CN103801175B - A kind of polyoxometallate and Synthesis and applications thereof - Google Patents
A kind of polyoxometallate and Synthesis and applications thereof Download PDFInfo
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- CN103801175B CN103801175B CN201210455613.5A CN201210455613A CN103801175B CN 103801175 B CN103801175 B CN 103801175B CN 201210455613 A CN201210455613 A CN 201210455613A CN 103801175 B CN103801175 B CN 103801175B
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- hydrogen sulfide
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Abstract
The present invention relates to a kind of polyoxometallate and Synthesis and applications thereof; By 0.5-2.0gMoO
3or GdO
3be dissolved in 10-20ml distilled water; 1.0-2.0gKOH is dissolved in the solution that 500-1000ml distilled water is configured to add in above-mentioned solution, and drips HClO
4mixed liquor acidity is made to remain on pH=4.0-5.0; Get 1.0-2.0gEu (NO
3)
36H
2o is dissolved in 10-20ml distilled water, under room temperature, stirring, slowly adds in aforementioned mixed liquor; Meanwhile, in mixed liquor, HClO is dripped
4keep pH=2.0-4.0; At ambient temperature, keep stirring 24-72h, filter, wash, the dry 12-48h of air at room temperature, obtains water-fast yellow powder; This desulfurizing agent oxidation susceptibility is high, and good stability does not produce pollution to pipeline and environment, and depriving hydrogen sulphide efficiency is high, can obtain elemental sulfur.
Description
Technical field:
The present invention relates to a kind of polyoxometallate and Synthesis and applications thereof.
Background technology:
Hydrogen sulfide is the gas that a kind of height stimulates, and have strong rotten egg smell, in gas, the existence of hydrogen sulfide not only can cause equipment and corrosion of piping, catalyst poisoning, and can serious threat personal safety.To concentration of hydrogen sulfide in ambient air, workshop air and industrial waste gas, there are strict requirements in China: in the ambient air of residential block, the maximum concentration of hydrogen sulfide must not more than 0.01mg/m
3; Shopwork place Air Hydrogen Sulfide maximum concentration must not more than 10mg/m
3; In town gas, concentration of hydrogen sulfide must not more than 20mg/m
3; In oil product refinery off gas, concentration of hydrogen sulfide requires that purification is to 10-20mg/m
3.
Removing for hydrogen sulfide, reported processing method is a lot, and these methods are mainly divided into two large classes: dry-desulphurizer sulfur removal technology and wet desulphurization agent sulfur removal technology.Dry-desulphurizer sulfur removal technology is because its technique is simple, be easy to operation, desulfurization precision is higher, and relative energy consumption is low and be widely used.Conventional dry-desulphurizer mainly contains: iron oxide, zinc oxide, normal activated carbon etc.This technique is generally usually used in removal or other the meticulous desulfurization of hydrogen sulfide in industrial tail gas, the desulfurizing agent great majority adopted can not regenerate or regeneration technology complexity, the removing of a large amount of hydrogen sulfide gas in improper natural gas, and cannot reclaim or recycle sulphur and form the wasting of resources.Wet desulphurization agent sulfur removal technology, general employing absorbing liquid absorbing hydrogen sulphide, under catalyst action, Oxidation of Hydrogen Sulfide is become sulphur, catalyst continues after can regenerating in air or oxygen to use.This technological reaction catalyst system and catalyzing is liquid-phase system, and efficiently, renewable, there is advantage hydrogen sulfide being converted into elemental sulfur simultaneously.
At present, wet desulphurization agent sulfur removal technology also has problems in stability of solution, control side reaction and the oxidant feature of environmental protection etc.Develop a kind of good stability, form the research emphasis that relatively simple and that environmental protection desulfuration efficiency is high oxidant becomes this technique.
Summary of the invention:
The object of this invention is to provide a kind of polyoxometallate as wet desulphurization agent deep removal hydrogen sulfide, its good stability and desulfuration efficiency is high.
Polyoxometallate of the present invention, structural formula: [H
24r
2mo
8o
39] nH
2o (R=Eu, Gd).
The preparation method of above-mentioned polyoxometallate, comprises the following steps:
By 0.5-2.0gMoO
3be dissolved in 10-20ml distilled water; 1.0-2.0gKOH is dissolved in the solution that 500-1000ml distilled water is configured to add in above-mentioned solution, and drips HClO
4mixed liquor acidity is made to remain on pH=4.0-5.0; Get 1.0-2.0gEu (NO
3)
36H
2o or Gd (NO
3)
36H
2o is dissolved in 10-20ml distilled water, under room temperature, stirring, slowly adds in aforementioned mixed liquor; Meanwhile, in mixed liquor, HClO is dripped
4keep pH=2.0-4.0; At ambient temperature, keep stirring 24-72h, filter, wash, the dry 12-48h of air at room temperature, obtains water-fast yellow powder.
Utilize polyoxometallate as wet desulphurization agent, be dissolved in distilled water, under uniform temperature and condition of normal pressure, the mist containing hydrogen sulfide is passed into above-mentioned solution, reach the object removing hydrogen sulfide;
By polyoxometallate 0.001-0.010g, be dissolved in 25-150ml distilled water;
Reaction temperature 15-50 DEG C;
Mist composition is by 1%H
2s Standard Gases flow is 10-100ml/min and O
2gas flow 10-100ml/min, mist entrance flow velocity 20-150ml/min.
The chemical transmitter course of reaction of this polyoxometallate absorbing hydrogen sulphide, comprises following five steps:
(1) polyoxometallate is prepared into the aqueous solution;
(2) hydrogen sulfide containing gas is passed into the above-mentioned aqueous solution, make hydrogen sulfide from gas phase main diffusion to gas-liquid interface;
(3) dissolve at interface hydrogen sulfide and be dissociated into HS
-, spread to liquid phase by interface simultaneously;
(4) HS
-, excessive H
2s and polyoxometallate generation redox reaction, generate elemental sulfur;
(5) along with the carrying out of redox reaction, dissociation equilibrium is destroyed, more H
2s spreads to liquid phase, participates in redox reaction, thus achieves the object removing hydrogen sulfide in gas phase.
Involved H 2 S-containing gas, comprises natural gas, industrial tail gas and industrial waste gas etc.
The method of a kind of deep removal hydrogen sulfide that the present invention relates to, with the polyoxometallate prepared by the present invention for oxidant, configure certain density polyoxometallic acid salting liquid and be placed in desulfurization reactor, at 15 DEG C-50 DEG C, the hydrogen sulfide containing mist of 20-150ml/min is passed into from reactor lower end, polyoxometallic acid salting liquid is passed through with the form of minute bubbles after the sand core funnel distribution of gas through reactor lower end, divide from reactor upper end and get tail gas and enter hydrogen sulfide analyzer and detect, detect once every 10min.Preparation method is simple for this method desulfurizer therefor, high and the good stability of oxidation susceptibility, environmental protection does not all produce pollution to pipeline and environment, whole process depriving hydrogen sulphide efficiency is high, and can elemental sulfur be obtained, there is certain economic benefit, the simple small investment of process equipment, be easy to industrialization promotion, meet national cleaner production and circular economy industrial policy.
The invention has the beneficial effects as follows: the present invention has prepared polyoxometallate, compared with other oxidants, desulfuration efficiency improves, reaction time shortens, process costs obviously reduces, and overcome the perishable pipeline of existing oxidant and form secondary pollution problems, provide a kind of hydrogen sulfide stripping method of efficient, environmental protection, the double goal reducing hydrogen sulfide content and cleaner production in the gases such as natural gas can be realized.
Detailed description of the invention:
Embodiment 1: the synthesis of wet desulphurization agent
By 1.93gMoO
3be dissolved in 10ml distilled water.1.5gKOH is dissolved in the solution that 1000ml distilled water is configured to add in above-mentioned solution, and drips HClO
4mixed liquor acidity is made to remain on pH=4.5.Get 1.49gEu (NO
3)
36H
2o is dissolved in 20ml distilled water, under room temperature, stirring, slowly adds in aforementioned mixed liquor.Meanwhile, in mixed liquor, HClO is dripped
4keep pH=3.0.At ambient temperature, keep stirring 48h, filter, wash, the dry 48h of air at room temperature, obtains water-fast yellow powder i.e. [H
24eu
2mo
8o
39] 6H
2o.
Embodiment 2: simulation H 2 S-containing gas
By 0.005gH
24eu
2mo
8o
39be dissolved in 50ml distilled water to pour in hydrogen sulfide desulfurization reactor.Setting reaction temperature 50 DEG C, setting 1%H
2s Standard Gases flow is 30ml/min and O
2gas flow 50ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reactor, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector to detect.Experimental result shows, the reaction time, in tail gas, hydrogen sulfide content was 0 within 2.5h.After 2.5h, in tail gas, hydrogen sulfide content increases gradually.
Embodiment 3: simulation H 2 S-containing gas
By 0.002gH
24gd
2mo
8o
39be dissolved in 25ml distilled water to pour in hydrogen sulfide desulfurization reactor.Setting reaction temperature 35 DEG C, setting 1%H
2s Standard Gases flow is 10ml/min and O
2gas flow 70ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reactor, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector to detect.Experimental result shows, the reaction time, in tail gas, hydrogen sulfide content was 0 within 8.5h.After 8.5h, in tail gas, hydrogen sulfide content increases gradually.
Embodiment 4: simulation H 2 S-containing gas
By 0.010gH
24eu
2mo
8o
39be dissolved in 70ml distilled water to pour in hydrogen sulfide desulfurization reactor.Setting reaction temperature 15 DEG C, setting 1%H
2s Standard Gases flow is 80ml/min and O
2gas flow 10ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reactor, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector to detect.Experimental result shows, the reaction time, in tail gas, hydrogen sulfide content was 0 within 3h.After 3h, in tail gas, hydrogen sulfide content increases gradually.
Embodiment 5: simulation H 2 S-containing gas
By 0.001gH
24gd
2mo
8o
39be dissolved in 150ml distilled water to pour in hydrogen sulfide desulfurization reactor.Setting reaction temperature 45 DEG C, setting 1%H
2s Standard Gases flow is 10ml/min and O
2gas flow 10ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reactor, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector to detect.Experimental result shows, the reaction time, in tail gas, hydrogen sulfide content was 0 within 4h.After 4h, in tail gas, hydrogen sulfide content increases gradually.
Embodiment 6: simulation H 2 S-containing gas
By 0.025gH
24gd
2mo
8o
39be dissolved in 80ml distilled water to pour in hydrogen sulfide desulfurization reactor.Setting reaction temperature 20 DEG C, setting 1%H
2s Standard Gases flow is 50ml/min and O
2gas flow 100ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reactor, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector to detect.Experimental result shows, the reaction time, in tail gas, hydrogen sulfide content was 0 within 3h.After 3h, in tail gas, hydrogen sulfide content increases gradually.
Embodiment 7: simulation H 2 S-containing gas
By 0.015gH
24eu
2mo
8o
39be dissolved in 100ml distilled water to pour in hydrogen sulfide desulfurization reactor.Setting reaction temperature 25 DEG C, setting 1%H
2s Standard Gases flow is 100ml/min and O
2gas flow 40ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reactor, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector to detect.Experimental result shows, the reaction time, in tail gas, hydrogen sulfide content was 0 within 3h.After 3h, in tail gas, hydrogen sulfide content increases gradually.
Claims (1)
1. an application for polyoxometallate, is characterized in that: utilize general structure to be [H
24r
2mo
8o
39] nH
2the polyoxometallate of O, R=Eu or Gd, as wet desulphurization agent, is dissolved in distilled water, under uniform temperature and condition of normal pressure, the mist containing hydrogen sulfide is passed into above-mentioned solution, reaches the object removing hydrogen sulfide;
By described polyoxometallate 0.001-0.010g, be dissolved in 25-150ml distilled water;
Reaction temperature 15-50 DEG C;
Mist composition is by 1%H
2s Standard Gases flow is 10-100ml/min and O
2gas flow 10-100ml/min, mist entrance flow velocity 20-150ml/min;
The synthetic method of described polyoxometallate: by 0.5-2.0gMoO
3be dissolved in 10-20ml distilled water; 1.0-2.0gKOH is dissolved in the solution that 500-1000ml distilled water is configured to add in above-mentioned solution, and drips HClO
4mixed liquor acidity is made to remain on pH=4.0-5.0; Get 1.0-2.0gEu (NO
3)
36H
2o or Gd (NO
3)
36H
2o is dissolved in 10-20ml distilled water, under room temperature, stirring, slowly adds in aforementioned mixed liquor; Meanwhile, in mixed liquor, HClO is dripped
4keep pH=2.0-4.0; At ambient temperature, keep stirring 24-72h, filter, wash, the dry 12-48h of air at room temperature, obtains water-fast yellow powder.
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|---|---|---|---|
| CN201210455613.5A CN103801175B (en) | 2012-11-14 | 2012-11-14 | A kind of polyoxometallate and Synthesis and applications thereof |
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|---|---|---|---|
| CN201210455613.5A CN103801175B (en) | 2012-11-14 | 2012-11-14 | A kind of polyoxometallate and Synthesis and applications thereof |
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|---|---|
| CN103801175A CN103801175A (en) | 2014-05-21 |
| CN103801175B true CN103801175B (en) | 2015-11-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688658B (en) * | 2016-01-22 | 2017-12-22 | 山东大学 | It is a kind of for the polyoxometallate of hydrogen sulfide stripping or the aqueous solution of monomer |
| CN106582278B (en) * | 2016-12-29 | 2022-10-11 | 山东大学 | Preparation method of heteropoly acid modified nano-ring composite material for removing NOx |
| CN106669420B (en) * | 2017-02-17 | 2019-08-16 | 山东大学 | A kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization |
| CN107265722B (en) * | 2017-08-08 | 2020-09-01 | 哈尔滨工业大学 | Method for realizing desulfurization of sodium sulfide-containing wastewater by using polyacid ionic liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283379A (en) * | 1979-06-20 | 1981-08-11 | Union Oil Company Of California | Method for removing hydrogen sulfide from gas streams |
| CN101918324A (en) * | 2007-10-31 | 2010-12-15 | 莫利康普矿物有限责任公司 | Aggregate composition for treating a contaminanted fluid |
-
2012
- 2012-11-14 CN CN201210455613.5A patent/CN103801175B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283379A (en) * | 1979-06-20 | 1981-08-11 | Union Oil Company Of California | Method for removing hydrogen sulfide from gas streams |
| CN101918324A (en) * | 2007-10-31 | 2010-12-15 | 莫利康普矿物有限责任公司 | Aggregate composition for treating a contaminanted fluid |
Non-Patent Citations (1)
| Title |
|---|
| Hydrothermal Assembly of a Novel Three-Dimensional Framework Formed by[GdMo12O42]9- Anions and Nine Coordinated GdIII Cations;Chuan-De Wu, et al.;《Journal of the American chemical》;20020320;第3836-3837页 * |
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