CN101787654B - Preparation method of heavy metal ion enrichment cellulosic material - Google Patents
Preparation method of heavy metal ion enrichment cellulosic material Download PDFInfo
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- CN101787654B CN101787654B CN2010101041212A CN201010104121A CN101787654B CN 101787654 B CN101787654 B CN 101787654B CN 2010101041212 A CN2010101041212 A CN 2010101041212A CN 201010104121 A CN201010104121 A CN 201010104121A CN 101787654 B CN101787654 B CN 101787654B
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Abstract
The invention relates to a preparation method of heavy metal ion enrichment cellulosic material; in the method, natural cellulosic material fiber is adopted as the matrix, tetramethyl silane is take as the precursor and the surface sol-gel method is utilized to deposit silica film on the surface of the filter paper fiber; subsequently, ligand molecule monolayer sensitive to copper ion and mercury ion are introduced through self-assembly to obtain the heavy metal ion enrichment cellulosic material; the heavy metal ion solution can be simply filtered by the material prepared by the method of the invention to realize the absorption effect. The heavy metal ion enrichment cellulosic material has superior heavy metal ion enrichment performance, broad raw material source range, low price, simple preparation method, high absorption speed, high sensitiveness and can realize the treatment of waste water containing heavy ions simply, rapidly and economically.
Description
Technical field
The present invention relates to a kind of preparation method of heavy metal ion enrichment cellulosic material, particularly copper ion and mercury ion are had the preparation method of the finishing cellulosic material of concentration effect.
Background technology
In recent decades, along with developing rapidly of modern industry, many pollutants that contain heavy metal ion get into atmosphere, water and soil environment, have caused the serious environmental pollution.Heavy metal ion is difficult for decomposing, and is prone to cause secondary pollution, can accumulate through the bioconcentration of food chain, just can endanger healthy in case take in human body.Therefore, the purification of heavy metal ion just seems most important in the sewage.At present, there are a lot of physics, chemical method to be used to heavy metal ion enrichment, wherein, mainly contain electrolysis, the precipitation method, absorption method etc.But the electrolysis energy consumption is higher, and causes secondary pollution easily; The precipitation method and physisorphtion can not be used for the detection of trace heavy metal ion.The chemistry chelating promptly adopts chelating agent to combine 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 the trace heavy metal ion and receive much concern.Though, the mesoporous silicon oxide [Feng, the X. that use sulfydryl modification were arranged in recent years; Fryxell, G.E.; Wang, L.-Q.; Kim, A.Y.; Liu, J.; Kemner, K.M.Science 1997,276,923-926], nanoporous active carbon [Xio, B. that oxygen and nitrogen are modified; Thomas, K.M.Langmuir 2005,21,3892-3902], amido modified block copolymer [Bell, C.A.; Smith, S.V.; Whittaker, M.R.; Whittake, r A.K.; Gahan, L.R.; Monteiro, M.J.Adv.Mater.2006,18,582-586] etc. material be used for the report that heavy metal ion is handled, but because of its processing and preparing process is complicated, running cost is higher and be difficult to promote the use of.
Summary of the invention
One of the object of the invention provides a kind of heavy metal ion enrichment cellulosic material and synthetic method thereof that can be simple, rapid, economical; The absorption that two heavy metal ion enrichment cellulosic materials with preparation of purpose are used for heavy metal ion realizes the heavy metal ion sewage disposal.
The preparation method of a kind of heavy metal ion enrichment cellulosic material of the present invention, adopting the native cellulose fibre material is matrix, is precursor with the tetramethoxy-silicane, with the surface deposition silicon dioxide film of surperficial sol-gel process at fiber; Self assembly is subsequently introduced copper ion and the responsive ligand molecular individual layer of mercury ion, obtains heavy metal ion enrichment cellulosic material, and preparation process is following:
1), the native cellulose material fiber is handled: the native cellulose fibre material is placed the suction filtration device, use the ethanol rinse, air flow is drained, and said native cellulose fibre material comprises: quantitative filter paper, cotton, cloth;
2), deposition of silica film: the methanol solution of preparation tetramethoxy-silicane; Tetramethoxy-silicane solution joined flow through the native cellulose fibre material in the suction filtration device; Successively through absorption, washing, hydrolysis and drying cycles process, at the surface deposition nanometer level silicon dioxide film of fiber;
3), self assembly siloxanes: under the room temperature; The fiber that obtains depositing nanometer level silicon dioxide film in the step 2 is soaked in NTMS (N-3-(trimethoxy is silica-based) propyl group ethylenediamine) or STMS (3-sulfydryl propyl trimethoxy silicane) solution; Self assembly NTMS molecular monolayer or STMS molecular monolayer are available from the cellulosic material behind the assembling siloxanes;
4), with the cellulosic material behind the self assembly siloxanes, through rinse, drying, obtain the heavy metal ion enrichment cellulosic material of self assembly NTMS molecular monolayer or STMS molecular monolayer.
The process of depositing nano level silicon dioxide film of the present invention is: the quantitative filter paper in the step 1 is placed the suction filtration device, and adding concentration is 500mM, and solvent is the tetramethoxy-silicane solution of methyl alcohol, leaves standstill a few minutes, deposition absorption; Vacuum slowly is evacuated to the liquid level of solution near the filter paper surface, guarantees that filter paper is immersed in the solution all the time, and with the unreacted tetramethoxy-silicane solution of washed with methanol, the back adds methyl alcohol, leaves standstill a few minutes, and vacuum is taken out and remained methyl alcohol, adds pure water again, leaves standstill a few minutes hydrolysis; Last air flow dry filter paper; Just accomplished circulation of deposition/hydrolysis; The thickness of layer of silicon dioxide layer is about 0.75nm, obtains the silicon dioxide film of the nanometer level of different-thickness through the different number of times of Control Circulation.
Employed filter paper is common quantitative filter paper commonly used among the present invention, but the native cellulose fibre material is not limited thereto, and also can adopt cotton fiber, fabric fibre.
The silica coating of the nanometer level of fiber surface deposition is 10 layers among the present invention.
Self assembling process of the present invention is: the filter paper that will deposit nanometer level silicon dioxide film under the room temperature soaked in NTMS or STMS solution 24 hours, and the concentration of said NTMS or STMS solution is 1mM, and solvent is a toluene; Stirring at room 1 hour; Use toluene, chloroform, ethanol subsequently respectively; Pure water rinse, vacuumize then.
Reagent N TMS among the present invention and the structural formula of STMS are following:
The siloxanes that contains the particular functional group described in the present invention is not limited to NTMS and STMS, can be other contain can with the siloxane molecule of the functional group of heavy metal ion chelating.
The heavy metal ion enrichment cellulosic material of mentioning among the present invention is through the incompatible realization heavy metal ion enrichment of the huge legendary turtle of particular functional group in the siloxane molecule and heavy metal ion.As shown in Figure 1, amino combines with copper ion, sulfydryl combines with mercury ion, adopts heavy metal ion enrichment cellulosic material of the present invention, is to pass through the simple filtration process of cellulosic material under freely filtering, just enriching heavy metal ion fast.
The heavy metal ion enrichment cellulosic material that preparation method of the present invention obtains is used for heavy metal ion adsorbed method; With heavy metal ion enrichment cellulosic material, place the suction filtration device, add copper ion or mercury ion solution; Heavy metal ion solution is freely filtered down through cellulosic material; To filtrate adds in the suction filtration device once more, circulating filtration repeatedly, absorbing copper ion or mercury ion; Nano-fiber material behind absorbing copper ion or the mercury ion is removed cellulose and organic layer through calcining, obtain silica/cupric oxide or mercury oxide composite nano-tube material, reclaim copper or mercury element.
The present invention adopts self assembly NTMS (N-3-(trimethoxy is silica-based) propyl group ethylenediamine) molecular monolayer, because NTMS contains amino, utilizes the huge legendary turtle cooperation usefulness of amino and copper ion, and this heavy metal ion enrichment cellulosic material can be used for the absorption of copper ion.With the heavy metal ion enrichment cellulosic material of self assembly NTMS molecular monolayer, place the suction filtration device, add the copper nitrate solution 50mL of concentration 10ppm; It is freely filtered down, and will filtrate adds in the suction filtration device once more, so circulates 10 times; Copper ion concentration is reduced to 5ppm in the solution; Nano-fiber material behind the absorbing copper ion was calcined 6 hours down at 600 degrees centigrade, obtained silica/cupric oxide composite nano-tube material, reclaim copper.
The present invention adopts self assembly STMS (3-sulfydryl propyl trimethoxy silicane) molecular monolayer, because STMS contains sulfydryl, utilizes the huge legendary turtle cooperation of sulfydryl and mercury ion to use; This heavy metal ion enrichment cellulosic material can be used for the absorption of mercury ion; The metal ion enrichment cellulosic material of self assembly STMS molecular monolayer is placed the suction filtration device, add the mercuric nitrate solution 50mL of concentration 30ppm, it is freely filtered down; To filtrate and add once more in the suction filtration device; Circulate 10 times, ion concentration of mercury is reduced to 15ppm in the solution, and the nano-fiber material behind the absorption mercury ion was calcined 6 hours down at 600 degrees centigrade; Obtain silica/mercury oxide composite nano-tube material, reclaim mercury element.
The present invention proposes a kind of is the technology that raw material prepares heavy metal ion enrichment cellulosic material with the native cellulose fibre, and the property of imitation native cellulose fibre realizes combining and the application of material of microcosmic and macroscopic view.The native cellulose fibre material that is adopted among the present invention is general quantitative filter paper commonly used, and used native cellulose fibre material is not limited thereto, and can also adopt cotton, natural fiber materials such as cloth.Quantitative filter paper has the fiber web of a lot of microfibers and nanometer level to be interwoven, and has abundant loose structure and very big specific area, and good flexible and mechanical strength, and simultaneously, the significant Superhydrophilic matter also utmost point is beneficial to it and is applied in the water environment.Elder generation is with the silicon dioxide film of surperficial sol-gel process at filter paper fibre cellulose fiber surface deposition nanometer level among the present invention; Improved the reactivity of filter paper fibre; The siloxane molecule individual layer that contains the heavy metal ion ligand molecule is introduced in self assembly subsequently, has obtained heavy metal ion enrichment cellulosic material.
The material of the enriching heavy metal ion that provides of the present invention is simple, rapid, economical.The employing natural fabric is a raw material; The ligand molecular of introducing the counterweight metal ion-sensitive with the method for self assembly prepares heavy metal ion enrichment cellulosic material, and the functional material that is designed has excellent heavy metal ion enrichment performance because of the loose structure and the high internal surface area of natural fiber cellulosic material.It is abundant that research proof with filter paper is that the heavy metal ion enrichment material of matrix preparation has raw material sources, and cheap, the preparation method is simple, and adsorption rate is fast, and characteristics such as sensitivity height have remarkable advantages in the heavy metal ion sewage treatment process.
Advantage of the present invention and effect:
1. the native cellulose fibre material (filter paper) that the present invention adopted has very strong toughness and mechanical strength, and the source is abundant, and is cheap.Native cellulose fibre material among the present invention is not limited to general quantitative filter paper, can also be the cotton of using always, other native cellulose fibre materials such as cloth.
2. the preparation process reaction mild condition of heavy metal ion enrichment cellulosic material among the present invention, method of operating is easy, and cost is low, and is pollution-free.In addition, the heavy metal ion enrichment cellulosic material of preparation has lasting chemical stability.
3. easy and simple to handle when the heavy metal ion enrichment cellulosic material for preparing among the present invention uses, only need simply make the solution of heavy metal ion filter this material, just can reach adsorption effect.
4. the heavy metal ion enrichment cellulosic material for preparing among the present invention has very big specific area, so its sensitivity is very high, can detect trace heavy metal ion (ppm level).
5. the heavy metal ion enrichment cellulosic material for preparing among the present invention is removed the recovery that cellulose and organic layer just can easily be realized heavy metal through calcining after Adsorption of Heavy Metal Ions.
Description of drawings
Accompanying drawing 1 heavy metal ion enrichment cellulosic material microstructure sketch map with and counterweight metal ion (Cu
2+, Hg
2+) huge legendary turtle close the enrichment sketch map.Accompanying drawing 1a heavy metal ion enrichment cellulosic material microstructure sketch map; Among the figure: 1 is NTMS or STMS molecular monolayer, and 2 is heavy metal ion, and the deposition of silica layer is gone up on 3 surfaces; 4 is cellulose nano-fibrous, and accompanying drawing 1b is that self assembly NTMS molecular monolayer huge legendary turtle is closed enrichment Cu
2+Sketch map, accompanying drawing 1c are that STMS molecular monolayer huge legendary turtle is closed enrichment Hg
2+Sketch map.
Accompanying drawing 2 heavy metal ion enrichment cellulosic material Adsorption of Heavy Metal Ions (Cu
2+, Hg
2+) front and back change in concentration sketch map.
Calcining obtains the electromicroscopic photograph of sample behind the accompanying drawing 3 heavy metal ion enrichment cellulosic material absorbing copper ions, and accompanying drawing 3a and 3b are the stereoscan photograph of silica/oxide copper nanometer tube, and accompanying drawing 3c is the transmission electron microscope photo of silica/oxide copper nanometer tube.Illustration is a photo of calcining the silica/cupric oxide sample that obtains among the accompanying drawing 3a.
Calcining obtains the electromicroscopic photograph of sample behind the accompanying drawing 4 heavy metal ion enrichment cellulosic materials absorption mercury ion, and accompanying drawing 4a and 4b are the stereoscan photograph of silica/mercury oxide nanotube, and accompanying drawing 4c is the transmission electron microscope photo of silica/mercury oxide nanotube.Illustration is a photo of calcining the silica/mercury oxide sample that obtains among the accompanying drawing 4a.
The infared spectrum of accompanying drawing 5 metal oxide nanotubes, curve a, b, c are respectively the infared spectrum of silica, silica/cupric oxide, silica/mercury oxide.
The EDX collection of illustrative plates of accompanying drawing 6 metal oxide nanotubes, accompanying drawing 6a, 6b, 6c are respectively the EDX collection of illustrative plates of silica, silica/cupric oxide, silica/mercury oxide.
The specific embodiment
Embodiment 1: prepare heavy metal ion enrichment cellulosic material with method provided by the invention, and with the bivalent cupric ion in this material processed aqueous solution:
At first, the heavy metal ion enrichment cellulosic material among preparation the present invention.
1) the tetramethoxy-silicane solution of preparation 500mM, solvent is a methyl alcohol, stirring at room 2 hours.
2) common quantitative filter paper (production of Co., Ltd of Hangzhou, Zhejiang province city Xinhua) is placed the suction filtration device, with ethanol rinse 2 to 3 times, air flow is drained.Get 20mL tetramethoxy-silicane solution and join in the suction filtration device, left standstill 15 minutes, tetramethoxy-silicane is deposited on the filter paper fibre.
3) low vacuum slowly filters tetramethoxy-silicane solution, when liquid level of solution is surperficial near filter paper, adds methyl alcohol rinse 2 to 3 times, leaves standstill 1 minute.
4) the low vacuum suction filtration is removed residue methyl alcohol, adds the pure water rinse then 2 to 3 times, leaves standstill 10 minutes, and last air flow is drained.
So far, accomplish a deposition cycle, deposition layer of silicon dioxide film.Repeating step 2) and 3) obtain 10 layers of silicon dioxide film for 10 times.
5) be NTMS (N-3-(trimethoxy the is silica-based) propyl group ethylenediamine) solution of solvent preparation 1mM with toluene, stirred 1 hour under the room temperature.
6) at room temperature, the filter paper that deposits nanometer level silicon dioxide film of preparation was soaked in NTMS solution 24 hours, use toluene then respectively; Chloroform, ethanol, pure water rinse; Last vacuumize has obtained NTMS molecular monolayer heavy metal ion enrichment cellulosic material.
Heavy metal ion enrichment fibrous material structure chart is seen accompanying drawing 1a, and deposition of silica layer 3 is gone up on cellulose nano-fibrous 4 surfaces, and it is the heavy metal ion copper ion that NTMS or STMS molecular monolayer 1,2 are arranged on the silicon dioxide layer 3, heavy metal ion (Cu
2+, Hg
2+) huge legendary turtle close the enrichment sketch map and see accompanying drawing 1b and Fig. 1 c.
NTMS molecular monolayer heavy metal ion enrichment material is used for the absorption of copper ion.
This heavy metal ion enrichment cellulosic material is placed the suction filtration device, add the copper nitrate solution 50mL of concentration 10ppm, it is freely filtered down, will filtrate adds in the suction filtration device once more, so circulates 10 times, and copper ion concentration just can be reduced to 5ppm (Fig. 2) in the solution.Nano-fiber material behind the absorbing copper ion was calcined 6 hours down at 600 degrees centigrade, can be obtained silica/cupric oxide composite nano-tube material.Accompanying drawing 3a is the stereoscan photograph of its micron level, can see its filamentary structure significantly.Accompanying drawing 3b and 3c are respectively high power stereoscan photograph and transmission electron microscope photo, can find out nano tube structure clearly, the about 10nm of thickness of pipe wall, because the cellulose fibre thickness is uneven, external diameter of pipe does not wait from tens to the hundreds of nanometer.Compare with pure filter paper fibre; Above-mentioned electromicroscopic photograph has proved that this heavy metal ion enrichment cellulosic material both macro and micro all well inherited the form of filter paper fibre, and the microcosmic surface form of this explanation filter paper fibre is not damaged because of finishing silicon dioxide layer and NTMS molecular monolayer with its macroscopical mechanical performance.The infared spectrum of silica/cupric oxide composite nano-tube material, shown in curve b in the accompanying drawing 5, wherein 676,594cm
-1The symmetrical stretching vibration of the corresponding Cu-O in the peak at place.And the EDX collection of illustrative plates of silica/cupric oxide composite nano-tube material (accompanying drawing 6b) is gone up the appearance at copper peak, has proved that very intuitively the heavy metal ion enrichment cellulosic material of preparation truly has adsorption effect to copper ion.
Embodiment 2: prepare heavy metal ion enrichment cellulosic material with method provided by the invention, and with the dimercurion in this material processed aqueous solution:
At first, the heavy metal ion enrichment cellulosic material among preparation the present invention.
According to embodiment 1 preparation method and step, difference is that employing toluene is STMS (the 3-sulfydryl propyl trimethoxy silicane) solution of solvent preparation 1mM, has obtained STMS molecular monolayer heavy metal ion enrichment cellulosic material.
Then, STMS molecular monolayer heavy metal ion enrichment material is used for the absorption of mercury ion.
STMS molecular monolayer heavy metal ion enrichment cellulosic material is placed the suction filtration device; Add the mercuric nitrate solution 50mL of concentration 30ppm, it is freely filtered down, will filtrate adds in the suction filtration device once more; So circulation is 10 times, and ion concentration of mercury just can be reduced to 15ppm (Fig. 2) in the solution.Nano-fiber material behind the absorption mercury ion was calcined 6 hours down at 600 degrees centigrade, can be obtained silica/mercury oxide composite nano-tube material.The stereoscan photograph of its micron level can be seen its filamentary structure significantly shown in accompanying drawing 3a.Accompanying drawing 3b and 3c are respectively high power stereoscan photograph and transmission electron microscope photo, can find out nano tube structure clearly, the about 10nm of thickness of pipe wall, and external diameter of pipe does not wait from tens to the hundreds of nanometer owing to cellulose fibre thickness inequality.Through comparing with pure filter paper fibre; Above-mentioned electromicroscopic photograph has proved that this heavy metal ion enrichment cellulosic material both macro and micro all well inherited the form of filter paper fibre, and the microcosmic surface form of this explanation filter paper fibre is not damaged because of finishing silicon dioxide layer and STMS molecular monolayer with its macroscopical mechanical performance.The infared spectrum of silica/mercury oxide composite nano-tube material, shown in curve c in the accompanying drawing 5,668cm wherein
-1The symmetrical stretching vibration of the corresponding Hg-O in the peak at place.And the heavy metal ion enrichment cellulosic material that the EDX collection of illustrative plates of silica/mercury oxide composite nano-tube material (accompanying drawing 6c) is gone up the appearance at mercury element peak has proved preparation very intuitively truly has adsorption effect to mercury ion.
Claims (9)
1. the preparation method of the two heavy metal species ion enrichment cellulosic materials that constitute of a copper, mercury element, adopting the native cellulose material fiber is matrix, is precursor with the tetramethoxy-silicane, with the surface deposition silicon dioxide film of surperficial sol-gel process at fiber; Self assembly is subsequently introduced copper ion and the responsive ligand molecular individual layer of mercury ion, obtains the enrichment cellulosic material of two heavy metal species ions of copper, mercury element formation, and preparation process is following:
1), the native cellulose material fiber is handled: the native cellulose material fiber is placed the suction filtration device, use the ethanol rinse, air flow is drained, and said native cellulose material fiber is quantitative filter paper or cotton or cloth;
2), deposition of silica film: the methanol solution of preparation tetramethoxy-silicane; Tetramethoxy-silicane solution joined flow through the native cellulose material fiber in the suction filtration device; Successively through absorption, washing, hydrolysis and drying cycles process, at the surface deposition nanometer level silicon dioxide film of fiber;
3), self assembly siloxanes: under the room temperature; With step 2) in obtain depositing nanometer level silicon dioxide film the native cellulose material fiber soak in NTMS or STMS siloxane solution; NTMS is: N-3-(trimethoxy is silica-based) propyl group ethylenediamine; STMS is: 3-sulfydryl propyl trimethoxy silicane, and self assembly NTMS molecular monolayer or STMS molecular monolayer are available from the cellulosic material behind the assembling siloxanes;
4), with the cellulosic material behind the self assembly siloxanes, through rinse, drying, obtain the enrichment cellulosic material of the two heavy metal species ions that the copper, mercury element of self assembly NTMS molecular monolayer or STMS molecular monolayer constitute.
2. preparation method according to claim 1 is characterized in that: the native cellulose material fiber is: quantitative filter paper.
3. preparation method according to claim 1 and 2; It is characterized in that: the process of depositing nano level silicon dioxide film is: the quantitative filter paper after will handling places the suction filtration device; Adding concentration is 500mM, and solvent is the tetramethoxy-silicane solution of methyl alcohol, leaves standstill deposition absorption; The liquid level that vacuum slowly is evacuated to solution guarantees that near the quantitative filter paper surface quantitative filter paper is immersed in the solution all the time, and with the unreacted tetramethoxy-silicane solution of washed with methanol, adding methyl alcohol in back leaves standstill final vacuum and takes out and remain methyl alcohol, adds pure water again, leaves standstill hydrolysis; Last air flow dry filter paper; Accomplished circulation of deposition/hydrolysis; The thickness of layer of silicon dioxide layer is 0.75nm, obtains the silicon dioxide film of the nanometer level of different-thickness through the different number of times of Control Circulation.
4. preparation method according to claim 3 is characterized in that: the silica coating of the nanometer level of fiber surface deposition is 10 layers.
5. preparation method according to claim 1; It is characterized in that: self assembly siloxanes process is: the filter paper that will deposit nanometer level silicon dioxide film under the room temperature soaked in NTMS or STMS solution 24 hours; The concentration of NTMS or STMS solution is 1mM; Solvent is a toluene, stirring at room 1 hour.
6. the preparation method of heavy metal ion enrichment cellulosic material according to claim 1, it is characterized in that: the cellulosic material behind the self assembly siloxanes is used toluene successively, chloroform, ethanol, pure water rinse respectively.
7. the enrichment cellulosic material of two heavy metal species ions of the copper of the described preparation method's acquisition of claim 1, mercury element formation is used for the adsorption method of two heavy metal species ions of copper, mercury element formation; It is characterized in that: with the copper of self assembly NTMS molecular monolayer or STMS molecular monolayer, the two heavy metal species ion enrichment cellulosic materials that mercury element constitutes; Place the suction filtration device; Add copper ion or mercury ion solution, the two heavy metal species ion solution that copper, mercury element constitute are freely filtered down through cellulosic material, and will filtrate adds in the suction filtration device once more; Circulating filtration repeatedly, absorbing copper ion or mercury ion; Nano-fiber material behind absorbing copper ion or the mercury ion is removed cellulose and organic layer through calcining, obtain silica and cupric oxide or silica and mercury oxide composite nano-tube material, reclaim copper or mercury element.
8. adsorption method according to claim 7 is characterized in that: the absorption of copper ion, with the heavy metal ion enrichment cellulosic material of self assembly NTMS molecular monolayer; Place the suction filtration device, add the copper nitrate solution 50mL of concentration 10ppm, it is freely filtered down; To filtrate and add once more in the suction filtration device; So circulation is 10 times, and copper ion concentration is reduced to 5ppm in the solution, and the nano-fiber material behind the absorbing copper ion was calcined 6 hours down at 600 degrees centigrade; Obtain silica and cupric oxide composite nano-tube material, reclaim copper.
9. adsorption method according to claim 7 is characterized in that: the absorption of mercury ion places the suction filtration device with the metal ion enrichment cellulosic material of self assembly STMS molecular monolayer; The mercuric nitrate solution 50mL that adds concentration 30ppm; It is freely filtered down, and will filtrate adds in the suction filtration device once more, circulates 10 times; Ion concentration of mercury is reduced to 15ppm in the solution; Nano-fiber material behind the absorption mercury ion was calcined 6 hours down at 600 degrees centigrade, obtained silica and mercury oxide composite nano-tube material, reclaim mercury element.
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| CN102658094B (en) * | 2012-05-04 | 2014-03-05 | 湖北天思科技股份有限公司 | Silicon oxide and cellulose nano composite adsorbent and preparation method thereof |
| EP2796434A1 (en) * | 2013-04-23 | 2014-10-29 | Redco NV | Process for the treatment of cellulose fibers |
| CN103585963B (en) * | 2013-08-15 | 2016-03-23 | 盐城工学院 | A kind of chromate waste water process biological adsorption agent preparation method and application thereof |
| CN103730645B (en) * | 2014-01-17 | 2015-11-18 | 江苏华盛精化工股份有限公司 | Coated carbon fiber nanometer composite material of a kind of silicon and its preparation method and application |
| CN104368316B (en) * | 2014-11-18 | 2016-05-04 | 辽宁大学 | A kind of hydrosulfide group cellulose class stalk adsorbent and preparation method and the recovery to noble silver |
| CN105331367B (en) * | 2015-10-29 | 2019-06-28 | 广西大学 | The preparation method of modified paper mill sludge soil heavy metal passivant |
| CN106178696B (en) * | 2016-07-04 | 2019-01-18 | 东南大学 | Nano-fiber material and preparation method for mercury polymorphic in atmosphere acquisition |
| FR3057581B1 (en) | 2016-10-14 | 2021-12-10 | Commissariat Energie Atomique | TEXTILE MATERIAL COATING PROCESS |
| FR3061724B1 (en) | 2017-01-06 | 2021-07-16 | Commissariat Energie Atomique | TEXTILE MATERIAL COATING PROCESS |
| CN109187384B (en) * | 2018-08-14 | 2021-02-05 | 广东省测试分析研究所（中国广州分析测试中心） | Mercury enrichment material in water sample and headspace mercury enrichment and measurement method |
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