CN106669420B - A kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization - Google Patents
A kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization Download PDFInfo
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- CN106669420B CN106669420B CN201710086849.9A CN201710086849A CN106669420B CN 106669420 B CN106669420 B CN 106669420B CN 201710086849 A CN201710086849 A CN 201710086849A CN 106669420 B CN106669420 B CN 106669420B
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- polyoxometallic acid
- hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
- B01D53/965—Regeneration, reactivation or recycling of reactants including an electrochemical process step
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
Abstract
The invention discloses a kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization, hydrogen sulfide containing gas is passed through from the bottom of polyoxometallic acid salting liquid, is exported after the absorption of polyoxometallic acid salting liquid from desulfurization reactor upper end.After reacting a period of time, the color of polyoxometallic acid salting liquid becomes navy blue from faint yellow, and the numerical value of hydrogen sulfide analyzer is more than stopping ventilation after certain value.Polyoxometallic acid salting liquid after desulfurization is electrolysed a period of time, the anion of polyoxometallate loses electronics in anode and is reproduced, and the hydrogen ion in solution obtains electronics in cathode and generates hydrogen.After the color of polyoxometallic acid salting liquid becomes faint yellow from navy blue, that is, indicate regenerated completion.The present invention realizes polyoxometallate desulfurization regeneration using the method for electrolysis, and regeneration efficiency is high, and stability is good, and realization is regenerated at the same time it can also produce hydrogen, has certain economic benefit, is conducive to industrialization promotion.
Description
Technical field
The invention belongs to the technical field of atmosphere pollution control, in particular to a kind of polyoxometallic acid saline solution desulfurization
Electrochemical regeneration method afterwards.
Background technique
Hydrogen sulfide is a kind of sour gas colourless, hypertoxic, with rotten egg smell.All can in many industrial processes
Hydrogen sulfide gas is generated, Long Term Contact can seriously affect human health, cause the corrosion of equipment and pipeline.Meanwhile hydrogen sulfide is also
It can cause catalyst poisoning, be one of the main matter for causing atmosphere pollution, greenhouse effects and depletion of the ozone layer.Hydrogen sulfide is day
Most important harmful substance in right gas, it is necessary to just can be carried out transport and utilization by processing.By desulfurization process, hydrogen sulfide is taken off
It removes and is converted into sulphur.According to the difference of desulphurization mechanism, the method for removing hydrogen sulfide is divided into dry and wet two major classes.Dry method
Sulfur removal technology due to simple process, easy to operate, desulfurization precision is high and is widely used.Common dry-desulphurizer is active
Charcoal, iron oxide, zinc oxide, molecular sieve etc..But the technique desulfurization load is low, cannot operate continuously because needing replacing desulfurizing agent,
Desulfurizer therefor majority cannot regenerate or regeneration technology is complicated, to abandon after desulfurization saturation, not only result in environmental problem, can also
Increase desulphurization cost.Wet desulphurization generally absorbs hydrogen sulfide with absorbing liquid, is under the effect of the catalyst single by Oxidation of Hydrogen Sulfide
Matter sulphur, doctor solution is reusable, is easy to regenerate.The technique has operating flexibility big, and doctor solution is renewable, and hydrogen sulfide is turned
The advantages of turning to elemental sulfur.
Polyoxometallate is divided into isopolyacid and heteropoly acid two major classes.Heteropoly compound by heteropolyanion, anti-lotus sun from
Son and crystallization water composition.According to the structure of heteropolyanion and hetero atom and the ligancy for matching atom, heteropoly compound is divided into
Six kinds of basic structures such as Keggin, Dawson.Heteropoly compound has acid and oxidation-reduction quality, it is inorganic, organise
It is widely used in all kinds of catalysis reaction learned.Nearest decades, heteropoly acid and its heteropoly compound have been used as one kind is novel to urge
Agent is widely used in each field of industrial production.
The conventional regeneration method of polyoxometallate is made more in the polyoxometallic acid salting liquid after air to be passed through to desulfurization
The anion of oxometallate becomes high-valence state from lower valency to realize regeneration, but this method is not to be suitble to all mostly gold
Belong to the regeneration of oxygen hydrochlorate, such as the molybdovanaphosphoric acid of some Dawson structures will face some reproduction times using air regenesis
The problems such as length, low efficiency.In addition to air regenesis, polyoxometallate can also pass through O3、Cl2、NO2、Fe3+It is regenerated Deng oxidation,
But these methods be all individually present it is some it is inconvenient, easily cause secondary pollution, the problems such as regeneration efficiency is low.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention provides the electrochemical regeneration side after a kind of polyoxometallic acid saline solution desulfurization
Method.Desulfurization performance absolutely not reduces after regeneration, and also there is no reduce for desulfurization performance after being used repeatedly.This base again
On plinth, it can also realize and persistently be carried out while polyoxometallate removing hydrogen sulfide and polyoxometallate regenerate later, and
And production hydrogen.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization handles removing hydrogen sulfide using electrolysis method
Polyoxometallic acid saline solution to get.
Preferably, the condition of the electrolysis method are as follows: DC current flow intensity is 0.01-0.15A, electrolysis time 1.5h-
10h。
Preferably, the polyoxometallic acid saline solution of the removing hydrogen sulfide obtains by the following method: to multi-metal oxygen
It is passed through that hydrogen sulfide gas becomes navy blue to the polyoxometallic acid saline solution or desulfuration efficiency is reduced in acid salt aqueous solution
75% hereinafter, to obtain the final product.
Preferably, the general structure of the polyoxometallate are as follows:
(NH4)11[Ln(PMo11O39)2]·mH2O；Wherein Ln indicates the rare earth elements such as Ce, Sm, Dy, Gd；M indicates the crystallization water
Quantity.
Preferably, the polyoxometallate is (NH4)11[Ce(PMo11O39)2]·mH2O aqueous solution, (NH4)11[Sm
(PMo11O39)2]·mH2O aqueous solution, (NH4)11[Dy(PMo11O39)2]·mH2O aqueous solution or (NH4)11[Gd(PMo11O39)2]·
mH2O aqueous solution.
Preferably, the concentration of the polyoxometallic acid saline solution is 0.001-0.002mol/L.
The present invention also provides a kind of for removing the polyoxometallic acid saline solution of hydrogen sulfide, and polyoxometallate is molten
It is made in distilled water, the uniform clarification of desulfurizing agent appearance color.Polyoxometallate is realized in anode by the method for electrolysis
Regeneration, while cathode can produce hydrogen.
It is described for remove hydrogen sulfide polyoxometallate the preparation method is as follows:
(1)(NH4)11[Ce(PMo11O39)2]·mH2The preparation of O:
By 3.65g (2.00mmol) H3PMo12O40It is dissolved in 20ml water, uses Li2CO3Adjust pH to 4.3.By 0.434g
(1.00mmol)Ce(NO3)3·6H2O is directly added into above-mentioned solution, and solution is changed into dark-brown by yellow green at once, further plus
Enter Li2CO3The pH of solution is adjusted to 4.3 by solid.Then 2.94g (54.9mmol) NH is added4Cl stirs 1h, adds several drops
For ethyl alcohol when agitation of solutions, solution cannot be miscible at once, refrigerates at 5 DEG C several days, there is brown crystal generation, and ethyl alcohol is used in filtering
After flushing, it is air-dried.
(2)(NH4)11[Sm(PMo11O39)2]·mH2The preparation of O:
Preparation method and (NH4)11[Ce(PMo11O39)2]·mH2O is similar, with 0.444g (1.00mmol) Sm (NO3)3·
6H2O replaces Ce (NO3)3·6H2Ethyl alcohol is changed to that a few drop acetonitriles are added, refrigerates at 5 DEG C several days by O, there is the production of yellow dish type crystal
Raw, filtering after being rinsed with ethyl alcohol, is air-dried.
(3)(NH4)11[Dy(PMo11O39)2]·mH2The preparation of O:
Preparation method and (NH4)11[Ce(PMo11O39)2]·mH2O is similar, with 0.457g (1.00mmol) Dy (NO3)3·
6H2O replaces Ce (NO3)3·6H2O is refrigerated several days at 5 DEG C, there is a generation of yellow flat crystal, filtering, after being rinsed with ethyl alcohol, air
It is dry.
(4)(NH4)11[Gd(PMo11O39)2]·mH2The preparation of O:
Preparation method and (NH4)11[Ce(PMo11O39)2]·mH2O is similar, with 0.451g (1.00mmol) Gd (NO3)3·
6H2O replaces Ce (NO3)3·6H2O is refrigerated several days at 5 DEG C, there is a generation of yellow flat crystal, filtering, after being rinsed with ethyl alcohol, air
It is dry.
0.1887-0.3775g polyoxometallate is dissolved in 50ml distilled water, can be used to hydrogen sulfide stripping experiment.
For removing the electrochemical regeneration of the polyoxometallic acid saline solution of hydrogen sulfide
A pair of of inert electrode is installed in the polyoxometallic acid saline solution for absorbing a period of time hydrogen sulfide, by two conducting wires
It is separately connected the cathode and anode of anodic-cathodic and DC power supply, electrolysis a period of time can realize polyoxometallic acid in anode
The regeneration of salt, and hydrogen can be produced in cathode.
Polyoxometallic acid saline solution of the present invention can be used for natural gas, industrial waste gas as oxidation desulfurizing agent
The removing of middle hydrogen sulfide.The specific method is as follows: the polyoxometallic acid saline solution of a certain concentration and volume is placed in desulphurization reaction
In device, reaction temperature is controlled by thermostat water bath, and the sulfide hydrogen simulation of a certain concentration and flow is passed through from the bottom of reactor
Gas, after polyoxometallic acid saline solution removes hydrogen sulfide, tail gas enters hydrogen sulfide analyzer by reactor upper end, to survey
Determine the content of hydrogen sulfide in tail gas.Tail gas empties after being absorbed by sodium hydroxide solution.After absorption after a period of time, more metals
Oxygen hydrochlorate becomes navy blue, and the content of hydrogen sulfide gradually increases in tail gas, and the numerical value that hydrogen sulfide analyzer is shown increases to centainly
Stop ventilation after value.Inert electrode is disposed in polyoxometallic acid salting liquid after desulfurization, is passed through direct current, electrolysis a period of time
Afterwards, the color of polyoxometallic acid salting liquid becomes faint yellow from navy blue, that is, indicates regenerated completion.In polyoxometallate
While solution regenerates, hydrogen can be generated in cathode.
The concentration of the polyoxometallic acid saline solution is 0.001-0.002mol/L, volume 50ml-100ml.
The desulfurization reactor is the glass reactor that bottom has sand core.
The sulfide hydrogen simulation gas carrier is N2, flow 400mL/min, concentration of hydrogen sulfide 1600-
2900mg/m3。
The reaction temperature is 25-80 DEG C.
The DC current flow intensity is 0.01-0.15A.
The electrolysis time is 1.5h-10h.
Desulfurization principle of the invention are as follows: in aqueous solution, the anion of polyoxometallate and the H entered in solution2S and
The HS dissociateed-Redox reaction occurs, molybdenum atom obtains electronics and is reduced, H2S and HS-It is oxidized to elemental sulfur.
Regeneration principle of the invention are as follows: the polyoxometallate after desulfurization is in reduction-state, installs additional in the solution a pair of lazy
Property electrode, the cathode and anode of anodic-cathodic and DC power supply are separately connected by two conducting wires, is passed through direct current, multi-metal oxygen
The molybdenum atom of hydrochlorate loses electronics in anode and is oxidized, and hydrogen ion obtains electronics and become hydrogen to be reduced in cathode.In external circuit
In, the electronics that the molybdenum atom around anode loses enters positive pole through conducting wire by anode, is passed through by the electronics that power cathode provides
The hydrogen ion around cathode is passed to after conducting wire arrival cathode.In interior circuit ie in solution, hydrogen ion is to movable cathode, more metals
The anion of the oxygen hydrochlorate Ghandler motion that faces south is dynamic.Interior external circuit forms a complete closed circuit, to realize polyoxometallate
Regeneration and produce hydrogen purpose.
Beneficial effects of the present invention
(1) present invention is prepared for a kind of novel polyoxometallate, for removing the hydrogen sulfide in gas.It is this kind of mostly golden
It is simple to belong to oxygen hydrochlorate preparation method, oxidation susceptibility is good and stablizes, and desulfuration efficiency is high, will not cause secondary dirt to pipeline and environment
Dye, and elemental sulfur can be obtained.Electrochemical regeneration is simple and easy, pollution-free, while realizing polyoxometallate regeneration, also
Hydrogen can be produced.Desulfurization performance absolutely not reduces after regeneration, and desulfurization performance is not yet after being used repeatedly
It reduces.On this basis, while can also realizing that polyoxometallate removing hydrogen sulfide and polyoxometallate regenerate later
It is lasting to carry out, and produce hydrogen.The present invention provides a kind of novel polyoxometallates and one for being used to remove hydrogen sulfide
Kind electrochemical regeneration method can have certain economic benefit, simple process, low energy consumption, easily with Recovered sulphur and production hydrogen
In industrialization promotion.
(2) preparation method of the present invention is simple, regeneration efficiency is high, practical, easy to spread.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
The preparation method of 1 polyoxometallic acid saline solution of embodiment
(1) 0.001mol/L (NH4)11[Ce(PMo11O39)2]·mH2The preparation of O aqueous solution
Weigh (NH made from 0.1880g4)11[Ce(PMo11O39)2]·mH2O is dissolved in 50ml distilled water.
(2) 0.001mol/L (NH4)11[Sm(PMo11O39)2]·mH2The preparation of O aqueous solution
Weigh (NH made from 0.1885g4)11[Sm(PMo11O39)2]·mH2O is dissolved in 50ml distilled water.
(3) 0.001mol/L (NH4)11[Dy(PMo11O39)2]·mH2The preparation of O aqueous solution
Weigh (NH made from 0.1891g4)11[Dy(PMo11O39)2]·mH2O is dissolved in 50ml distilled water.
(4) 0.001mol/L (NH4)11[Gd(PMo11O39)2]·mH2The preparation of O aqueous solution
Weigh (NH made from 0.1888g4)11[Gd(PMo11O39)2]·mH2O is dissolved in 50ml distilled water.
(5) 0.002mol/L (NH4)11[Sm(PMo11O39)2]·mH2The preparation of O aqueous solution
Weigh (NH made from 0.3775g4)11[Sm(PMo11O39)2]·mH2O is dissolved in 50ml distilled water.
Embodiment 2 simulates H 2 S-containing gas
By 50ml 0.001mol/L (NH4)11[Sm(PMo11O39)2]·mH2O aqueous solution pours into desulfurization reactor, reaction
Temperature is 25 DEG C.Be passed through flow be 400ml/min, concentration 1600mg/m3H 2 S-containing gas, hydrogen sulfide contains in tail gas
Amount is measured by hydrogen sulfide analyzer.Tail gas is finally handled by sodium hydroxide solution absorption.Hydrogen sulfide stripping efficiency is kept in 70min
86% or more.
Embodiment 3 simulates H 2 S-containing gas
By 50ml 0.002mol/L (NH4)11[Sm(PMo11O39)2]·mH2O aqueous solution pours into desulfurization reactor, reaction
Temperature is 25 DEG C.Be passed through flow be 400ml/min, concentration 1600mg/m3H 2 S-containing gas, hydrogen sulfide contains in tail gas
Amount is measured by hydrogen sulfide analyzer.Tail gas is finally handled by sodium hydroxide solution absorption.Hydrogen sulfide stripping efficiency is protected in 360min
It holds 88% or more.
Embodiment 4 simulates H 2 S-containing gas
By 50ml 0.002mol/L (NH4)11[Sm(PMo11O39)2]·mH2O aqueous solution pours into desulfurization reactor, reaction
Temperature is 25 DEG C.Be passed through flow be 400ml/min, concentration 2900mg/m3H 2 S-containing gas, hydrogen sulfide contains in tail gas
Amount is measured by hydrogen sulfide analyzer.Tail gas is finally handled by sodium hydroxide solution absorption.Hydrogen sulfide stripping efficiency is protected in 240min
It holds 84% or more.
Electrochemical regeneration processing after 5 polyoxometallic acid saline solution desulfurization of embodiment
50ml 0.002mol/L(NH4)11[Sm(PMo11O39)2]·mH2After O aqueous solution desulfurization 270min, desulfuration efficiency drop
As low as 75% hereinafter, more metal hydrochloride solution colours become navy blue, inert electrode is installed additional in the solution, is led by two
Line is separately connected the cathode and anode of anodic-cathodic and DC power supply, is passed through the direct current of 0.15A, after being electrolysed 6h, solution colour
Become faint yellow from navy blue, that is, indicates that regeneration is completed.
The hydrogen sulfide absorption of polyoxometallic acid saline solution after the regeneration of embodiment 6
By the 50ml 0.002mol/L (NH after regeneration4)11[Sm(PMo11O39)2]·mH2O aqueous solution pours into desulphurization reaction
In device, reaction temperature is 25 DEG C.Be passed through flow be 400ml/min, concentration 2900mg/m3H 2 S-containing gas, in tail gas
The content of hydrogen sulfide is measured by hydrogen sulfide analyzer.Tail gas is finally handled by sodium hydroxide solution absorption.Hydrogen sulfide in 300min
Removal efficiency is maintained at 85% or more.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (1)
1. a kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization, which is characterized in that handled using electrolysis method
Remove hydrogen sulfide polyoxometallic acid saline solution to get；
The electrolysis method is direct current solution；
The DC current flow intensity of the direct current solution is 0.01-0.15A；
The electrolysis method processing time is 1.5h-10h；
The polyoxometallic acid saline solution of the removing hydrogen sulfide obtains by the following method: into polyoxometallic acid saline solution
It is passed through that hydrogen sulfide gas to the polyoxometallic acid saline solution becomes navy blue or desulfuration efficiency is reduced to 75% hereinafter, i.e.
?；
The general structure of the polyoxometallate are as follows:
(NH4)11[Ln(PMo11O39)2]·mH2O；Wherein Ln indicates rare earth element ce, Sm, Dy or Gd；The number of the m expression crystallization water
Amount；
The concentration of the polyoxometallic acid saline solution is 0.001-0.002mol/L.
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| CN103801175B (en) * | 2012-11-14 | 2015-11-18 | 中国石油天然气股份有限公司 | A kind of polyoxometallate and Synthesis and applications thereof |
| CN103846003B (en) * | 2012-11-30 | 2015-10-28 | 中国石油天然气股份有限公司 | A kind of method removing hydrogen sulfide gas |
| CN103894058B (en) * | 2012-12-27 | 2016-06-08 | 中国石油天然气股份有限公司 | A kind of method utilizing polyoxometallate elimination hydrogen sulfide gas |
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