CN103418232A - Mercury remover and preparation method thereof - Google Patents
Mercury remover and preparation method thereof Download PDFInfo
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- CN103418232A CN103418232A CN2012101552274A CN201210155227A CN103418232A CN 103418232 A CN103418232 A CN 103418232A CN 2012101552274 A CN2012101552274 A CN 2012101552274A CN 201210155227 A CN201210155227 A CN 201210155227A CN 103418232 A CN103418232 A CN 103418232A
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Abstract
The invention discloses a mercury remover and a preparation method thereof. The active components at least comprise MSSH, wherein M is a metal which can generate a trivalent ion. The invention further discloses a preparation method of the mercury remover on the basis of the disclosure of the mercury remover. The mercury remover has a very high binding force for mercury, the bonding strength between the mercury remover and mercury is stronger than that between the metal sulfide and mercury, and thus the problem of low utilization rate of metal sulfide during the mercury removing process, causing by the bad binding force between the metal sulfide and mercury, and the low mercury capacity during the mercury removing process, is solved.
Description
Technical field
The present invention relates to a kind of mercury removal agent and preparation method thereof, belong to the mercury removal agent technical field.
Background technology
All contain mercury in the industrial gas such as coke-stove gas, water-gas and natural gas, mercury becomes air toxic of greatest concern after sulfur dioxide and nitrogen oxide owing to having hypertoxicity, effumability, persistence and deposition in vivo.Mercury causes very large harm to organism and environment, this is because organism can react the hypertoxic methyl mercury of formation after absorbing mercury in vivo, methyl mercury can be combined with the sulfydryl of enzyme and be formed mercaptides, causes the activity of enzyme to be suppressed, thereby has destroyed the analytic metabolism function of biological cell.In addition, methyl mercury can also make the permeability of cell change, and destroys intracellular ionic equilibrium, suppresses nutriment and enters cell, causes meronecrosis; Therefore, after mercury is absorbed by plants, can cause plant leaf blade come off, withered, mercury reaches in animal body after a certain amount of and can cause animal to be poisoned to death.Most serious of all, the mankind are as the afterbody of food chain, and the mercury in the other biological body, after enrichment, can circulation entering human body, causes great harm to human health, and therefore administering heavy metal Hg has become the current very urgent problem that will solve.
Mercury mainly is present in coke-stove gas, water-gas and natural gas with three kinds of forms, comprises gaseous mercury simple substance (Hg
0), gaseous oxidation mercury (Hg
2+) and particle mercury.The method that removes mercury comprises wet method demercuration and dry method demercuration.Wet method demercuration technology is relatively good for the removal effect of gaseous oxidation mercury and particle mercury, and clearance can reach more than 76%, and is only 30% to the gaseous elemental mercury clearance, is difficult to adapt to the needs that mercury is administered.
Dry method demercuration technology is to utilize active carbon, calcium agent adsorbent, zeolitic material or other adsorbents to remove mercury.But, because the utilization rate of acticarbon is low, the power consumption large, cost is high, be difficult to be widely applied; Calcium agent adsorbent and zeolitic material adsorbent are also very low to the removal efficiency of gaseous elemental mercury, therefore also are difficult to thoroughly solve the problem of demercuration.
Along with various countries researcher going deep into gradually mercury removal agent research, although there is the researcher to find that elemental sulfur has very high adhesion to particle mercury, but its adhesion to gaseous mercury simple substance and gaseous state mercury oxide a little less than, therefore there is the researcher to propose to adopt metal sulfide to remove mercury as adsorbent, for example Canadian Patent document CA1099489A1 discloses a kind of mercury removal agent for gas, it comprises carrier and loads on carrier the metal sulfide for Adsorption of Mercury, metal sulfide comprises vulcanized lead, calcium sulfide, antimony trisulfide, arsenones, iron sulfide, nickel sulfide and zinc sulphide, after mercury in gas is adsorbed by metal sulfide, reaction generates mercuric sulphide, after separating, the mercuric sulphide of generation is discharged.In above-mentioned technology, adopt metal sulfide as mercury removal agent, although its demercuration rate can reach more than 90%, it is lower that but its mercury holds, for identical mercurous gas treatment amount, need to change continually mercury removal agent just can reach containing effectively the removing of mercury in mercury gas, the Efficiency Decreasing that will cause like this demercuration to be processed; And the replacing of mercury removal agent frequently, the useless agent of mercury removal agent that the meeting output is a large amount of, when post-processed is carried out in useless agent to these mercury removal agents, need to expend large-area soil and expense and complete landfill, also easily causes the adverse effect to environment.
Summary of the invention
Technical problem to be solved by this invention is that the mercury appearance of metal sulfide mercury removal agent in prior art is low, the problem that the demercuration treatment effeciency is low; And then provide mercury removal agent of a kind of Gao Gongrong of having and preparation method thereof.
For solving the problems of the technologies described above, the invention provides a kind of mercury removal agent, its active component at least comprises: MSSH, wherein, M is for forming the metal of trivalent ion.
Described metal is aluminium, gallium, indium, thallium, bismuth or transition metal.
Described transition metal is iron, manganese, scandium, vanadium, chromium or cobalt.
Described mercury removal agent also comprises binding agent.
The weight ratio of described MSSH and binding agent is (90-99.5): (0.5-10).
Described mercury removal agent is comprised of described MSSH and binding agent, and the content of described MSSH is 90-99.5wt%, and the content of described binding agent is 0.5-10wt%.
Described binding agent is one or more in sesbania gum, guar gum, CMC and alumino-silicate cement.
The preparation method of described mercury removal agent, carry out presulfurization to the oxyhydroxide of the metal that can form trivalent ion, obtains mercury removal agent after presulfurization.
The temperature of described presulfurization is 20-110 ℃.
The temperature of described presulfurization is 20-80 ℃.
The described oxyhydroxide that forms the metal of trivalent ion is aluminum oxyhydroxide, FeOOH, hydroxyl oxidize manganese, hydroxyl oxidize scandium, hydroxyl oxidize gallium, hydroxyl oxidize vanadium, chromium oxyhydroxide, hydroxyl oxidize indium, hydroxy cobalt oxide, hydroxyl oxidize bismuth or hydroxyl oxidize thallium.
Described FeOOH is amorphous FeOOH.
Utilize hydrogen sulfide gas to carry out presulfurization to the described oxyhydroxide that forms the metal of trivalent ion.
Can form after the oxyhydroxide presulfurization of metal of trivalent ion the purposes as mercury removal agent.
The demercuration temperature of mercury removal agent is-30-110 ℃.
Described demercuration temperature is-30-50 ℃.
The present invention compares and has following beneficial effect with the prior art scheme:
(1) mercury removal agent of the present invention, its active component at least comprises MSSH, wherein M is for forming the metal of trivalent ion.MSSH(metal sulfydryl sulfide) in, contain sulfenyl and sulfydryl simultaneously, the inventor finds after deliberation: sulfydryl has very high adhesion for the mercury in waste gas, it is on the one hand the summation that the electronics that has due to sulfydryl itself is sulphur atom and hydrogen atom, it is stronger that electron rich structure makes sulfydryl compare sulfenyl for the adhesion of mercury, more easily realizes removing containing mercury in mercury gas; On the other hand, M-S in sulfydryl and S-H key are not at grade, this sulfenyl that just makes the MSSH molecule is compared in metal sulfide the distance between sulfenyl with the distance of sulfydryl more approaching, once mercury contacts with metal sulfydryl sulfide, formed suction-operated is very strong, be that MSSH has very high adhesion to mercury, its combination degree is better than the adhesion of metal sulfide to mercury.Avoided thus in the prior art adhesion of metal sulfide mercury removal agent and mercury not good enough, mercury removal agent mercury holds low, and causes the problem of the frequent replacing of mercury removal agent needs.
(2) mercury removal agent of the present invention, also include binding agent, binding agent can improve the adhesion of active component MSSH, promotes moulding, prevent that mercury removal agent is in use crushed and cause coming off, losing of active component, thereby improved the service life of mercury removal agent.
(3) preparation method of mercury removal agent of the present invention, its oxyhydroxide of take the metal that can form trivalent ion is active component, it is carried out can changing metal sulfydryl sulfide into after the presulfurization processing, directly as mercury removal agent; This preparation method is simple, with low cost.
The specific embodiment
Embodiment 1
Amorphous FeOOH is filled in the bed of fixed bed reactors, pass into the gas that contains hydrogen sulfide in reactor, at the temperature of 80 ℃, amorphous FeOOH fixed bed is carried out to presulfurization, after presulfurization, amorphous FeOOH changes FeSSH(sulfydryl iron sulfide into), be mercury removal agent 1.
In the present embodiment, amorphous FeOOH is the CDS-100, the NDS-2 that produce of Beijing Sanju New Environmental Protection Materials Co., Ltd, the product of the models such as SDS-100, SDS-200.
Embodiment 2
Add sodium hydroxide solution in copperas solution, carry out neutralization reaction under 10 ~ 39 ℃, hierarchy of control pH value is 6.0-7.5, the white precipitate of the generation in solution becomes when blackish green, solution is diluted, pass into wherein air and reacted, when system pH reaches 3-4, make needle-like oyster iron oxide yellow crystal seed; The iron oxide yellow crystal seed obtained is diluted, be warming up to 80-83 ℃, pass into wherein large quantity of air, maintenance system pH value is 2-3, and oxidation obtains alpha-feooh more than 40 hours.
Alpha-feooh is filled in the bed of fixed bed reactors, pass into the gas that contains hydrogen sulfide in reactor, at the temperature of 60 ℃, the alpha-feooh fixed bed is carried out to presulfurization, after presulfurization, alpha-feooh changes FeSSH(sulfydryl iron sulfide into), be mercury removal agent 2.
Embodiment 3
To Al
2(SO
4)
3The pH value that adds potassium hydroxide alkali lye regulator solution in solution is 6-8, is washed with water to without SO after filtering out precipitation
4 2-, under 60 ℃ dry 8 hours afterwards, obtain AlOOH.
AlOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 20 ℃, the AlOOH fixed bed is carried out to presulfurization, after presulfurization, AlOOH changes AlSSH(sulfydryl aluminium sulfide into), be mercury removal agent 3.
Embodiment 4
To ScCl
3The pH value that adds potassium hydroxide alkali lye regulator solution in solution is 6-8, is washed with water to without Cl after filtering out precipitation
-, under 70 ℃ dry 8 hours afterwards, obtain ScOOH.
ScOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 110 ℃, the ScOOH fixed bed is carried out to presulfurization, after presulfurization, ScOOH changes ScSSH(sulfydryl scandium sulfide into), be mercury removal agent 4.
Embodiment 5
To VSO
4The pH value that adds potassium hydroxide alkali lye regulator solution in solution is 6-8, is washed with water to without SO after filtering out precipitation
4 2-, then pass into air and carry out oxidation, under 60 ℃ dry 5 hours afterwards, obtain VOOH.
VOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 60 ℃, the VOOH fixed bed is carried out to presulfurization, after presulfurization, VOOH changes VSSH(sulfydryl vanadic sulfide into), be mercury removal agent 5.
Embodiment 6
To CrSO
4The pH value that adds the sodium hydroxide lye regulator solution in solution is 6-8, is washed with water to without SO after filtering out precipitation
4 2-, then pass into air and carry out oxidation, under 50 ℃ dry 10 hours afterwards, obtain CrOOH.
CrOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 90 ℃, the CrOOH fixed bed is carried out to presulfurization, after presulfurization, CrOOH changes CrSSH(sulfydryl chromic sulfide into), be mercury removal agent 6.
Embodiment 7
To MnCl
2The pH value that adds potassium hydroxide alkali lye regulator solution in solution is 6-8, is washed with water to without Cl after filtering out precipitation
-, then pass into air and carry out oxidation, under 70 ℃ dry 4 hours afterwards, obtain MnOOH.
MnOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 50 ℃, the MnOOH fixed bed is carried out to presulfurization, after presulfurization, MnOOH changes MnSSH(sulfydryl manganese sulfide into), be mercury removal agent 7.
Embodiment 8
To CoCl
2The pH value that adds potassium hydroxide alkali lye regulator solution in solution is 6-8, is washed with water to without Cl after filtering out precipitation
-, then pass into air and carry out oxidation, under 50 ℃ dry 8 hours afterwards, obtain CoOOH.
CoOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 40 ℃, the CoOOH fixed bed is carried out to presulfurization, after presulfurization, CoOOH changes CoSSH(sulfydryl cobalt sulfide into), be mercury removal agent 8.
Embodiment 9
To BiCl
3The pH value that adds potassium hydroxide alkali lye regulator solution in solution is 6-8, is washed with water to without Cl after filtering out precipitation
-, under 50 ℃ dry 8 hours afterwards, obtain BiOOH.
BiOOH is filled in the bed of fixed bed reactors, in reactor, passes into the gas that contains hydrogen sulfide, at the temperature of 30 ℃, the BiOOH fixed bed is carried out to presulfurization, after presulfurization, BiOOH changes BiSSH(sulfydryl bismuth sulfide into), be mercury removal agent 9.
Embodiment 10
Sesbania gum adds the water wiring solution-forming, is placed with the FeOOH powder in coating pan.Roll and adhere to the FeOOH powder putting into coating pan after the nucleation particle surface spraying sesbania gum solution such as millet, and then spraying sesbania gum solution, continue to roll, adhere to, until be shaped to spherically, round dry 10h under 80 ℃ is obtained to the round of FeOOH and sesbania gum moulding.
Round is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 80 ℃, obtain FeSSH(sulfydryl iron sulfide after presulfurization) with the mixture of sesbania gum, it is mercury removal agent 10, wherein the content of FeSSH is 99.3wt%, and the content of sesbania gum is 0.7wt%.
Embodiment 11
After adding in AlOOH guar gum binding agent and water mechanical mixture evenly, mediate extruded moulding, under 110 ℃, dry 3h obtains the strip of AlOOH and guar gum mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 20 ℃, obtain AlSSH(sulfydryl aluminium sulfide after presulfurization) with the mixture of guar gum binding agent, it is mercury removal agent 11, wherein the content of AlSSH is 99.5wt%, and the content of guar gum is 0.5wt%.
Embodiment 12
After adding in ScOOH CMC binding agent and water mechanical mixture evenly, mediate extruded moulding, under 80 ℃, dry 10h obtains the strip of ScOOH and CMC mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 110 ℃, obtain ScSSH(sulfydryl scandium sulfide after presulfurization) with the mixed-forming thing of CMC binding agent, it is mercury removal agent 12, wherein the content of ScSSH is 90wt%, and the content of CMC is 10wt%.
Embodiment 13
Sesbania gum adds the water wiring solution-forming, is placed with the VOOH powder in coating pan.Roll and adhere to the VOOH powder putting into coating pan after the nucleation particle surface spraying sesbania gum solution such as millet, and then spraying sesbania gum solution, continue to roll, adhere to, until be shaped to spherically, round dry 7h under 60 ℃ is obtained to the round of VOOH and sesbania gum moulding.
The article shaped of VOOH and sesbania gum binding agent is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 90 ℃, obtain VSSH(sulfydryl vanadic sulfide after presulfurization) with the mixture of sesbania gum binding agent, it is mercury removal agent 13, wherein the content of VSSH is 99.3wt%, and the content of sesbania gum is 0.7wt%.
Embodiment 14
After adding in CrOOH alumino-silicate cement and water mechanical mixture evenly, mediate extruded moulding, under 100 ℃, dry 4h obtains the strip of CrOOH and the moulding of alumino-silicate cement mixing.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 40 ℃, obtain CrSSH(sulfydryl chromic sulfide after presulfurization) with the mixture of alumino-silicate cement, it is mercury removal agent 14, wherein the content of CrSSH is 85wt%, and the content of alumino-silicate cement is 15wt%.
Embodiment 15
After adding in MnOOH guar gum and water mechanical mixture evenly, mediate extruded moulding, under 90 ℃, dry 6h obtains the strip of MnOOH and guar gum mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 70 ℃, obtain MnSSH(sulfydryl manganese sulfide after presulfurization) with the mixed-forming thing of guar gum, it is mercury removal agent 15, wherein the content of MnSSH is 95wt%, and the content of guar gum is 5wt%.
Embodiment 16
After adding in CoOOH CMC binding agent and water mechanical mixture evenly, mediate extruded moulding, under 80 ℃, dry 6h obtains the strip of CoOOH and CMC mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 50 ℃, obtain CoSSH(sulfydryl cobalt sulfide after presulfurization) with the mixed-forming thing of CMC binding agent, it is mercury removal agent 16, wherein the content of CoSSH is 98wt%, and the content of CMC is 2wt%.
Embodiment 17
After adding in BiOOH guar gum and water mechanical mixture evenly, mediate extruded moulding, under 110 ℃, dry 3h obtains the strip of BiOOH and guar gum mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 80 ℃, obtain BiSSH(sulfydryl bismuth sulfide after presulfurization) with the mixed-forming thing of guar gum, it is mercury removal agent 17, wherein the content of BiSSH is 96wt%, and the content of guar gum is 4wt%.
Embodiment 18
After adding in BiOOH sesbania gum, CuS and water mechanical mixture evenly, mediate extruded moulding, under 100 ℃, dry 5h obtains the strip of BiOOH, CuS and sesbania gum mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, make this fixed bed carry out presulfurization under 80 ℃, obtain BiSSH(sulfydryl bismuth sulfide after presulfurization), the mixed-forming thing of CuS and sesbania gum, it is mercury removal agent 18, wherein the content of BiSSH is 94wt%, the content of CuS is 2wt%, and the content of sesbania gum is 4wt%.
Embodiment 19
Add guar gum, CoCl in MnOOH
3After even with the water mechanical mixture, mediate extruded moulding, under 110 ℃, dry 3h obtains MnOOH, CoCl
3Strip with the guar gum mixed-forming.
Strip is filled in the bed of fixed bed reactors, to passing into the gas that contains hydrogen sulfide in reactor, makes this fixed bed carry out presulfurization under 60 ℃, obtain MnSSH(sulfydryl manganese sulfide after presulfurization), CoCl
3With the mixed-forming thing of guar gum, mercury removal agent 19, and wherein the content of MnSSH is 92wt%, CoCl
3Content be 5wt%, the content of guar gum is 3wt%.
Oxyhydroxide in above-described embodiment can be the oxyhydroxide of any existing crystal formation.
Embodiment 20
The isolated aeroseal of mercury removal agent 1 is filled in the fixed bed bed, is 800h at-30 ℃, normal pressure, air speed
-1Condition under, with the natural gas that contains 10ppm mercury by this fixed bed bed.After demercuration in gas remaining mercury with liquor potassic permanganate, absorb, then after being reduced to Elemental Mercury with hydrochloric acid hydrogen amine, with mercury vapourmeter, detect, the demercuration rate of gained mercury removal agent is 99.9%.
Embodiment 21
The isolated aeroseal of mercury removal agent 3 is filled in the fixed bed bed, is 1000h at 110 ℃, normal pressure, air speed
-1Condition under, the water-gas that the mercury content of take is 8ppm is by this fixed bed bed.After demercuration in gas remaining mercury with liquor potassic permanganate, absorb, then after being Elemental Mercury with Reduction with Stannous Chloride, with mercury vapourmeter, detect, gained demercuration rate is 99.6%.
Embodiment 22
It is 500h that the isolated aeroseal of mercury removal agent 10 is filled in to inherent 50 ℃ of fixed bed bed, normal pressure, air speed
-1Condition under, with the coke-stove gas that contains 6ppm mercury by this fixed bed bed.After demercuration in gas remaining mercury with liquor potassic permanganate, absorb, then after being reduced to Elemental Mercury with hydrochloric acid hydrogen amine, with mercury vapourmeter, detect, gained demercuration rate is 99.4%.
Characterize example
The oxyhydroxide that forms the metal of trivalent ion of the present invention obtains metal sulfydryl sulfide after presulfurization, for the structure to this material further proves, adopts following method to carry out, and below take FeOOH as example:
(1) be that mercury removal agent 1 use dissolving with hydrochloric acid is mixed with solution by the material that in above-described embodiment 1, FeOOH generates after presulfurization, get respectively the above-mentioned solution of 3 parts of 20ml, be labeled as successively sample 1, sample 2 and sample 3, choose sample 3 for blank solution.
To dripping the potassium ferrocyanide solution of 1mol/L, solution turned blue in sample 1;
To dripping the potassium ferricyanide solution of 1mol/L in sample 2, color is constant.
Hence one can see that, and FeOOH iron in the material of presulfurization gained is to exist with three valence states, is not divalent state.
(2) exist with three valence states according to (1) drawn FeOOH iron in presulfurization gained material, can infer that the process that the FeOOH presulfurization is:
2FeOOH+3H
2S → Fe
2S
3H
2O+3H
2O (formula 1)
Or FeOOH+2H
2S → FeSSH+2H
2O (formula 2)
It is 54% that the theory of formula 1 is calculated Sulfur capacity, and it is 72% that the theory of formula 2 is calculated Sulfur capacity.
(3) get the 5g FeOOH, under normal temperature (finger ring border temperature, be generally-5-45 ℃) normal pressure (finger ring border pressure, be generally 1 atmospheric pressure), with containing H
2The Standard Gases test that S is 40000ppm, adopt the comprehensive Microcoulomb instrument of domestic WK-2C (Jiangsu Electrical Analysis Instrument Factory's production) to be detected, the detection limit of this instrument is 0.2ppm, the Sulfur capacity of practical measurement is 71%, in conjunction with (2) known FeOOH presulfurization actual be the process of formula 2, FeOOH is FeSSH through the material of presulfurization gained.
Comparative Examples
Load there is is the silica of iron sulfide use as mercury removal agent, wherein the content of iron sulfide is 30wt%, the content of silica is 70wt%, mercury removal agent is ground into to 20-40 purpose particle and is accurate to 0.0001g with the accurate weighing 3g(of assay balance) be filled in the 6ml purification reactor that internal diameter is 8mm, the two ends of reactor are blocked with cotton, in normal temperature, normal pressure, air speed, are 2000h
-1Condition under, with the nitrogen that contains 4ppm mercury by this purification reactor.After demercuration in gas remaining mercury with liquor potassic permanganate, absorb, then after being reduced to Elemental Mercury with hydrochloric acid hydrogen amine, with mercury vapourmeter, detect, stop test while recording the mercury that contains 0.02ppb in the gas after demercuration.The mercury appearance that records this mercury removal agent is 2.1%, and the demercuration rate is 96%.
Test case
By embodiment 1-19, prepared mercury removal agent 1-19 is ground into 20-40 purpose particle, be accurate to 0.0001g with the accurate weighing 3g(of assay balance respectively) fill it in the 6ml purification reactor that internal diameter is 8mm, the two ends of reactor are blocked with cotton, in normal temperature, normal pressure, air speed, are 2000h
-1Condition under, with the nitrogen that contains 4ppm mercury by this purification reactor.After demercuration in gas remaining mercury with liquor potassic permanganate, absorb, then after being reduced to Elemental Mercury with hydrochloric acid hydrogen amine, with mercury vapourmeter, detect, stop test while recording the mercury that contains 0.02ppb in the gas after demercuration.Demercuration effect to this mercury removal agent is measured, and acquired results is as follows:
| Mercury removal agent | 1 | 2 | 3 | 4 | 5 | 6 |
| Mercury holds (%) | 4.8% | 3.9% | 1.5% | 3.5% | 3.2% | 4.5% |
| Mercury removal agent | 7 | 8 | 9 | 10 | 11 | 12 |
| Mercury holds (%) | 4.7% | 4.3% | 3.1% | 4.1% | 1.1% | 4.3% |
| Mercury removal agent | 13 | 14 | 15 | 16 | 17 | 18 |
| Mercury holds (%) | 4.0% | 3.9% | 2.9% | 2.4% | 0.9% | 1.4% |
| Mercury removal agent | 19 | |||||
| Mercury holds (%) | 1.2% |
Contrast above-described embodiment and Comparative Examples are known, the demercuration efficiency of the mercury removal agent that the present invention prepares is higher than the mercury removal agent in Comparative Examples, and in embodiment except mercury removal agent 3,11,17,18,19, the mercury appearance of mercury removal agent is all held higher than the mercury of mercury removal agent in Comparative Examples, and mercury removal agent of the present invention is widely used in removing the mercury in natural gas, water-gas and coke-stove gas.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it; but; those skilled in the art should be understood that any form that does not exceed the claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (16)
1. a mercury removal agent, its active component at least comprises:
MSSH, wherein, M is for forming the metal of trivalent ion.
2. mercury removal agent according to claim 1, is characterized in that, described metal is aluminium, gallium, indium, thallium, bismuth or transition metal.
3. mercury removal agent according to claim 2, is characterized in that, described transition metal is iron, manganese, scandium, vanadium, chromium or cobalt.
4. according to the arbitrary described mercury removal agent of claim 1-3, it is characterized in that, described mercury removal agent also comprises binding agent.
5. mercury removal agent according to claim 4, is characterized in that, the weight ratio of described MSSH and binding agent is (90-99.5): (0.5-10).
6. according to the arbitrary described mercury removal agent of claim 1-4, it is characterized in that, described mercury removal agent is comprised of described MSSH and binding agent, and the content of described MSSH is 90-99.5wt%, and the content of described binding agent is 0.5-10wt%.
7. according to the arbitrary described mercury removal agent of claim 4-6, it is characterized in that, described binding agent is one or more in sesbania gum, guar gum, CMC and alumino-silicate cement.
8. the preparation method of the arbitrary described mercury removal agent of claim 1-7, is characterized in that, the oxyhydroxide of the metal that can form trivalent ion is carried out to presulfurization, obtains mercury removal agent after presulfurization.
9. the preparation method of mercury removal agent according to claim 8, is characterized in that, the temperature of presulfurization is 20-110 ℃.
10. the preparation method of mercury removal agent according to claim 9, is characterized in that, the temperature of described presulfurization is 20-80 ℃.
11. the preparation method of according to Claim 8 or 9 or 10 described mercury removal agents, it is characterized in that, the described oxyhydroxide that forms the metal of trivalent ion is aluminum oxyhydroxide, FeOOH, hydroxyl oxidize manganese, hydroxyl oxidize scandium, hydroxyl oxidize gallium, hydroxyl oxidize vanadium, chromium oxyhydroxide, hydroxyl oxidize indium, hydroxy cobalt oxide, hydroxyl oxidize bismuth or hydroxyl oxidize thallium.
12. the preparation method of mercury removal agent according to claim 11, is characterized in that, described FeOOH is amorphous FeOOH.
13. the preparation method of according to Claim 8-12 arbitrary described mercury removal agents, is characterized in that, utilizes hydrogen sulfide gas to carry out presulfurization to the described oxyhydroxide that forms the metal of trivalent ion.
14. can form after the oxyhydroxide presulfurization of metal of trivalent ion the purposes as mercury removal agent.
15. purposes according to claim 14, is characterized in that, the demercuration temperature of mercury removal agent is-30-110 ℃.
16. purposes according to claim 15, described demercuration temperature is-30-50 ℃.
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| CN103418232B (en) | 2017-07-21 |
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