CN102872800B - Preparation method of heavy metal mercury-enriched material - Google Patents
Preparation method of heavy metal mercury-enriched material Download PDFInfo
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- CN102872800B CN102872800B CN201110192612.1A CN201110192612A CN102872800B CN 102872800 B CN102872800 B CN 102872800B CN 201110192612 A CN201110192612 A CN 201110192612A CN 102872800 B CN102872800 B CN 102872800B
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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 Pd 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 technical field of environmental detection.
Background technology
Along with developing rapidly of modern industry, many pollutants containing heavy metal ion enter air, water and soil environment, cause serious environmental pollution.Heavy metal ion is not easily decomposed, and easily causes secondary pollution, can be accumulated by the bioconcentration of food chain, just can endanger healthy once take in human body.Therefore, most important to the accurate detection of heavy metal ion in water.
Mercury is a kind of poisonous silvery white heavy metal element, and it is liquid metals unique under normal temperature, and dissociate and be present in nature and be present in cinnabar, calomel and other several ore deposits, symbol of element Hg, is commonly called as " mercury ".The inorganic compound of common mercury is 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 synthesis 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 metal such as gold, silver and thallium; Chemical industry mercury is made negative electrode and is produced caustic soda and chlorine with electrolytic salt solution; Some compounds of mercury are pharmaceutically having sterilization, diuresis and analgesic activity, and mercury silver alloy is good dental material, and what have is also used as treatment evil sore, mange etc. as medicine, all can cause poisoning when oral, excessive its dust of suction and skin application.
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 air, then can cause slow poisoning more than 0.1mg/m.The mercury of compound state is many in Powdered, can absorb through respiratory tract, skin, alimentary canal.Secondly the acute toxicity target organ mainly kidney of mercury is alimentary canal, lung etc.; Chronic toxicity target organ then mainly brain, alimentary canal and kidney.Its toxic mechanism roughly can be summarised as 3 points: 1, enzyme inhibition: mercury is for the various active groups of enzyme as amino, carboxyl, hydroxyl, phosphoryl, and particularly sulfydryl has high affinity, can combine with it and make enzyme deactivation; 2, activate mediated responses: after phospholipid hydrolysis procedure activation, arachidonic acid, thromboxane, oxygen radical etc. can be made to generate in a large number, cause tissue damage; 3, immunity is pathogenic: mercury not only can cause immunity glomerular injury, still can suppress T lymphocyte function, thus obstacle Organism immunoregulation is machine-processed.
Because mercury content is very low, Accurate Determining generally to need enrichment.At present, there is a lot of physics, an enrichment that chemical method is used to mercury, wherein, mainly contain electrolysis, the precipitation method, absorption method etc.But electrolysis energy consumption is higher, and easily causes secondary pollution; The precipitation method and physisorphtion can not be used for the detection of trace heavy metal ion.Chemistry closes by huge legendary turtle, namely adopts the coordination of intercalating agent and heavy metal ion in conjunction with Adsorption of Heavy Metal Ions, because of its can with heavy metal ion selectively acting, and can trace heavy metal ion be detected and receive much concern.Although, the material such as nano porous active carbon, amido modified block copolymer having the mesoporous silicon oxide, oxygen and the nitrogen that use coloured glaze base to modify to modify in recent years is 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 object of this invention is to provide a kind of preparation method of heavy metal Hg enrichment material.Concrete preparation method is:
(1) by clean, oven dry, the rice husk powder of pulverizing and the phosphoric acid solution of mass fraction 40% ~ 68%, the ratio being 1 ~ 3: 1 in rice husk powder and phosphoric acid solution mass ratio mixes, kneading is stirred 1 ~ 2 hour at 50 ~ 100 DEG C, add the methanol solution of tetramethoxy-silicane, continue to stir kneading 1 ~ 2 hour;
(2) above-mentioned compound is extruded on former, and be placed in drying box 80 ~ 120 DEG C of dryings 1.5 ~ 2.5 hours, be then placed in the isolated air heat treatment of 360 ~ 500 DEG C of resistance furnaces 2 ~ 3 hours, obtain granular materials;
(3) by palladium bichloride and glucose soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to be uniformly mixed 1 ~ 2 hour, discard filtrate to be directly placed in drying box and to dry, and at 150 ~ 220 DEG C heat reduction 5 ~ 10 minutes, obtain heavy metal Hg enrichment material.
Wherein, in step (2), extruded granular materials is that maximum particle diameter is no more than the spherical or cylindricality of 4 millimeters or goose is avette or sheet or bar shaped particle.In step (3), the main component of gained enrichment material is active carbon, and the mass fraction of Pd particle is 0.2 ~ 2.0%, SiO
2the mass fraction of particle is 2 ~ 8%.
With this material load Filter column or directly with treat that the water sample of enrichment mixes and soak, by mercury enrichment wherein, then can soak 8 hours with 25% phosphate aqueous solution, mercury can be proceeded to solution in the form of an ion.
Advantage of the present invention and effect:
1, can Sync enrichment free metal mercury and chemical combination state mercury;
2, preparation process is easy, and cost is low, non-secondary pollution;
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 with treat that the water sample of enrichment mixes or is placed in gaseous sample and can obtain enrichment object.
Detailed description of the invention
Embodiment 1
(1) by clean, oven dry, the rice husk powder of pulverizing and the phosphoric acid solution of mass fraction 43%, the ratio being 1.1: 1 in rice husk powder and phosphoric acid solution mass ratio mixes, at 52 DEG C, stir kneading 1 hour, add the methanol solution of tetramethoxy-silicane, continue to stir kneading 2 hours;
(2) above-mentioned compound is extruded on former, and be placed in drying box 82 DEG C of dryings 1.8 hours, be then placed in the isolated air heat treatment of 370 DEG C of resistance furnaces 3 hours, obtain granular materials;
(3) by palladium bichloride and glucose soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to be uniformly mixed 1 hour, discard filtrate to be directly placed in drying box and to dry, and at 160 DEG C heat reduction 8 minutes, obtain heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pd particle is 1.0%, SiO
2the mass fraction of particle is 3%.
Load the Filter column of more than 40 centimetres with this material, pending water sample normal pressure is crossed post once, can by the mercury ion enrichment more than 70% in water; By pending gaseous sample by this post once, can by Trace Mercury steam occlusion more than 80%; Then soak 8 hours with 25% phosphate aqueous solution, mercury can be proceeded to solution in the form of an ion.
Embodiment 2
(1) by clean, oven dry, the rice husk powder of pulverizing and the phosphoric acid solution of mass fraction 50%, the ratio being 2: 1 in rice husk powder and phosphoric acid solution mass ratio mixes, at 60 DEG C, stir kneading 1 hour, add the methanol solution of tetramethoxy-silicane, continue to stir kneading 2 hours;
(2) above-mentioned compound is extruded on former, and be placed in drying box 90 DEG C of dryings 2 hours, be then placed in the isolated air heat treatment of 380 DEG C of resistance furnaces 2 hours, obtain granular materials;
(3) by palladium bichloride and glucose soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to be uniformly mixed 1 hour, discard filtrate to be directly placed in drying box and to dry, and at 180 DEG C heat reduction 9 minutes, obtain heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pd particle is 0.5%, SiO
2the mass fraction of particle is 2.5%.
Load the Filter column of more than 40 centimetres with this material, pending water sample normal pressure is crossed post once, can by the mercury ion enrichment more than 70% in water; By pending gaseous sample by this post once, can by Trace Mercury steam occlusion more than 80%; Then soak 8 hours with 25% phosphate aqueous solution, mercury can be proceeded to solution in the form of an ion.
Embodiment 3
(1) by clean, oven dry, the rice husk powder of pulverizing and the phosphoric acid solution of mass fraction 60%, the ratio being 2.5: 1 in rice husk powder and phosphoric acid solution mass ratio mixes, at 80 DEG C, stir kneading 2 hours, add the methanol solution of tetramethoxy-silicane, continue to stir kneading 1 hour;
(2) above-mentioned compound is extruded on former, and be placed in drying box 100 DEG C of dryings 2.4 hours, be then placed in the isolated air heat treatment of 450 DEG C of resistance furnaces 2 hours, obtain granular materials;
(3) by palladium bichloride and glucose soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to be uniformly mixed 2 hours, discard filtrate to be directly placed in drying box and to dry, and at 200 DEG C heat reduction 6 minutes, obtain heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pd particle is 1.3%, SiO
1the mass fraction of particle is 4.1%.
Load the Filter column of more than 40 centimetres with this material, pending water sample normal pressure is crossed post once, can by the mercury ion enrichment more than 75% in water; By pending gaseous sample by this post once, can by Trace Mercury steam occlusion more than 80%; Then soak 8 hours with 25% phosphate aqueous solution, mercury can be proceeded to solution in the form of an ion.
Embodiment 4
(1) by clean, oven dry, the rice husk powder of pulverizing and the phosphoric acid solution of mass fraction 65%, the ratio being 2.8: 1 in rice husk powder and phosphoric acid solution mass ratio mixes, at 95 DEG C, stir kneading 1 hour, add the methanol solution of tetramethoxy-silicane, continue to stir kneading 2 hours;
(2) above-mentioned compound is extruded on former, and be placed in drying box 115 DEG C of dryings 1.5 hours, be then placed in the isolated air heat treatment of 480 DEG C of resistance furnaces 2 hours, obtain granular materials;
(3) by palladium bichloride and glucose soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to be uniformly mixed 1 hour, discard filtrate to be directly placed in drying box and to dry, and at 210 DEG C heat reduction 6 minutes, obtain heavy metal Hg enrichment material.
The main component of resulting materials is active carbon, and the mass fraction of Pd particle is 1.5%, SiO
2the mass fraction of particle is 7.5%.
Load the Filter column of more than 40 centimetres with this material, pending water sample normal pressure is crossed post once, can by the mercury ion enrichment more than 70% in water; By pending gaseous sample by this post once, can by Trace Mercury steam occlusion more than 80%; Then soak 8 hours with 25% phosphate aqueous solution, mercury can be proceeded to solution in the form of an ion.
Claims (2)
1. a preparation method for heavy metal Hg enrichment material, its preparation process is:
(1) by clean, oven dry, the rice husk powder of pulverizing and the phosphoric acid solution of mass fraction 40% ~ 68%, the ratio being 1 ~ 3: 1 in rice husk powder and phosphoric acid solution mass ratio mixes, kneading is stirred 1 ~ 2 hour at 50 ~ 100 DEG C, add the methanol solution of tetramethoxy-silicane, continue to stir kneading 1 ~ 2 hour;
(2) above-mentioned compound is extruded on former, and be placed in drying box 80 ~ 120 DEG C of dryings 1.5 ~ 2.5 hours, be then placed in the isolated air heat treatment of 360 ~ 500 DEG C of resistance furnaces 2 ~ 3 hours, obtain granular materials;
(3) by palladium bichloride and glucose soluble in water, under constantly stirring, above-mentioned granular materials is added wherein, continue to be uniformly mixed 1 ~ 2 hour, discard filtrate to be directly placed in drying box and to dry, and at 150 ~ 220 DEG C heat reduction 5 ~ 10 minutes, obtain heavy metal Hg enrichment material, wherein the mass fraction of Pd particle is 0.2 ~ 2.0%, SiO
2the mass fraction of particle is 2 ~ 8%.
2. the preparation method of a kind of heavy metal Hg enrichment material according to claim 1, is characterized in that described extruded granular materials is that maximum particle diameter is no more than the spherical or cylindricality of 4 millimeters or goose is avette or sheet or bar shaped particle.
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| CN201110192612.1A CN102872800B (en) | 2011-07-11 | 2011-07-11 | Preparation method of heavy metal mercury-enriched material |
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| CN102872800B true CN102872800B (en) | 2015-05-20 |
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| CN112175685B (en) * | 2019-07-02 | 2022-05-10 | 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 |
Citations (3)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5471142B2 (en) * | 2008-09-29 | 2014-04-16 | ソニー株式会社 | POROUS CARBON MATERIAL COMPOSITE AND PROCESS FOR PRODUCING THE SAME, AND ADSORBENT, COSMETIC, PURIFIER, AND PHOTOCATALYST COMPOSITE MATERIAL |
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2011
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Patent Citations (3)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 稻壳基活性炭制备及活性炭表面改性研究;厉悦;《中南林学院林产化工专业硕士学位论文》;20051116;第3页1.2.2.2.2化学活化法，第5页倒数第1行至第6页第2行，第16页2.3.2.2不去除硅条件下磷酸法制备活性炭，第30页4磷酸法制备稻壳活性炭的研究 * |
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