CN102872800A - Preparation method of heavy metal mercury-enriched material - Google Patents
Preparation method of heavy metal mercury-enriched material Download PDFInfo
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- CN102872800A CN102872800A CN2011101926121A CN201110192612A CN102872800A CN 102872800 A CN102872800 A CN 102872800A CN 2011101926121 A CN2011101926121 A CN 2011101926121A CN 201110192612 A CN201110192612 A CN 201110192612A CN 102872800 A CN102872800 A CN 102872800A
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Abstract
The invention relates to a preparation method of a heavy metal mercury-enriched material, comprising the following steps of: stirring and kneading washed, dried and crushed rich shell powder and a phosphoric acid solution and a methanol solution of tetramethoxysilane, carrying out extrusion moulding, drying in a drying box, carrying out heat treatment in an electric resistance furnace in the absence of air so as to obtain a granular material; dissolving palladium chloride and glucose in water, continuously stirring, adding the above granular material, stirring and mixing, removing a filtrate, directly putting into the drying box for drying, and reducing by heating so as to obtain a heavy metal mercury-enriched material. A main component of the obtained material is active carbon. The mass fraction of Pb particles is 0.2-2.0% and the mass fraction of SiO2 particles is 2-8%. By the use of the material, free mercury and mercury compounds in a water sample and a gas sample can be enriched and are soak in 25% of an aqueous phosphoric acid solution for 8 hours, so as to transfer mercury into a solution in the form of ions. The preparation process requires a mild condition. The preparation method is simple and convenient to operate, requires low cost, and has no pollution. The enrichment material has good mechanical strength and chemical stability, and can be recycled and reused.
Description
Technical field
The present invention relates to a kind of preparation method of heavy metal Hg enrichment material, belong to the environment measuring technical field.
Background technology
Along with developing rapidly of modern industry, many pollutants that contain heavy metal ion enter atmosphere, water and soil environment, have caused serious environmental pollution.Heavy metal ion is difficult for decomposing, and easily causes secondary pollution, can accumulate by the bioconcentration of food chain, just can endanger healthy in case take in human body.Therefore, most important to the accurate detection of heavy metal ion in the water.
Mercury is a kind of poisonous silvery white heavy metal element, and it is liquid metals unique under the normal temperature, free be present in nature and be present in cinnabar, calomel and other several ore deposits, and symbol of element Hg is commonly called as " mercury ".The inorganic compound of common mercury such as mercuric nitrate (Hg (NO
3)
2), mercuric chloride (HgCl
2), calomel (Hg
2Cl
2), mercuric bromide (HgBr
2), mercuric arsenate (HgAsO
4), mercuric sulphide (HgS), mercuric sulfate (HgSO
4), mercury oxide (HgO), mercury cyanide (Hg (CN)
2) etc., can be used for the synthetic of mercury compound, or as catalyst, pigment, coating etc.; Metallurgical industry is commonly used amalgam process (mercury can dissolve other metal and form amalgam) and is extracted the metals such as gold, silver and thallium; Chemical industry is made negative electrode with mercury and is produced caustic soda and chlorine with electrolytic salt solution; Some compounds of mercury are pharmaceutically having sterilization, diuresis and analgesic activity, and the mercury silver alloy is good dental material, and what have also dislikes sore, mange etc. as medicine as treatment, all can cause poisoning when oral, excessive its dust of suction and skin coating.
In total consumption of mercury, free metal mercury accounts for about 30%, and the mercury of compound state accounts for about 70%.Mercury belongs to extremely toxic substance, can cause acute poisoning when free mercury concentration is 1.2～8.5mg/m in the air, surpasses 0.1mg/m and then can cause slow poisoning.The mercury of compound state is Powdered more, can absorb through respiratory tract, skin, alimentary canal.The acute toxicity target organ of mercury mainly is kidney, is alimentary canal, lung etc. secondly; The chronic toxicity target organ then mainly is brain, alimentary canal and kidney.Its toxic mechanism can roughly be summarised as 3 points: 1, enzyme inhibition: such as amino, carboxyl, hydroxyl, phosphoryl, particularly sulfydryl has high affinity to mercury for the various active groups of enzyme, can be with it in conjunction with making enzyme deactivation; 2, activate mediated responses: after activating such as the phosphatide hydrolytic process, can make a large amount of generations such as arachidonic acid, thromboxane, oxygen radical, cause tissue damage; 3, immunity is pathogenic: mercury not only can cause the immunity glomerular injury, still can suppress the T lymphocyte function, thereby the obstacle Organism immunoregulation is machine-processed.
Because mercury content is very low, Accurate Determining generally to need enrichment.At present, there are a lot of physics, chemical method to be used to the enrichment of mercury, wherein, mainly contain electrolysis, the precipitation method, absorption method etc.But the electrolysis energy consumption is higher, and causes easily secondary pollution; The precipitation method and physisorphtion can not be used for the detection of trace heavy metal ion.The chemistry huge legendary turtle is closed, and namely adopts intercalating agent to be combined Adsorption of Heavy Metal Ions with the coordination of heavy metal ion, because of its can with the heavy metal ion selectively acting, and can detect trace heavy metal ion and receive much concern.Although, there were in recent years the nano porous active carbon of mesoporous silicon oxide, oxygen and the nitrogen modification of using the coloured glaze base to modify, the amido modified materials such as block copolymer to be used for the report of heavy mental treatment, but because its processing preparation process is complicated, running cost is higher and be difficult to promote the use of.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of heavy metal Hg enrichment material.Concrete preparation method is:
(1) the rice husk powder of will clean, dry, pulverizing and the phosphoric acid solution of mass fraction 40%～68%, be that 1～3: 1 ratio is mixed in rice husk powder and phosphoric acid solution mass ratio, mediated 1～2 hour 50～100 ℃ of lower stirrings, the methanol solution that adds tetramethoxy-silicane continues to stir and mediated 1～2 hour;
(2) with the extrusion modling on former of above-mentioned compound, and place 80～120 ℃ of dryings of drying box 1.5～2.5 hours, then place 360～500 ℃ of resistance furnace secluding airs heat treatment 2～3 hours, obtain granular materials;
(3) palladium bichloride and glucose is soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to mix 1～2 hour, discard filtrate and directly place drying box to dry, and 150～220 ℃ of lower heat reductions 5～10 minutes, namely get the heavy metal Hg enrichment material.
Wherein, the granular materials of extrusion modling is that maximum particle diameter is no more than 4 millimeters sphere or cylindricality or goose is avette or sheet or bar shaped particle in the step (2).The main component of gained enrichment material is active carbon in the step (3), and the mass fraction of Pb particle is 0.2～2.0%, SiO
2The mass fraction of particle is 2～8%.
Load Filter column or directly mix immersion with the water sample for the treatment of enrichment with this material, then mercury enrichment wherein can be soaked 8 hours with 25% phosphate aqueous solution, can change mercury over to solution with ionic species.
Advantage of the present invention and effect:
1, can Sync enrichment free state mercury metal and chemical combination attitude mercury;
2, preparation process is easy, low, the non-secondary pollution of cost;
3, enrichment material has good mechanical strength and chemical stability, can recycle;
4, enrichment material is easy to use, can load Filter column or directly mixes with the water sample for the treatment of enrichment or place gaseous sample can obtain the enrichment purpose.
The specific embodiment
Embodiment 1
(1) the rice husk powder of will clean, dry, pulverizing and the phosphoric acid solution of mass fraction 43%, be that 1.1: 1 ratio is mixed in rice husk powder and phosphoric acid solution mass ratio, mediated 1 hour 52 ℃ of lower stirrings, add the methanol solution of tetramethoxy-silicane, continue to stir and mediated 2 hours;
(2) with the extrusion modling on former of above-mentioned compound, and place 82 ℃ of dryings of drying box 1.8 hours, then place 370 ℃ of resistance furnace secluding airs heat treatment 3 hours, obtain granular materials;
(3) palladium bichloride and glucose is soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to mix 1 hour, discard filtrate and directly place drying box to dry, and 160 ℃ of lower heat reductions 8 minutes, namely get the heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pb particle is 1.0%, SiO
2The mass fraction of particle is 3%.
With the Filter column of this material filling more than 40 centimetres, pending water sample normal pressure is crossed post once, can be with the mercury ion enrichment in the water more than 70%; With pending gaseous sample by this post once, can be with the occlusion of Trace Mercury steam more than 80%; Then soaked 8 hours with 25% phosphate aqueous solution, can change mercury over to solution with ionic species.
Embodiment 2
(1) the rice husk powder of will clean, dry, pulverizing and the phosphoric acid solution of mass fraction 50%, be that 2: 1 ratio is mixed in rice husk powder and phosphoric acid solution mass ratio, mediated 1 hour 60 ℃ of lower stirrings, add the methanol solution of tetramethoxy-silicane, continue to stir and mediated 2 hours;
(2) with the extrusion modling on former of above-mentioned compound, and place 90 ℃ of dryings of drying box 2 hours, then place 380 ℃ of resistance furnace secluding airs heat treatment 2 hours, obtain granular materials;
(3) palladium bichloride and glucose is soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to mix 1 hour, discard filtrate and directly place drying box to dry, and 180 ℃ of lower heat reductions 9 minutes, namely get the heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pb particle is 0.5%, SiO
2The mass fraction of particle is 2.5%.
With the Filter column of this material filling more than 40 centimetres, pending water sample normal pressure is crossed post once, can be with the mercury ion enrichment in the water more than 70%; With pending gaseous sample by this post once, can be with the occlusion of Trace Mercury steam more than 80%; Then soaked 8 hours with 25% phosphate aqueous solution, can change mercury over to solution with ionic species.
Embodiment 3
(1) the rice husk powder of will clean, dry, pulverizing and the phosphoric acid solution of mass fraction 60%, be that 2.5: 1 ratio is mixed in rice husk powder and phosphoric acid solution mass ratio, mediated 2 hours 80 ℃ of lower stirrings, add the methanol solution of tetramethoxy-silicane, continue to stir and mediated 1 hour;
(2) with the extrusion modling on former of above-mentioned compound, and place 100 ℃ of dryings of drying box 2.4 hours, then place 450 ℃ of resistance furnace secluding airs heat treatment 2 hours, obtain granular materials;
(3) palladium bichloride and glucose is soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to mix 2 hours, discard filtrate and directly place drying box to dry, and 200 ℃ of lower heat reductions 6 minutes, namely get the heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pb particle is 1.3%, SiO
2The mass fraction of particle is 4.1%.
With the Filter column of this material filling more than 40 centimetres, pending water sample normal pressure is crossed post once, can be with the mercury ion enrichment in the water more than 75%; With pending gaseous sample by this post once, can be with the occlusion of Trace Mercury steam more than 80%; Then soaked 8 hours with 25% phosphate aqueous solution, can change mercury over to solution with ionic species.
Embodiment 4
(1) the rice husk powder of will clean, dry, pulverizing and the phosphoric acid solution of mass fraction 65%, be that 2.8: 1 ratio is mixed in rice husk powder and phosphoric acid solution mass ratio, mediated 1 hour 95 ℃ of lower stirrings, add the methanol solution of tetramethoxy-silicane, continue to stir and mediated 2 hours;
(2) with the extrusion modling on former of above-mentioned compound, and place 115 ℃ of dryings of drying box 1.5 hours, then place 480 ℃ of resistance furnace secluding airs heat treatment 2 hours, obtain granular materials;
(3) palladium bichloride and glucose is soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to mix 1 hour, discard filtrate and directly place drying box to dry, and 210 ℃ of lower heat reductions 6 minutes, namely get the heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pb particle is 1.5%, SiO
2The mass fraction of particle is 7.5%.
With the Filter column of this material filling more than 40 centimetres, pending water sample normal pressure is crossed post once, can be with the mercury ion enrichment in the water more than 70%; With pending gaseous sample by this post once, can be with the occlusion of Trace Mercury steam more than 80%; Then soaked 8 hours with 25% phosphate aqueous solution, can change mercury over to solution with ionic species.
Claims (3)
1. the preparation method of a heavy metal Hg enrichment material, its preparation process is:
(1) the rice husk powder of will clean, dry, pulverizing and the phosphoric acid solution of mass fraction 40%～68%, be that 1～3: 1 ratio is mixed in rice husk powder and phosphoric acid solution mass ratio, mediated 1～2 hour 50～100 ℃ of lower stirrings, the methanol solution that adds tetramethoxy-silicane continues to stir and mediated 1～2 hour;
(2) with the extrusion modling on former of above-mentioned compound, and place 80～120 ℃ of dryings of drying box 1.5～2.5 hours, then place 360～500 ℃ of resistance furnace secluding airs heat treatment 2～3 hours, obtain granular materials;
(3) palladium bichloride and glucose is soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to mix 1～2 hour, discard filtrate and directly place drying box to dry, and 150～220 ℃ of lower heat reductions 5～10 minutes, namely get the heavy metal Hg enrichment material.
2. the preparation method of a kind of heavy metal Hg enrichment material according to claim 1, the mass fraction that it is characterized in that Pb particle in the described heavy metal Hg enrichment material is 0.2～2.0%, SiO
2The mass fraction of particle is 2～8%.
3. the preparation method of a kind of heavy metal Hg enrichment material according to claim 1, the granular materials that it is characterized in that described extrusion modling is that maximum particle diameter is no more than 4 millimeters sphere or cylindricality or goose is avette or sheet or bar shaped particle.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175685A (en) * | 2019-07-02 | 2021-01-05 | 中国石油天然气股份有限公司 | System and method for reducing deposited mercury volatilization in natural gas processing equipment |
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| JP3736021B2 (en) * | 1997-04-17 | 2006-01-18 | Ｊｆｅスチール株式会社 | Method for separating and analyzing silicon and phosphorus |
| CN101306813A (en) * | 2008-07-04 | 2008-11-19 | 南京大学 | Method for preparing smooth cord-grass active carbon for treating cadmium-containing waste water |
| CN101347728A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Process for preparing Pd/carbon catalyst of high activity |
| CN101888970A (en) * | 2008-09-29 | 2010-11-17 | 索尼公司 | Porous carbon material composite, method for producing same, adsorbent, cosmetic preparation, purifying agent and photocatalyst composite material |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3736021B2 (en) * | 1997-04-17 | 2006-01-18 | Ｊｆｅスチール株式会社 | Method for separating and analyzing silicon and phosphorus |
| CN101347728A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Process for preparing Pd/carbon catalyst of high activity |
| CN101306813A (en) * | 2008-07-04 | 2008-11-19 | 南京大学 | Method for preparing smooth cord-grass active carbon for treating cadmium-containing waste water |
| CN101888970A (en) * | 2008-09-29 | 2010-11-17 | 索尼公司 | Porous carbon material composite, method for producing same, adsorbent, cosmetic preparation, purifying agent and photocatalyst composite material |
Non-Patent Citations (2)
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| 厉悦: "稻壳基活性炭制备及活性炭表面改性研究", 《中南林学院林产化工专业硕士学位论文》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175685A (en) * | 2019-07-02 | 2021-01-05 | 中国石油天然气股份有限公司 | System and method for reducing deposited mercury volatilization in natural gas processing equipment |
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