CN103894058B - A kind of method utilizing polyoxometallate elimination hydrogen sulfide gas - Google Patents
A kind of method utilizing polyoxometallate elimination hydrogen sulfide gas Download PDFInfo
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Abstract
The present invention relates to a kind of method utilizing polyoxometallate elimination hydrogen sulfide gas; By polyoxometallate 0.001-0.010g, being dissolved in 15-100ml distilled water and be placed in desulfurization reactor, at 10-60 DEG C of temperature and condition of normal pressure, the mixing gas containing hydrogen sulfide passes into elimination hydrogen sulfide in solution, polyoxometallate general structure is H22[MoV xMoVI y-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��mH2O is wherein: V, VI represent Mo atom quantivalence+5 and+6 respectively; X, y represent Mo respectivelyVAnd Mo��Quantity; The method desulfurizer therefor preparation method is simple, and oxidation susceptibility is high and good stability, and pipeline and environment are not all produced to pollute by environmental protection, and whole process depriving hydrogen sulphide efficiency is high, and can obtain elemental sulfur, the simple small investment of process equipment.
Description
Technical field:
The present invention relates to a kind of method utilizing double; two carbon symmetrical ellipse type lanthanum molybdenum multi-metal oxygen hydrochlorate elimination hydrogen sulfide gas.
Background technology:
Hydrogen sulfide is the gas that a kind of height stimulates, and has strong rotten egg abnormal smells from the patient, and 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 exceed 0.01mg/m3; Shopwork place Air Hydrogen Sulfide maximum concentration must not exceed 10mg/m3; In town gas, concentration of hydrogen sulfide must not exceed 20mg/m3; In oil product refinery off gas, concentration of hydrogen sulfide requires to purify to 10-20mg/m3��
For the elimination of hydrogen sulfide, reported processing method is a lot, and these methods are broadly divided into two big classes: dry-desulphurizer sulfur removal technology and wet desulphurization agent sulfur removal technology. Dry-desulphurizer sulfur removal technology is owing to its technique is simple, easily operated, desulfurization precision is higher, and relative energy consumption is low and is widely used. Conventional dry-desulphurizer mainly has: ferrum oxide, zinc oxide, normal activated carbon etc. What this technique was generally usually used in industrial tail gas hydrogen sulfide remove or other fine desulfurization, the desulfurizing agent great majority adopted can not regenerate or regeneration technology is complicated, the elimination of a large amount of hydrogen sulfide gas in improper natural gas, and cannot reclaim or recycle the sulfur formation wasting of resources. Wet desulphurization agent sulfur removal technology, is generally adopted absorption liquid and absorbs hydrogen sulfide, Oxidation of Hydrogen Sulfide becomes sulfur under catalyst action, and catalyst can be continuing with after regenerating in air or oxygen. This technological reaction catalyst system and catalyzing is liquid-phase system, and efficiently, renewable, there is the advantage that hydrogen sulfide is converted into elemental sulfur simultaneously.
At present, wet desulphurization agent sulfur removal technology there is a problem in stability of solution, control side reaction and the oxidant feature of environmental protection etc.Develop a kind of good stability, form relatively easy and that environmental protection desulfuration efficiency is high oxidant and become the research emphasis of this technique.
Summary of the invention:
It is an object of the invention to provide a kind of method utilizing polyoxometallate elimination hydrogen sulfide gas, adopt polyoxometallate as wet desulphurization agent, its good stability and desulfuration efficiency are high.
The principle of the invention:
Polyoxometallate absorbs the chemical transmitter course of reaction of hydrogen sulfide, including following five steps:
(1) polyoxometallate is prepared into aqueous solution;
(2) hydrogen sulfide containing gas is passed into 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, being spread to liquid phase by interface simultaneously;
(4) HS-, excessive H2S and polyoxometallate generation redox reaction, generate elemental sulfur;
(5) along with the carrying out of redox reaction, dissociation equilibrium is destroyed, more H2S spreads to liquid phase, participates in redox reaction, it is achieved thereby that the purpose of elimination hydrogen sulfide in gas phase.
The wet desulphurization agent of a kind of deep removal hydrogen sulfide of offer of the present invention, this desulfurizing agent is mainly polyoxometallate, including: H22[MoV xMo�� y-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��mH2O(is wherein: V, VI represent Mo atom quantivalence+5 and+6 respectively; X, y represent Mo respectivelyVAnd Mo��Quantity).
The preparation method of polyoxometallate desulfurizing agent of the present invention, comprises the following steps:
By 1-3g(0.8-2.4mmol) solid [NH4]6[Mo7O24]��4H2O is dissolved in 20-100ml distilled water, is subsequently adding 20-100ml(270-1348mmol) C2H5CO2H, keeps temperature 10-15 DEG C, and dropping ammonia is by above-mentioned solution control ph at 3.9-4.1, and keep nitrogen protection to utilize ultraviolet radiation above-mentioned solution that 500w ultrahigh pressure mercury lamp produces 5-15 days, by being filtrated to get the navy blue molybdenum intermediate of illumination reaction generation;
Navy blue for 0.1-1.0g molybdenum intermediate is dissolved in 10-100ml distilled water, adds 0.01-0.1g(0.01-0.1mmol) LaCl3��7H2O. Stirring is until being completely dissolved; Being kept 3-10 days by this solution when 0-10 DEG C, by filtering, cold water washs, air drying prepares blue H22[MoV xMoVI y-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��mH2O��
Wherein involved H 2 S-containing gas, including natural gas, industrial tail gas and industrial waste gas etc.
The invention has the beneficial effects as follows: the present invention is prepared for the polyoxometallate that a class is novel, it can be used as desulfurizing agent, utilize hydrogen sulfide to liquid phase diffusion and the oxidized mechanism of action, be finally reached the purpose of elimination hydrogen sulfide. Compared with other oxidants, desulfuration efficiency improves, response time shortens, process costs substantially reduces, and overcome the perishable pipeline formation secondary pollution problems of existing oxidant, provide a kind of hydrogen sulfide stripping method of novel, efficient, environmental protection, it may be achieved reduce the double goal that in the gases such as natural gas, hydrogen sulfide content produces with cleaning.
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, by 0.001-0.010g polyoxometallate, it is dissolved in 15-100ml distilled water, it is placed in desulfurization reactor, at 10 DEG C 60 DEG C, the hydrogen sulfide containing mixing gas of 20-180ml/min is passed into from reactor lower end, with the form of minute bubbles by polyoxometallic acid saline solution after the gas sand core funnel distribution through reactor lower end, divide from reactor upper end take tail gas enter hydrogen sulfide analyzer detect, every 10min detect once.This method desulfurizer therefor preparation method is simple, oxidation susceptibility height and good stability, pipeline and environment are not all produced to pollute by environmental protection, whole process depriving hydrogen sulphide efficiency is high, and elemental sulfur can be obtained, there is certain economic benefit, the simple small investment of process equipment, it is prone to industrialization promotion, meets country's cleaning and produce and circular economy industrial policy.
Detailed description of the invention:
Embodiment 1: the synthesis of wet desulphurization agent
By 1.73g(1.4mmol) solid [NH4]6[Mo7O24]��4H2O is dissolved in 35ml distilled water, is subsequently adding 35ml(472mmol) C2H5CO2H, keeps temperature 10-15 degree Celsius, dropping ammonia by above-mentioned solution control ph at 3.9-4.1, keep nitrogen protection the to utilize above-mentioned solution of ultraviolet radiation that 500w ultrahigh pressure mercury lamp produces 10 days. By being filtrated to get the navy blue molybdenum intermediate that illumination reaction produces.
Navy blue for 0.1g molybdenum intermediate is dissolved in 20ml distilled water, adds 0.03g(0,08mmol) LaCl3��7H2O. Stirring is until being completely dissolved. Being kept 7 days by this solution when 4 degrees Celsius, by filtering, cold water washs, air drying prepares blue H22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O��
Embodiment 2: simulation H 2 S-containing gas
By 0.003gH22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O is dissolved in 35ml distilled water and pours in hydrogen sulfide desulfurization reactor. Set reaction temperature 60 DEG C, set 1%H2S Standard Gases flow is 20ml/min and O2Gas flow 40ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reacted device, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector detection. Test result indicate that, the response time, in tail gas, hydrogen sulfide content was 0 within 2.5h. After 2.5h, in tail gas, hydrogen sulfide content is gradually increased.
Embodiment 3: simulation H 2 S-containing gas
By 0.005gH22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O is dissolved in 50ml distilled water and pours in hydrogen sulfide desulfurization reactor. Set reaction temperature 35 DEG C, set 1%H2S Standard Gases flow is 30ml/min and O2Gas flow 50ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reacted device, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector detection. Test result indicate that, the response time, in tail gas, hydrogen sulfide content was 0 within 4.5h. After 4.5h, in tail gas, hydrogen sulfide content is gradually increased.
Embodiment 4: simulation H 2 S-containing gas
By 0.001gH22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O is dissolved in 15ml distilled water and pours in hydrogen sulfide desulfurization reactor. Set reaction temperature 15 DEG C, set 1%H2S Standard Gases flow is 60ml/min and O2Gas flow 15ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reacted device, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector detection. Test result indicate that, the response time, in tail gas, hydrogen sulfide content was 0 within 1h. After 1h, in tail gas, hydrogen sulfide content is gradually increased.
Embodiment 5: simulation H 2 S-containing gas
By 0.010gH22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O is dissolved in 70ml distilled water and pours in hydrogen sulfide desulfurization reactor. Set reaction temperature 45 DEG C, set 1%H2S Standard Gases flow is 80ml/min and O2Gas flow 35ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reacted device, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector detection. Test result indicate that, the response time, in tail gas, hydrogen sulfide content was 0 within 6.5h. After 6.5h, in tail gas, hydrogen sulfide content is gradually increased.
Embodiment 6: simulation H 2 S-containing gas
By 0.020gH22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O is dissolved in 20ml distilled water and pours in hydrogen sulfide desulfurization reactor.Set reaction temperature 25 DEG C, set 1%H2S Standard Gases flow is 100ml/min and O2Gas flow 10ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reacted device, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector detection. Test result indicate that, the response time, in tail gas, hydrogen sulfide content was 0 within 8.5h. After 8.5h, in tail gas, hydrogen sulfide content is gradually increased.
Embodiment 7: simulation H 2 S-containing gas
By 0.015gH22[MoV 20MoVI 76-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��54.5H2O is dissolved in 100ml distilled water and pours in hydrogen sulfide desulfurization reactor. Set reaction temperature 10 DEG C, set 1%H2S Standard Gases flow is 180ml/min and O2Gas flow 45ml/min, imports hydrogen sulfide desulfurization reactor from bottom after gas is stable, and after reacted device, in tail gas, hydrogen sulfide hydrogen content adopts hydrogen sulfide detector detection. Test result indicate that, the response time, in tail gas, hydrogen sulfide content was within 5h. After 5h, in tail gas, hydrogen sulfide content is gradually increased.
Claims (2)
1. the method utilizing polyoxometallate elimination hydrogen sulfide gas, it is characterized in that: by polyoxometallate 0.001-0.010g, being dissolved in 15-100ml distilled water is placed in desulfurization reactor, at 10-60 DEG C of temperature and condition of normal pressure, the mixing gas containing hydrogen sulfide is passed into elimination hydrogen sulfide in solution;
Polyoxometallate general structure is
H22[MoV xMoVI y-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��mH2O; Wherein: V, VI represent Mo atom quantivalence+5 and+6 respectively; X, y represent Mo respectivelyVAnd Mo��Quantity;
Its synthetic method:
By 1-3g solid [NH4]6[Mo7O24]��4H2O is dissolved in 20-100ml distilled water, is subsequently adding 20-100mlC2H5CO2H, keeps temperature 10-15 DEG C, and dropping ammonia is by above-mentioned solution control ph at 3.9-4.1, and keep nitrogen protection to utilize ultraviolet radiation above-mentioned solution that 500w ultrahigh pressure mercury lamp produces 5-15 days, by being filtrated to get the navy blue molybdenum intermediate of illumination reaction generation;
Navy blue for 0.1-1.0g molybdenum intermediate is dissolved in 10-100ml distilled water, adds 0.01-0.1gLaCl3��7H2O, this solution, until being completely dissolved, is kept 3-10 days by stirring when 0-10 DEG C, and by filtering, cold water washs, air drying prepares blue H22[MoV xMoVI y-O301(H2O)29{La(H2O)6}2{La(H2O)5}6]��mH2O��
2. the method utilizing polyoxometallate elimination hydrogen sulfide gas according to claim 1, is characterized in that: mixing gas inlet flow rate 20-180ml/min.
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| CN106669420B (en) * | 2017-02-17 | 2019-08-16 | 山东大学 | A kind of electrochemical regeneration method after polyoxometallic acid saline solution desulfurization |
| CN111320208B (en) * | 2020-02-20 | 2021-07-20 | 华南理工大学 | Method for preparing POMs (polyoxymethylene) by photoinduced in-situ aggregation |
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| Title |
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| {Mo96La8} Eggshell Ring and Self-Assembly to {Mo132} Keplerate through Mo-blue Intermediate, Involved in UV-Photolysis of [Mo7O24]6-/Carboxylic Acid System at pH 4;Toshihiro Yamase et al.;《Inorganic Chemistry》;20100920;第49卷;第9426-9437页 * |
| Dawson磷钼钒酸的合成、脱硫与微波辅助空气再生;马云倩等;《无机化学学报》;20121031;第28卷(第10期);第2179-2185页 * |
| New Method for H2S Removal in Acid Solutions;Alberto de Angelis et al.;《ChemSusChem》;20101231;第3卷;第829-833页 * |
| 杂多化合物脱硫化氢动力学研究;王睿等;《环境科学学报》;20001130;第20卷(第6期);第767-771页 * |
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