CN101862645A - Novel heavy metal absorbent - Google Patents
Novel heavy metal absorbent Download PDFInfo
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- CN101862645A CN101862645A CN200910130485A CN200910130485A CN101862645A CN 101862645 A CN101862645 A CN 101862645A CN 200910130485 A CN200910130485 A CN 200910130485A CN 200910130485 A CN200910130485 A CN 200910130485A CN 101862645 A CN101862645 A CN 101862645A
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Abstract
The invention relates to a preparation method of sulfur carbon nano composite material absorbent and application of the absorbent in recovery of heavy metal from a liquid phase or a gas phase. The preparation method of the absorbent comprises the following steps: fully stirring and mixing active carbon and sulfur substance in water by a vortex friction mixing method; and introducing molten-state sulfur substance on the surface in the pore canal of the active carbon particle by a melt infiltration method. In the sulfur carbon nano composite material, the sulfur substance is evenly attached on the surface and in pore canal of the active carbon material particle in an amorphous thin coating form. The sulfur carbon nano composite material has the remarkable characteristics of very large active specific surface area. The absorption principle is that a nano-thin layer of sulfur substance is used as a metal capture agent and a particle containing heavy metal, or steam, liquid drop and ion containing heavy metal to form a certain chemical action, and thereby the application that the heavy metal can be absorbed from the liquid phase and the gas phase can be realized.
Description
Technical field:
The present invention relates to a kind of new adsorbent that can reclaim heavy metal from liquid phase or in the gas phase, i.e. sulphur carbon nano-composite material adsorbent.The present invention relates to the application of this preparation of adsorbent method and this adsorbent absorption heavy metal from liquid phase and in the gas phase.
Background technology:
The compound that is present in the heavy metal in liquid phase or the gas phase or contains heavy metal is discharged in the middle of the natural environment, is not only the huge waste to resource, more people's health is caused great threat simultaneously.A variety of industrial wastewaters are exactly solution or the suspension that contains heavy metal; The hot brine that nuclear power station produces is the precious metal that contains low concentration, such as porpezite and ruthenium gold.Not treated heavy metal solution or suspension can cause the severe contamination of water resource and soil.These heavy metals may enter human body by food chain at last.On the other hand, especially mercury and compound thereof may directly be breathed and entered human body to swim in airborne heavy metal.About 10 kilograms mercury will be discharged in one month in one tame medium scale thermal power plant in air; Handling discarded fluorescent lamp improperly also is the important source of mercury pollution in the atmosphere; At dentist's clinic, as filling tooth material, the generally use of amalgam material more makes doctor and patient directly contact the mercury vapour of high concentration.Enter the heavy metal in the human body, usually can't natural metabolism, but deposition constantly, thereby to people's health particularly infant's health cause great infringement.For on the economic benefit and the reason in the ecological environmental protection, from liquid phase and in the gas phase, reclaim these heavy metals and have crucial meaning.This needs economy and adsorbent efficiently badly.
For the recovery of heavy metal in the liquid phase, existing processes all can not realize reclaiming from low concentration solution economical, efficiently.United States Patent (USP) 3985554 and United States Patent (USP) 4687514 proposes to use the metallic particles with reduction to come heavy metal ion in the reducing solution, thereby is settled out these heavy metals, and this method need be used the higher metal particle of price.United States Patent (USP) 4289531 propositions use the very high animal hair of protein content as the precious metal ion adsorbent, but because the chemical composition of animal hair is very complicated, thereby the later stage refinement that is adsorbed metal is caused very big obstacle.United States Patent (USP) 4619744 proposes to use water-soluble macromolecular material to come complexation heavy metal ion, makes it with the complex form precipitation, thereby isolate heavy metal from solution.But the production cost of these functional polymers is very high.United States Patent (USP) 4802920 proposes to use the pitch of sulfonation to reclaim metal as adsorbent, and it is not high that the shortcoming of this method is that this adsorbent reclaims the efficient of metal, and it is very big to refine the difficulty that is adsorbed metal.The method that United States Patent (USP) 5690806 uses electrolysis and active carbon adsorption to combine, this method require to use complicated accurate collection apparatus.United States Patent (USP) 7138643 has been introduced and has been used attached to the organophosphor on the activated carbon as the ion-exchange reagent method of folding and unfolding injectivity isotope metal back and forth.United States Patent (USP) 7300639 proposes to use a kind of extractant that contains hydrogen phosphide to extract the palladium of low concentration.Though phosphorus-containing compound has the effect of the heavy metal ion of catching, the toxicity of phosphide has limited this class The Application of Technology.Rely on the huge legendary turtle cooperation to require metal target to be had very strong active force attached to the adsorbing functional group of the execution on the carrier with the strategy of catching heavy metal ion; Simultaneously these functional groups will evenly distribute on carrier, and dispersiveness will reach maximization as far as possible, thereby make the area that has adsorption activity on the adsorbent big as far as possible.
For the compound that adsorbs heavy metal, especially mercury and mercury from gas phase, people have also done a large amount of work.United States Patent (USP) 1984164 and United States Patent (USP) 3662523 are introduced the absorbent charcoal material of the compound-modified mistake of using iodine and iodine respectively, adsorb the mercury in thermal power plant's waste gas.But because iodine and compound thereof are to be easy to distillation, perhaps the material of Fen Xieing causes the stable bad of these adsorbents.United States Patent (USP) 4196173 uses the active carbon of chlorinations or bromination as adsorbent, but needs to use chlorine with very severe corrosive and toxicity or simple substance bromine as oxidant in the preparation process of these materials.The production cost of the active carbon of modified is very high, more than 15 times of normally common active carbon cost.The titanic oxide material of the modified oxide of United States Patent (USP) 7404939 use vanadium is as adsorbent, but the adsorption activity of this material is starkly lower than the absorbent charcoal material of halogen modified.Sulphur simple substance can react with mercury simple substance, but the known material that contains sulphur simple substance does not all have enough big specific activity surface area, finishes the absorption to mercury efficiently.Present business-like removal of mercury material can not be removed the mercury in the gas phase effectively, economically.
The present invention introduces a kind of new adsorbent, and this material can adsorb heavy metal from liquid phase or in the gas phase.It is simple that this new adsorbent has production technology, cheap for manufacturing cost, and the high distinguishing feature of absorption property.
Summary of the invention:
The objective of the invention is to create a kind of economy, new adsorbent reclaims the heavy metal in the liquid phase or in the gas phase efficiently; Further, the objective of the invention is to use this novel sulphur carbon nano-composite material to reclaim heavy metal from solution, especially precious metal perhaps adsorbs particulate or the drop that contains heavy metal, perhaps steam, especially mercury from gas phase.The metal target that can be adsorbed among the present invention comprises all heavy metals, and their compound.Include but not limited to: manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, the alloy of bismuth and these metals.The existence form of heavy metal in liquid phase can be the metal particle or the alloy particle of zero-valent state, can be the metal ion of dissolving, also can be present in the compound.Heavy metal can be the metal particle or the alloy particle of zero-valent state in gas phase, for mercury, then is droplet or steam, also may reside in compound or the dust.Among the present invention, the solvent of liquid phase can be a water, but is not limited to water.Among the present invention, gas phase can be an air, but is not limited to air.
The present invention uses active carbon and elemental sulfur as feedstock production sulphur carbon nano-composite material, is used for adsorbing the heavy metal in the liquid phase or in the gas phase.Among the present invention, it is the material of main chemical composition element with elemental carbon that term " active carbon " means any except that diamond.Term among the present invention: " carbon " is meant that atomic number (atom proton number) is the various isotopes of 6 element.Active carbon can be any raw material of wood-charcoal material that is purchased, and also can be the non-raw material of wood-charcoal material that is purchased for preparing with any known method.Absorbent charcoal material includes but not limited to: football alkene, SWCN, double-walled carbon nano-tube, multi-walled carbon nano-tubes, the mesoporous charcoal of regular pore canal, the mesoporous charcoal in irregular duct, micropore charcoal, macroscopic pores charcoal, graphite, impalpable structure raw material of wood-charcoal material, carbon black, carbon fiber, carbonized polymeric.Among the present invention, the term in the active carbon " activity " is without any tangible physics or chemical sense.The specific area of absorbent charcoal material used herein can be between 0.1 square metre of every gram to 10000 square metre every gram, and preferred specific area is between 500 square metres of every grams to 6000 square metre every gram.The specific volume of active carbon can whenever restrain 20 cubic centimetres of every grams between 0.0001 cubic centimetre, and preferred specific volume whenever restrains 3 cubic centimetres of every grams between 0.1 cubic centimetre.The average pore size of the pore passage structure of active carbon can be between 0.1 dust to 1 millimeter, and preferred average pore size is between 0.5 nanometer to 100 nanometer.The pore passage structure of active carbon can be a long-range order, regularly arranged, also can be partly or completely unordered.The granular size of absorbent charcoal material can be a size arbitrarily, and grain sizes (diameter) is between 30 nanometers to 10 micron.To the selection of active carbon, preferred specific area is big, and specific volume is big, the absorbent charcoal material that particle size is little.Term among the present invention: " sulphur " is meant that atomic number (atom proton number) is 16 element.Being used for preparing the elemental sulfur of sulphur carbon nano-composite material adsorbent among the present invention, can be any elemental sulfur that is purchased, and can be the elemental sulfur for preparing with any known method, also can be that occurring in nature is naturally occurring.
The sulphur carbon nano-composite material is by whirlpool friction mixing method, and the method for fault sulphur simple substance fusing infiltration is synthesized.Preparation sulphur carbon nano-composite material, at first elemental sulfur and active carbon will reach good mixability.Among the present invention, release a kind of new sulphur charcoal mixed method, that is, sulphur simple substance and active carbon are mixed the aqueous phase of vigorous stirring, and this mixed method is named as whirlpool friction mixing method here.Aqueous phase, the active force that belongs to the active carbon of hydrophobic material and the similar blind date between the simple substance sulphur granule has guaranteed that they have an opportunity to meet, and under intense stirring condition, very strong rubbing action can take place between active carbon and the simple substance sulphur granule, because elemental sulfur is the very soft molecular crystal material of quality, only there is active force very weak Van der Waals force relatively in the molecular crystal between the sulfur molecule, so with the charcoal friction of granule effect can make part sulphur simple substance from original body mutually sulfur granules be scraped off, embed on the coarse surface of active carbon.This rubbing action makes active carbon and elemental sulfur can trend towards mixing substantially, embeds mutually even, increases contact area each other.The sulphur carbon mixture obtains after filtering.In mixture, sulphur simple substance can account for 0.1% to 90% of mixture gross mass.Preferred mass percentage is between 1% to 30%.Next, the elemental sulfur in the sulphur carbon mixture that obtains by whirlpool friction mixing method is to form nano thin-layer by the method for melting infiltration in the duct of absorbent charcoal material particle He on the surface.Term " thawing " means a kind of material at a certain temperature by solid-state transformation to liquid state.Term " infiltration " means in the pore passage structure that a kind of liquid is distributed to another kind of solid-state material here or lip-deep process especially.Because elemental sulfur and active carbon all are good hydrophobic materials, they have the characteristics of typical similar blind date, and interface tension force is very low.After the fusing of sulphur simple substance, molten sulfur is owing to capillarity promotes, by diffusion and infiltration, fully contact with the activated carbon granule surface as much as possible, be inhaled in the pore passage structure of raw material of wood-charcoal material or on the surface, thereby be coated on equably on the charcoal particle, form very thin sulphur coating.The mixture of molten sulfur and charcoal after supercooling, molten sulfur be cured on the surface of absorbent charcoal material particle with the duct in, become solid-state sulphur with impalpable structure.Arrive this, finished sulphur carbon nano-composite material preparation of adsorbent.Term: " amorphous " means sulfur molecule here and irregularly arranges, and do not have the molecule crystallographic texture of rule.To the temperature of sulphur carbon mixture heating should be between 119 ℃ and 200 ℃ certain temperature.When being lower than 119 ℃, sulphur simple substance can not form molten mass; Be higher than under the 200C condition sulfur molecule (S in the sulphur simple substance
8) can open octatomic ring, aggregate into the sulphur macromolecule (S of long-chain then
n, n＞8), the viscosity that this has increased molten sulfur simple substance has on the contrary reduced the flowability of sulphur simple substance, be unfavorable in its duct that is distributed to activated carbon granule equably and the surface on.
Among the present invention, remarkable technical characterictic in the preparation of sulphur carbon nano-composite material is: at first sulphur simple substance and active carbon are mixed effectively with whirlpool friction mixing method, introduce the sulphur coating effectively on the surface of activated carbon granule and in the duct by the fusing permeating method then.This amorphous sulphur is with on the surface of extremely thin one deck attached to the charcoal particle, and thickness of thin layer can be lower than 10 nanometers; Under suitable situation, can be lower than 3 nanometers; The thickness of sulphur thin layer is minimum among the present invention can arrive about 1 nanometer.Because the thickness of sulphur layer can be extremely low, so, be referred to as the sulphur carbon nano-composite material to the sulphur carbon composite among the present invention.
The sulphur carbon nano-composite material is to utilize the extensive chemical of sulphur nano thin-layer and metal to be used for realizing to the absorption of metal target in liquid phase or the gas phase.This is an another remarkable technical characterictic of the present invention.In adsorption process, as the material with adsorption activity, the sulphur coating has catches the particulate that contains heavy metal, perhaps drop, steam, the perhaps huge effect of heavy metal ion.This suction-operated will be given the credit to sulfur molecule (S
8) in the nonbonding orphan to valence electron.Great coordination can take place with the outermost layer unoccupied orbital (d track) of metal unoccupied orbital, especially transition metal to valence electron in these orphans, forms the Coordinative Chemistry key of certain intensity, thereby realizes catching of ABSORBENTS ABSORPTION metal.Being different from the absorption principle to other transition heavy metals, in the liquid phase or the absorption of air-borne mercury simple substance, is the combination reaction of utilizing sulphur simple substance and mercury simple substance, generates mercuric sulphide.Because the distribution of sulphur on the charcoal particle surface is extremely even, institute is so that the sulphur carbon nano-composite material possesses the very large remarkable technical advantage of specific activity surface area.For the absorption of heavy metal in the low concentration solution, the sulphur carbon nano-composite material is contacted fully with solution.For a spot of solution, the sulphur carbon nano-composite material directly can be distributed in the solution, then mixture is stirred fully, after mixture is filtered, obtain solid, promptly finish to the absorption of heavy metal in the solution with separate.For a large amount of solution, can use any known method by flow of solution, and circulation can decide the circulation adsorption time according to the exposure level of solution and sulphur carbon nano-composite material and the speed of flow of solution ceaselessly by the adsorbent equipment of sulphur carbon nano-composite material is housed.When the sulphur carbon nano-composite material reach absorption saturated after, can extract metal ingredient on the adsorbent with any known method, thereby realize recovery metal.
Description of drawings:
Fig. 1: by the elemental sulfur of whirlpool friction mixing method preparation and the electron scanning micrograph of the particle of the mixture of mesoporous charcoal with regular pore canal structure.Particle is positioned in the middle of the photo, and background is a black on every side.
Fig. 2: the X ray electron spectrum distribution map of carbon among Fig. 1 in the compound particles of elemental sulfur and mesoporous charcoal and element sulphur.
Fig. 3: after chloroplatinic acid is attracted on the sulphur carbon nano-composite material, the black background transmission electron microscope photo of mixture.Among the figure, bright spot is the chloroplatinic acid particulate, and particle size is about 1 nanometer; Grey color part is the sulphur carbon nano-composite material among the figure.Background is a black on every side.
Fig. 4: after chloroplatinic acid is adsorbed by the sulphur carbon nano-composite material, the aerial thermogravimetric analysis figure of mixture.Firing rate, 20 ℃ of per minutes.
Fig. 5: a kind of sulphur carbon nano-composite material adsorbent that uses is to the circulate schematic flow sheet of device of absorption of heavy metal in the solution.
The specific embodiment:
Following examples only are used to illustrate the present invention, and instruction those skilled in the art use the present invention, and these examples do not limit the present invention in any way.
Embodiment one:
Have meso-porous carbon material (CMK-3) 9.5 grams of regular pore canal structure and be purchased elemental sulfur 0.5 gram a kind of, be distributed in the container that fills 500 ml deionized water, with whirlpool friction mixing method two kinds of materials are mixed, promptly utilize electromagnetic agitation that mixture is stirred tempestuously and reach 2 hours.Mixture is filtered, remove the water in the mixture.What electron scanning micrograph showed among Fig. 1 is a surface topography by a particle of the sulphur carbon mix of whirlpool friction mixing method preparation, and the list structure of rule can be observed.Fig. 2 shows is the carbon in that sulphur carbon mixture particle and the X ray electronic energy spectrum of element sulphur among Fig. 1.Can see that element sulphur is distributed among the whole sulphur carbon mixture particle equably.The information that comprehensive scanning electron micrograph and X ray electronic energy spectrum provide can find that quite a few elemental sulfur has been distributed among the duct of mesoporous carbon, and this shows that this new whirlpool friction mixing method is very effective.Next, the material all in one piece of mixture is put into 125 ℃ of baking ovens, heats after 2 hours, a kind of with mesoporous carbon material with regular pore canal structure as the sulphur carbon nano-composite material of carrier just preparation finished.
Embodiment two:
With a kind of active carbon that is purchased, Graphon (Ketjen Black) 9.5 gram and be purchased elemental sulfur 0.5 gram adds one and fills in 500 milliliters the container of deionized water, utilize electromagnetic agitation that mixture is stirred 2 hours fully then after.Mixture is filtered, remove the water in the said mixture.Mixture is put into 125 ℃ of baking ovens, heat after 2 hours, a kind of sulphur carbon nano-composite material just preparation has finished.
Embodiment three:
It is that (chemical formula is H for 50/1000000ths chloroplatinic acid that sulphur carbon nano-composite material synthetic among the embodiment two 0.1 gram is distributed to 2 liters of concentration
2PtCl
6) the aqueous solution in.Subsequently mixture is stirred fully and reach 30 minutes.Then the solid filtering in the mixture is come out, thereby finish the separation of platinum element from solution.The composite that adsorbed chloroplatinic acid, its black background transmission electron microscope photo as shown in Figure 3.The bright spot that distributes among Fig. 3 is from the chloroplatinic acid particle with high cloud density that is attracted on the sulphur carbon nano-composite material.What Fig. 4 showed is the thermogravimetric analysis of adsorbing the composite of chloroplatinic acid.By analysis, be not difficult to learn that the sulphur carbon nano-composite material can adsorb the metal platinum of own wt 35% to the thermogravimetric result of the test.
Embodiment four:
The assembling of the adsorbent equipment of heavy metal in the low concentration solution, as shown in Figure 5.In each contactor, put into the sulphur carbon nano-composite material that 50 gram embodiment two synthesize.Driving mass percent concentration by pump is that 0.01% chloroplatinic acid aqueous solution flows, and solution flows through 3 contactors that the sulphur carbon nano-composite material is housed successively, and under the driving of pump, solution circulated 3 hours in adsorbent equipment.The solution that circulation was adsorbed is derived at last.The solution that adsorbed is carried out the analysis of inductively coupled plasma spectrometry method, and the concentration of finding chloroplatinic acid drops to percent 0.8 of initial concentration.Sulphur carbon nano-composite material in the adsorbent equipment can be reused.After the adsorption capacity limit that reaches these materials,, thereby obtain the oxide of heavy metal sulphur carbon nano-composite material adsorbent roasting in air of reclaiming.
Embodiment five:
It is to reach 72 hours in 1 cubic metre the closed container that whole parts of a fluorescent tube of just having broken and 5 gram sulphur carbon nano-composite materials are positioned over a volume jointly.Measure mercury vapour concentration in this container, note; With the whole parts of the fluorescent tube of other 1 same model after breaking be positioned over reached 72 hours in another closed container with 1 cubic metre of volume after, measure the mercury vapour concentration in this container.The concentration of finding mercury vapour in the former container is 2.1% of latter's container.
Claims (7)
1. sulphur carbon nano-composite material preparation of adsorbent method, and this adsorbent adsorbs the application of heavy metal in liquid phase or in the gas phase, it is characterized in that: in sulphur carbon nano-composite material preparation of adsorbent, at first utilize whirlpool friction mixing method that elemental sulfur and active carbon are mixed fully, solid mixture heating to obtaining after filtering then, thus realize sulphur simple substance be coated on the activated carbon granule surface with thin layer form and the duct in purpose; And then adsorbing heavy metal from liquid phase or in the gas phase, sulphur simple substance nano thin-layer and heavy metal in the sulphur carbon nano-composite material adsorbent form certain chemical action, thereby catch heavy metal; Especially, absorption simple substance mercury is to generate mercuric sulphide by sulphur simple substance in the sulphur carbon nano-composite material and the reaction of mercury simple substance to realize.
2. the heavy metal in the claim 1 includes but not limited to: manganese, iron, cobalt, nickel, copper, zinc; yttrium, zirconium, niobium, molybdenum, technetium; ruthenium, rhodium, palladium, silver, cadmium; hafnium, tantalum, tungsten, rhenium, osmium; iridium, platinum, gold, mercury, thallium; lead, bismuth and their alloy, the existence form of these metals: can be the metal of zero-valent state or alloying pellet, steam, drop, can be the ion in the solution, also may reside among compound particle or the dust granules.
3. the friction of the whirlpool in the claim 1 mixing method is to place aqueous phase to stir tempestuously active carbon and elemental sulfur, thereby realizes the abundant mixing of active carbon and elemental sulfur.
4. the coating of the sulphur simple substance thin layer in the claim 1 is to realize by the method for melting infiltration.
5. in the sulphur carbon nano-composite material adsorbent in the claim 1, elemental sulfur can account for percentage by weight 0.1% to 90%.
6. the heating process in the claim 1 is to realize under certain temperature between 119 ℃ and 200 ℃.
In the claim 1 for the catching of heavy metal in the liquid phase, necessary condition is that adsorbent is contacted fully with heavy metal solution or suspension.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249291A (en) * | 2011-04-07 | 2011-11-23 | 四川大学 | Process for control synthesis of nanometer mercuric sulfide particles based on sheep-anti-human antibody as soft template |
| CN103066248A (en) * | 2012-12-21 | 2013-04-24 | 中南大学 | Method for chemical doping of plumbum (Pb) on surface of cathode carbon material used for ultrabattery |
| CN103194696A (en) * | 2013-03-27 | 2013-07-10 | 南昌市婧麒服饰有限公司 | Ocean precipitation process for improving radiation protection performance of metal and iron-based mixture |
| CN104294044A (en) * | 2014-10-20 | 2015-01-21 | 贵研铂业股份有限公司 | Preparation method of activated carbon capable of selectively adsorbing palladium |
| CN104741077A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method of carbon adsorption material |
| CN105289490A (en) * | 2015-11-12 | 2016-02-03 | 福州大学 | Loaded-type bamboo shell adsorbent used for absorbing and separating rhenium as well as preparation method thereof |
| CN114716778A (en) * | 2022-03-25 | 2022-07-08 | 江苏新日电动车股份有限公司 | Spraying-free composite material for preventing heavy metal pollution and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559668A (en) * | 2004-03-11 | 2005-01-05 | 上海交通大学 | Electrochemical regeneration method of flue gas demercury adsorbing material |
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2009
- 2009-04-16 CN CN200910130485A patent/CN101862645A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559668A (en) * | 2004-03-11 | 2005-01-05 | 上海交通大学 | Electrochemical regeneration method of flue gas demercury adsorbing material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249291A (en) * | 2011-04-07 | 2011-11-23 | 四川大学 | Process for control synthesis of nanometer mercuric sulfide particles based on sheep-anti-human antibody as soft template |
| CN102249291B (en) * | 2011-04-07 | 2013-06-19 | 四川大学 | Process for control synthesis of nanometer mercuric sulfide particles based on sheep-anti-human antibody as soft template |
| CN103066248A (en) * | 2012-12-21 | 2013-04-24 | 中南大学 | Method for chemical doping of plumbum (Pb) on surface of cathode carbon material used for ultrabattery |
| CN103066248B (en) * | 2012-12-21 | 2015-11-18 | 中南大学 | A kind of method of superbattery negative pole charcoal material surface chemical doping Pb |
| CN103194696A (en) * | 2013-03-27 | 2013-07-10 | 南昌市婧麒服饰有限公司 | Ocean precipitation process for improving radiation protection performance of metal and iron-based mixture |
| CN103194696B (en) * | 2013-03-27 | 2015-08-19 | 南昌市婧麒服饰有限公司 | Improve ocean depositing technology and the iron based mixture of metal anti-radiation |
| CN104741077A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Preparation method of carbon adsorption material |
| CN104741077B (en) * | 2013-12-31 | 2018-06-19 | 西北大学 | A kind of preparation method of carbon adsorbing material |
| CN104294044A (en) * | 2014-10-20 | 2015-01-21 | 贵研铂业股份有限公司 | Preparation method of activated carbon capable of selectively adsorbing palladium |
| CN105289490A (en) * | 2015-11-12 | 2016-02-03 | 福州大学 | Loaded-type bamboo shell adsorbent used for absorbing and separating rhenium as well as preparation method thereof |
| CN105289490B (en) * | 2015-11-12 | 2018-05-04 | 福州大学 | A kind of support type bamboo shoot shell adsorbent for adsorbing separation rhenium and preparation method thereof |
| CN114716778A (en) * | 2022-03-25 | 2022-07-08 | 江苏新日电动车股份有限公司 | Spraying-free composite material for preventing heavy metal pollution and preparation method thereof |
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Application publication date: 20101020 |