sorption enhanced obtain containing Fe²⁺Aqueous sulfuric acid be anolyte, Fe²⁺Fe is obtained in the regeneration of anode generation electrochemical oxidation reactions³⁺, obtain containing Fe³⁺Aqueous sulfuric acid as SO₂Absorb and turn The absorbent of change process recycles；Both Fe was achieved at negative electrode²⁺Removing and coproduction H₂, make Fe at anode again³⁺Regeneration.

Desulfurization co-producing hydrogen the most according to claim 1 and the method for sulphuric acid, it is characterised in that the concrete step of step () Rapid as follows:

(1) absorbent preparation: in absorbent dosing apparatus, sulphuric acid and water are mixed to prepare aqueous sulfuric acid, then by iron sulfate It is dissolved in this aqueous sulfuric acid, prepares containing Fe³⁺Aqueous sulfuric acid, this solution uses as absorbent；

(2)SO₂Sorption enhanced: at SO₂In sorption enhanced device, with previous step prepare containing Fe³⁺Aqueous sulfuric acid for absorb Agent, Fe³⁺For oxidant, by SO₂Absorption is dissolved in aqueous sulfuric acid, absorbs the SO dissolved₂With Fe³⁺Reaction is converted into H₂SO₄, Fe simultaneously³⁺It is reduced to Fe²⁺；

(3) solid-liquid separation: in solid-liquid separation equipment, carries out solid-liquid separation removing solid-state miscellaneous by material obtained in the previous step Matter, obtains containing Fe²⁺Aqueous sulfuric acid.

Desulfurization co-producing hydrogen the most according to claim 1 and the method for sulphuric acid, it is characterised in that the concrete step of step (two) Rapid as follows:

(1) anolyte preparation: step () is obtained containing Fe²⁺Aqueous sulfuric acid directly as anolyte；Or at sun In the liquid dosing apparatus of pole, sulphuric acid is mixed with water, then dissolves in ferrous sulfate, obtain containing Fe²⁺Aqueous sulfuric acid as anolyte；

(2) catholyte preparation: sulphuric acid and water mixed preparing are obtained aqueous sulfuric acid, or removing Fe step (three) obtained²⁺ Aqueous sulfuric acid as catholyte.

(3)Fe³⁺Regeneration and coproduction H₂: in isolating membrane electrochemical reactor, with sulphuric acid as supporting electrolyte, in aqueous sulfuric acid Fe²⁺Fe is generated at anode generation electrochemical oxidation reactions³⁺, containing Fe³⁺Aqueous sulfuric acid can be as SO₂Sorption enhanced mistake The absorbent of journey recycles；H with aqueous sulfuric acid as catholyte, in solution⁺Obtain at negative electrode generation electrochemical reducting reaction To H₂；Realize Fe³⁺Regeneration and coproduction H₂Paired electrochemical synthesis.

Desulfurization co-producing hydrogen the most according to claim 1 and the method for sulphuric acid, it is characterised in that the concrete step of step (three) Rapid as follows:

(2) catholyte preparation: step () is obtained containing Fe²⁺Aqueous sulfuric acid directly as catholyte；Or negative electrode In liquid dosing apparatus, sulphuric acid is mixed with water, make aqueous sulfuric acid as catholyte；

(3)Fe³⁺Regeneration and removing Fe²⁺Co-production H₂: in isolating membrane electrochemical reactor, with sulphuric acid as supporting electrolyte, sun Fe in extremely indoor aqueous sulfuric acid²⁺Fe is generated at anode generation electrochemical oxidation reactions³⁺, obtain containing Fe³⁺Sulphuric acid water-soluble Liquid enters step () as SO₂The absorbent of sorption enhanced process recycles；Fe in aqueous sulfuric acid in cathode chamber²⁺? Negative electrode generation reduction reaction electro-deposition generates Fe, the Fe in removing solution²⁺, H simultaneously⁺Reduction obtains H₂, remove Fe²⁺Sulphuric acid water Solution enters next step；

(4) aqueous sulfuric acid concentration: previous step is removed Fe²⁺Aqueous sulfuric acid through absorption SO₃Or after dehydration by evaporation, system The standby aqueous sulfuric acid product obtained.

Desulfurization co-producing hydrogen the most according to claim 2 and the method for sulphuric acid, it is characterised in that:

In aqueous sulfuric acid described in step () (1st) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe³⁺Concentration is 0.2mol/L-2.0mol/L, operation temperature is 20 DEG C-60 DEG C；

SO described in step () (2nd) step₂Absorption plant is spray tower, spray column, packed tower, tubulent contact tower, sieve-plate tower and Wen Qiu In any one of absorber, operation temperature is 20 DEG C-60 DEG C；

Step (one) (3rd) step solid-liquid separation equipment is piping filter, filter press, centrifuge, drum filtering-machine, circle Disk filter, leaf filter any one.

Desulfurization co-producing hydrogen and the method for sulphuric acid the most according to claim 3, it is characterised in that:

In aqueous sulfuric acid described in step (two) (1st) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration is 0.2mol/L-2.0mol/L, operation temperature is 20 DEG C-60 DEG C；

In aqueous sulfuric acid described in step (two) (2nd) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration≤ 0.2mol/L, operation temperature is 20 DEG C-60 DEG C；

Isolating membrane described in step (two) (3rd) step is acidproof cation exchange membrane；

Anode described in step (two) (3rd) step is PbO₂Electrode, graphite electrode, the geometric shape of anode can be flat board, netted With any one of three-dimension fixed-bed electrode or porous electrode；

Negative electrode described in step (two) (3rd) step is ferrum, and the geometric shape of negative electrode can be flat board, netted and three-dimensional fixed bed electricity Any one of pole or porous electrode；

Step (two) (3rd) step Fe³⁺Regeneration and coproduction H₂During, anode operation electric current density is 10mA/cm²-300mA/cm², Operation temperature is 20 DEG C-80 DEG C；

Step (two) (3rd) step Fe³⁺Regeneration and coproduction H₂During, cathode operation electric current density is 10mA/cm²-600mA/cm², Operation temperature is 20 DEG C-80 DEG C.

In aqueous sulfuric acid described in step (three) (1st) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration is 0.2mol/L-2.0mol/L, operation temperature is 20 DEG C-60 DEG C；

In aqueous sulfuric acid described in step (three) (2nd) step, the concentration of sulphuric acid is 0.2mol/L-8.0mol/L, Fe²⁺Concentration is 0.2mol/L-2.0mol/L, operation temperature is 20 DEG C-60 DEG C；

Isolating membrane described in step (three) (3rd) step is acidproof cation exchange membrane；

Anode described in step (three) (3rd) step is PbO₂Electrode, graphite electrode, the geometric shape of anode can be flat board, netted With any one of three-dimension fixed-bed electrode or porous electrode；

Negative electrode described in step (three) (3rd) step is ferrum, and the geometric shape of negative electrode can be flat board, netted and three-dimensional fixed bed electricity Any one of pole or porous electrode；

Step (three) (3rd) step Fe³⁺Regeneration and removing Fe²⁺Co-production H₂During, anode operation electric current density is 10mA/cm²- 300mA/cm², operation temperature is 20 DEG C-80 DEG C；

Step (three) (3rd) step Fe³⁺Regeneration and removing Fe²⁺Co-production H₂During, cathode operation electric current density is 10mA/cm²- 600mA/cm², operation temperature is 20 DEG C-80 DEG C.

The method of step (three) (4th) step aqueous sulfuric acid concentration is for absorbing SO₃Or dehydration by evaporation or combinations thereof.