CN109277074A - A kind of preparation method of metal ion adsorption material - Google Patents
A kind of preparation method of metal ion adsorption material Download PDFInfo
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- CN109277074A CN109277074A CN201811147549.8A CN201811147549A CN109277074A CN 109277074 A CN109277074 A CN 109277074A CN 201811147549 A CN201811147549 A CN 201811147549A CN 109277074 A CN109277074 A CN 109277074A
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Abstract
The present invention provides a kind of preparation methods of metal ion adsorption material, include: S1) nano titanium oxide powder, zinc oxide nano-powder, alkali metal hydroxide are mixed in water with silica-alumina gel, hydro-thermal reaction is carried out, the titania nanotube intermediate of load zinc oxide is obtained；S2 after) handling the titania nanotube intermediate of the load zinc oxide with acid solution, roasting obtains metal ion adsorption material.Compared with prior art, the present invention carries out pipe surface load and filling in pipe to titania nanotube using Zinc oxide nanoparticle material, can effectively adsorb to metal ion electrically charged in ethyl orthosilicate；And since titania nanotube structure has great specific surface area, its contact with metal ion adsorption material is increased, to improve the adsorption efficiency of metal ion adsorption material；Furthermore metal ion adsorption material can be such that active material will not fall off and avoid secondary pollution using silica-alumina gel as support materials.
Description
Technical field
The invention belongs to adsorbent material technical field more particularly to a kind of preparation methods of metal ion adsorption material.
Background technique
Semiconductor IC industry is new high-tech industry with the fastest developing speed at present, the increasingly weight by various countries
Depending on, development speed have exceeded fastly people's it is anticipated that the ultra-pure electronic chemical product to match therewith world's average growth rate per annum
It is maintained at 8% or more, is field with fastest developing speed in chemical industry.
In recent years, the ultra-pure electronic chemical product industrial development in China is synchronous with the world, and development is swift and violent, in recent years ultra-pure electricity
The sub- manufacturing average growth rate per annum of chemicals has been more than 20%, is the high technology content risen now, high investment, high added value
New high-tech industry will become one of industry with the fastest developing speed, most active in chemical industry.Also, ultra-pure electricity
Sub- chemicals is important one of the backing material of semiconductor IC industry, and the quality of quality will directly affect semiconductor
The quality of integrated power chips.
Ethyl orthosilicate (TEOS) is mainly used for the integrated electricity of semiconductor as one kind important in ultra-pure electronic chemical product
TEOS is specially flashed to gaseous state from liquid first, then 700~750 by the LPCVD technique in the chip manufacturing proces of road
DEG C, it is decomposed under 50Pa pressure and deposits generation silica membrane in silicon chip surface.
The minim metal doped of silica membrane will change its semiconducting behavior, just will affect the property of final chip
Energy.It therefore, be to the metal ion strict control in raw material TEOS in semiconductor integrated circuit chip production process.But
The purifying process removed both at home and abroad to metal ion in TEOS at present, mainly in the way of rectifying, and rectifying mode is to boiling
The point biggish impurity composition of difference can effectively remove, and undesirable to metal ion removal effect.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of metal ion adsorption material
The metal ion adsorption material of method, this method preparation can effectively remove the metal ion in ethyl orthosilicate.
The present invention provides a kind of preparation methods of metal ion adsorption material, comprising:
S1) nano titanium oxide powder, zinc oxide nano-powder, alkali metal hydroxide and silica-alumina gel are mixed in water
It closes, carries out hydro-thermal reaction, obtain the titania nanotube intermediate of load zinc oxide；
S2 after) handling the titania nanotube intermediate of the load zinc oxide with acid solution, roasting obtains metal
Ion adsorbing material.
Preferably, the nano titanium oxide powder is the nano titanium oxide powder based on Anatase；The zinc oxide nano
Rice flour body is preferably the zinc oxide nano-powder based on buergerite phase.
Preferably, the partial size of the nano titanium oxide powder is 10~50nm；The partial size of the zinc oxide nano-powder is 2
~10nm.
Preferably, the molar ratio of the nano titanium oxide powder and zinc oxide nano-powder is (0.2~0.6): (0.1~
0.3)。
Preferably, the molar ratio of the nano titanium oxide powder and alkali metal hydroxide is (0.2~0.6): (0.4~
6)；The ratio of the nano titanium oxide powder and water is preferably (0.2~0.6) mol:(200~600) ml.
Preferably, the ratio of the nano titanium oxide powder and silica-alumina gel is (0.2~0.6) mol:(30~100) g.
Preferably, the step S1) specifically: by nano titanium oxide powder, zinc oxide nano-powder and alkali metal hydrogen-oxygen
Compound is mixed with water, and silica-alumina gel is then added and carries out hydro-thermal reaction after concussion mixing, obtains the titanium dioxide of load zinc oxide
Titanium nanotube intermediate.
Preferably, the concussion mixed time is 0.5~2h；The temperature of the hydro-thermal reaction is 120 DEG C~160 DEG C；
The time of the hydro-thermal reaction is 6~10h.
Preferably, the pH value of the acid solution is 3~5；The time of the acid solution processing is 5~10h；The roasting
Temperature is 300 DEG C~400 DEG C；The time of the roasting is 1~2h.
The present invention also provides a kind of adsorption of metal ions devices, including above-mentioned metal ion adsorption material.
The present invention provides a kind of preparation methods of metal ion adsorption material, comprising: S1) by nano titanium oxide powder,
Zinc oxide nano-powder, alkali metal hydroxide mix in water with silica-alumina gel, carry out hydro-thermal reaction, obtain load zinc oxide
Titania nanotube intermediate；S2) the titania nanotube intermediate of the load zinc oxide is handled with acid solution
Afterwards, it roasts, obtains metal ion adsorption material.Compared with prior art, the present invention is using Zinc oxide nanoparticle material to two
Titanium oxide nanotubes carry out pipe surface load and filling in pipe, by the coupling between nanoparticle, obtain semiconductors coupling
Body, since the fermi level of two kinds of semiconductors is different, photo-generated carrier is transmitted and is divided between the different semiconductor of energy gap
Analysis, to inhibit the compound of photo-generated carrier, can produce a large amount of electrons and holes, and then can be effectively to ethyl orthosilicate
In electrically charged metal ion adsorbed；And it, can be with since titania nanotube structure has great specific surface area
Contact of the ethyl orthosilicate gas with metal ion adsorption material is increased, while ethyl orthosilicate gas can also pass freely through metal
The inside of ion adsorbing material further increases its contact with metal ion adsorption material, to improve metal ion
The adsorption efficiency of adsorbent material；Furthermore metal ion adsorption material can make active material will not using silica-alumina gel as support materials
It falls off and avoids secondary pollution, while can also realize reuse.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of metal ion adsorption material, comprising: S1) by nano titanium oxide powder,
Zinc oxide nano-powder, alkali metal hydroxide mix in water with silica-alumina gel, carry out hydro-thermal reaction, obtain load zinc oxide
Titania nanotube intermediate；S2) the titania nanotube intermediate of the load zinc oxide is handled with acid solution
Afterwards, it roasts, obtains metal ion adsorption material.
The present invention is not particularly limited the source of all raw materials, is commercially available.
Wherein, the nano titanium oxide powder is nano titanium oxide powder well known to those skilled in the art, can
For one of Detitanium-ore-type, rutile-type and brookite type nano titanium oxide powder or a variety of, special limitation, this hair are had no
It is preferably the nano titanium oxide powder based on Anatase in bright；The partial size of the nano titanium oxide powder is preferably 10~
50nm。
The zinc oxide nano-powder be zinc oxide nano-powder well known to those skilled in the art, can for
One of zincblende lattce structure, NaCl structure, CsCl structure and wurtzite structure or a variety of zinc oxide nano-powders, have no spy
Different limitation, the zinc oxide nano-powder in the present invention preferably based on buergerite phase；The partial size of the zinc oxide nano-powder
Preferably 2~10nm.
Nano titanium oxide powder, zinc oxide nano-powder, alkali metal hydroxide are mixed in water with silica-alumina gel, it is excellent
After choosing first mixes nano titanium oxide powder, zinc oxide nano-powder, alkali metal hydroxide with water, silica-alumina gel is added；
The molar ratio of the nano titanium oxide powder and zinc oxide nano-powder is preferably (0.2~0.6): (0.1~0.3)；The alkali
Metal hydroxides is alkali metal hydroxide well known to those skilled in the art, has no special limitation, in the present invention
Preferably sodium hydroxide and/or potassium hydroxide；The molar ratio of the nano titanium oxide powder and alkali metal hydroxide is preferably
(0.2~0.6): (0.4~6)；The ratio of the nano titanium oxide powder and water preferably (0.2~0.6) mol:(200~
600)ml；In the present invention, it is preferred to for by alkali metal hydroxide and water in the form of alkali metal hydroxide aqueous solution and oxygen
Change nano-ti powder body and zinc oxide nano-powder mixing；The concentration of the alkali metal hydroxide aqueous solution is preferably 5~
10mol/L。
After mixing, silica-alumina gel is added, then preferred concussion mixing, then carries out hydro-thermal reaction；The titanium dioxide
The ratio of nano-powder and silica-alumina gel is preferably (0.2~0.6) mol:(30~100) g；The concussion mixed time is preferred
For 0.5~2h；The temperature of the hydro-thermal reaction is preferably 120 DEG C~160 DEG C；The time of the hydro-thermal reaction is preferably 6~
10h；The hydro-thermal reaction preferably carries out in closed autoclave, more preferably carries out in closed water heating kettle；The hydro-thermal
The liner of kettle is preferably polytetrafluoroethylene material, and outer wall is preferably metal material, after heating, it is possible to produce high temperature and pressure it is anti-
Answer environment.
It after hydro-thermal reaction, preferably washes, obtains the titania nanotube intermediate of load zinc oxide；Time of the washing
Number preferably 2~10 times, more preferably 3~7 times, be further preferably 5~6 times.
In the initial stage of hydro-thermal reaction, due to the effect of alkali metal hydroxide, titanium dioxide nanocrystalline grain is changed into
Product with sheet-like morphology, this is because by the oxidation state multiform reacted with alkali hydroxide soln at stratiform
The alkali metal titanium salt of structure, to can lead to the generation of tablet；With the increase of hydrothermal conditions, tablet is gradually crimped
At short nanotube, this spontaneous curling is the collective effect multifactor due to electrostatic, surface area and elastic deformation etc., with drop
Low energy；When further extending the hydro-thermal reaction time, nanotube can further increase, but when nanotube is long to a certain extent
Afterwards, i.e., no longer increase with the increase of the hydro-thermal reaction time.
The titania nanotube intermediate of the load zinc oxide is handled with acid solution；The side of the acid solution processing
Method is method well known to those skilled in the art, has no special limitation, will preferably load the two of zinc oxide in the present invention
Titanium oxide nanotubes intermediate impregnates in acid solution；The acid solution is preferably hydrochloric acid solution；The pH value of the acid solution is excellent
It is selected as 3~5；The time of the immersion, that is, acid solution processing time is preferably 5~10h.
It after acid solution processing, preferably washes, after dry, then is roasted, obtain metal ion adsorption material；The washing
It is preferred that being cleaned using deionized water；The temperature of the drying is preferably 60 DEG C~100 DEG C, and more preferably 70 DEG C~90 DEG C, then it is excellent
It is selected as 80 DEG C；The temperature of the roasting is preferably 300 DEG C~400 DEG C；The time of the roasting is preferably 1~2h.
The present invention carries out pipe surface load and filling in pipe to titania nanotube using Zinc oxide nanoparticle material,
By the coupling between nanoparticle, semiconductors coupling body is obtained, its essence is a kind of semiconductors to another semiconductor
Modification；Since the fermi level of two kinds of semiconductors is different, photo-generated carrier carried out between the different semiconductor of energy gap transmission and
Analysis, to inhibit the compound of photo-generated carrier, can produce a large amount of electrons and holes, and then can be effectively to positive silicic acid second
Electrically charged metal ion is adsorbed in ester；And it, can since titania nanotube structure has great specific surface area
To increase contact of the ethyl orthosilicate gas with metal ion adsorption material, while ethyl orthosilicate gas can also pass freely through gold
Belong to ion adsorbing material inside, further increase its contact with metal ion adsorption material, thus improve metal from
The adsorption efficiency of sub- adsorbent material；Furthermore metal ion adsorption material can make active material not using silica-alumina gel as support materials
It can fall off and avoid secondary pollution, while can also realize reuse.
The present invention has also passed through a kind of adsorption of metal ions device, including above-mentioned metal ion adsorption material；The gold
Category ion adsorbing material, which is preferably seated in rustless steel container, obtains adsorption of metal ions device.
The adsorption of metal ions device can be connected to ultrapure ethyl orthosilicate preparation process in the way of a preparation and a use
In production line.
In order to further illustrate the present invention, with reference to embodiments to a kind of metal ion adsorption material provided by the invention
Preparation method detailed description.
Reagent used in following embodiment is commercially available.
Embodiment 1
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 2
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.2mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 3
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.3mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 4
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.4mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 5
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.6mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 6
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 600ml5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 7
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 10mol/L, is then added
30g silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 8
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 70g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 9
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, is then added
100g silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 2h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 10
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 160 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 11
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 10h are loaded after cleaning 5 times with deionized water
The titania nanotube intermediate of zinc oxide.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 12
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 160 DEG C of heat preservation 10h are loaded after cleaning 5 times with deionized water
The titania nanotube intermediate of zinc oxide.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 13
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 5 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 14
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
The titania nanotube intermediate for loading zinc oxide is impregnated into 10h in the HCl solution that pH value is 3, then is spent
Ionized water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 15
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
The titania nanotube intermediate for loading zinc oxide is impregnated into 10h in the HCl solution that pH value is 5, then is spent
Ionized water cleaning, dries in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Embodiment 16
Mutually it is by nano titanium oxide powder (partial size 10nm), the 0.1mol buergerite based on 0.2mol spherical shape Anatase
Main zinc oxide nano-powder (partial size 2nm) is uniformly mixed with the sodium hydroxide solution of 200ml 5mol/L, and 30g is then added
Silica-alumina gel comes into full contact with silica-alumina gel and solution, obtains mixture after concussion mixes 0.5h.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h, after cleaning 5 times with deionized water, obtains load oxygen
Change the titania nanotube intermediate of zinc.
By the titania nanotube intermediate for loading zinc oxide pH value be 3 HCl solution in impregnate 5h, then spend from
Sub- water cleaning, dries in 80 DEG C of baking ovens, is put into 400 DEG C of sintering furnaces and is sintered 2h, obtain metal ion adsorption material.
Comparative example 1
By the nano titanium oxide powder (partial size 10nm) and 200ml 5mol/L based on 0.2mol spherical shape Anatase
Sodium hydroxide solution is uniformly mixed, and 30g silica-alumina gel is then added keeps silica-alumina gel and solution abundant after concussion mixes 0.5h
Contact, obtains mixture.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h obtain titanium dioxide after cleaning 5 times with deionized water
Titanium nanotube intermediate.
Titania nanotube intermediate is impregnated into 5h in the HCl solution that pH value is 3, then is cleaned with deionized water, in
It is dried in 80 DEG C of baking ovens, is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Comparative example 2
By the hydroxide of zinc oxide nano-powder (partial size 2nm) and 200ml 5mol/L based on 0.1mol buergerite phase
Sodium solution is uniformly mixed, and 30g silica-alumina gel is then added to be come into full contact with silica-alumina gel and solution, obtain after concussion mixes 0.5h
To mixture.
Mixture is placed in closed water heating kettle, 120 DEG C of heat preservation 6h obtain centre after cleaning 5 times with deionized water
Body.
Intermediate is impregnated into 5h in the HCl solution that pH value is 3, then is cleaned with deionized water, is dried in 80 DEG C of baking ovens,
It is put into 300 DEG C of sintering furnaces and is sintered 1h, obtain metal ion adsorption material.
Metal ion adsorption material obtained in 1~embodiment of embodiment 16 and comparative example 1~2 is respectively charged into stainless steel
In container, the lower part of the rustless steel container is provided with gas access, and top is provided with gas vent, and ethyl orthosilicate is heated
It to 150 DEG C, is passed through after forming ethyl orthosilicate gas by gas access, collects the ethyl orthosilicate that gas vent obtains, and examine
The content of wherein metal ion is surveyed, the test of metal ion uses icp ms (ICP-MS), tied
Fruit is shown in Table 1~table 4, and on-line analysis detects metal ion in high-purity ethyl orthosilicate and requires no more than 0.02ppb.
The content of metal ion in 1 ethyl orthosilicate unstrpped gas of table
The content of metal ion after 2 ethyl orthosilicate gas treatment of table
The content of metal ion after 3 ethyl orthosilicate gas treatment of table
The content of metal ion after 4 ethyl orthosilicate gas treatment of table
Claims (10)
1. a kind of preparation method of metal ion adsorption material characterized by comprising
S1) nano titanium oxide powder, zinc oxide nano-powder, alkali metal hydroxide are mixed in water with silica-alumina gel, into
Row hydro-thermal reaction obtains the titania nanotube intermediate of load zinc oxide；
S2 after) handling the titania nanotube intermediate of the load zinc oxide with acid solution, roasting obtains metal ion
Adsorbent material.
2. preparation method according to claim 1, which is characterized in that the nano titanium oxide powder is based on Anatase
Nano titanium oxide powder；The zinc oxide nano-powder is preferably the zinc oxide nano-powder based on buergerite phase.
3. preparation method according to claim 1, which is characterized in that the partial size of the nano titanium oxide powder be 10~
50nm；The partial size of the zinc oxide nano-powder is 2~10nm.
4. preparation method according to claim 1, which is characterized in that the nano titanium oxide powder and zinc oxide nano
The molar ratio of body is (0.2~0.6): (0.1~0.3).
5. preparation method according to claim 1, which is characterized in that the nano titanium oxide powder and alkali metal hydroxide
The molar ratio of object is (0.2~0.6): (0.4~6)；The ratio of the nano titanium oxide powder and water is preferably (0.2~0.6)
Mol:(200~600) ml.
6. preparation method according to claim 1, which is characterized in that the ratio of the nano titanium oxide powder and silica-alumina gel
Example is (0.2~0.6) mol:(30~100) g.
7. preparation method according to claim 1, which is characterized in that the step S1) specifically: by Preparation of Nanocrystal TiO
Body, zinc oxide nano-powder are mixed with alkali metal hydroxide with water, and silica-alumina gel is then added and carries out water after concussion mixing
Thermal response obtains the titania nanotube intermediate of load zinc oxide.
8. preparation method according to claim 7, which is characterized in that the concussion mixed time is 0.5~2h；It is described
The temperature of hydro-thermal reaction is 120 DEG C~160 DEG C；The time of the hydro-thermal reaction is 6~10h.
9. preparation method according to claim 1, which is characterized in that the pH value of the acid solution is 3~5；The acid is molten
The time of liquid processing is 5~10h；The temperature of the roasting is 300 DEG C~400 DEG C；The time of the roasting is 1~2h.
10. a kind of adsorption of metal ions device, which is characterized in that including metal prepared by claim 1~9 any one from
Sub- adsorbent material.
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