CN107551986A - Zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent and preparation method thereof - Google Patents
Zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent and preparation method thereof Download PDFInfo
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- CN107551986A CN107551986A CN201710893529.4A CN201710893529A CN107551986A CN 107551986 A CN107551986 A CN 107551986A CN 201710893529 A CN201710893529 A CN 201710893529A CN 107551986 A CN107551986 A CN 107551986A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 100
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 50
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QMGSCCRUAVAONE-UHFFFAOYSA-N zinc zirconium Chemical compound [Zn].[Zn].[Zn].[Zr] QMGSCCRUAVAONE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 111
- 230000007062 hydrolysis Effects 0.000 claims abstract description 41
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012266 salt solution Substances 0.000 claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910001868 water Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000013049 sediment Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 150000003754 zirconium Chemical class 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 239000003463 adsorbent Substances 0.000 claims description 40
- 239000010931 gold Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000000975 co-precipitation Methods 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 8
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000002411 adverse Effects 0.000 claims description 5
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- 238000001514 detection method Methods 0.000 claims description 3
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- 229910052785 arsenic Inorganic materials 0.000 abstract description 67
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 65
- 238000009826 distribution Methods 0.000 abstract description 6
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FJIGPNKYHKBULA-UHFFFAOYSA-N [Ag].NC(=S)S Chemical compound [Ag].NC(=S)S FJIGPNKYHKBULA-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 1
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent and preparation method thereof.IB races metal salt solution, zinc solution and zirconium salt solution are prepared into mixed salt solution first；Then using the deionized water of presetting pH value as bottom liquid, mixed salt solution and precipitant solution is added and are co-precipitated, endpoint pH control is 7 ~ 10；Completion of dropwise addition, continue to stir, carry out the heating hydrolysis of sediment；Centrifuge to obtain hydrolysate；The arsenic-removing adsorption agent is made in scrubbed again, centrifugation, drying, roasting.Arsenic-removing adsorption agent produced by the present invention, specific surface area is larger, pore-size distribution is narrow, metal nanoparticle high degree of dispersion is loaded to amorphous state composite oxide carrier, have the characteristics that clearance is high, adsorption capacity is big, usage amount is few and the rate of adsorption is fast, the advanced treating available for low-concentration arsenic-contaminated thing and low concentration waste water containing arsenic in underground water, surface water.
Description
Technical field
The invention belongs to arsenic-removing adsorption agent preparing technical field, and in particular to a kind of zinc zirconium mixed oxide load IB races gold
Belong to nano-particle arsenic-removing adsorption agent and preparation method thereof.
Background technology
The normal inorganic arsenic containing higher concentration in the waste water of the industrial discharges such as chemical industry, metallurgy, relieving haperacidity, agricultural chemicals and mining,
Mainly exist with trivalent arsenic and pentavalent arsenic morphology, the two ratio depends on the oxidation-reduction potential and pH value of waste water.Trivalent arsenic
Toxicity is higher than pentavalent arsenic 25 ~ 60 times, though the toxicity of pentavalent arsenic is relatively low, all can seriously pollute environment, destroy water ecological setting,
Even endanger human health.Therefore, it is necessary to carry out purified treatment to it before arsenic-containing waste water discharge, reach quality standard for surface water
After discharge（< 0.05 mg/L）, to ensure the water quality safety of surface water and groundwater.Industrial wastewater middle and high concentration arsenic is gone at present
About 0.5 mg/L can be reached using ripe coagulation/precipitation-filtering integrated technology, processing water outlet arsenic concentration except main；But enter one
Step reduces the concentration of arsenic（< 0.01 mg/L）, large excess of chemical agent need to be added so that cost for wastewater treatment increases severely, be same
When produce substantial amounts of arsenic slag, easily cause secondary pollution.Using ion-exchange or membrane filtration technique, processing cost is high, operation fortune
Row and maintenance technology require high, are not suitable for the extensive, industrial treatment of high-concentration waste water.Absorption method is a kind of efficient, applicable
Low-concentration arsenic treatment technology in extensive range, there is efficient, economic, easy to operate, reproducible utilization, have a wide range of application and without two
The advantages that secondary pollution.The key of adsorption treatment technology is arsenic-removing adsorption agent, and the adsorbent that arsenic-containing water processing at present uses is main
It is coated sand, activated alumina and modified activated carbon etc..These adsorbents have that adsorption capacity is small, adsorptive selectivity is low or absorption
The problems such as agent dissolution.Therefore, exploiting economy, efficient, quick, safe and reliable and the new of reproducible utilization remove arsenic adsorbent material,
Be China and foreign countries Environmental Scientific Research worker at present and future studies focus.
The oxide and hydroxide of literature survey and the metal such as experiment discovery, aluminium, iron, manganese, zinc, titanium, zirconium, to arsenic in water
It is respectively provided with preferable adsorption effect；Its compound (hydrogen) oxide can further improve the adsorption capacity to arsenic.Chinese invention patent
Apply " methods of production of high-efficient arsenic-removing sorbent Fe-Zr composite oxides "（Application No. 200810056344.9）There is provided
Fe-Zr composite oxides have good adsorption effect to high concentration trivalent arsenic, but to the absorption of low concentration trivalent arsenic, pentavalent arsenic
It is relatively low to measure capacity.A kind of Chinese invention patent application " Zr dopingβThe preparation side of-FeOOH anion exchange arsenic-removing adsorption agents
Method "（Application No. 200810117202.9）Disclose a kind of preparation method of arsenic-removing adsorption agent, this method is simple, expense compared with
It is low, be easy to apply, it is but relatively low to the adsorbance capacity of low concentration trivalent arsenic, pentavalent arsenic, and with the increase of adsorbance, absorption
The Cl of agent release-Dramatically increase.Chinese invention patent " a kind of arsenic-removing adsorption agent-iron copper composite oxides and preparation method thereof "
（Patent No. CN103127899B）A kind of preparation method of arsenic-removing adsorption agent is disclosed, preparation technology is simple, relative inexpensiveness,
There is good removal effect to pentavalent arsenic and trivalent arsenic, but the stirring and adsorbing time is longer.Martinson and Reddy exist
“Adsorption of arsenic(III) and arsenic(V) by cupric oxide nanoparticles”
（Journal of Colloid and Interface Science, 336 (2009): 406–411）Reported in one text
For CuO nano-particles to pentavalent arsenic and the absorption property of trivalent arsenic, maximum adsorption capacity is respectively 22.6,26.9 mg/g, is had fast
Speed absorption（The min of equilibration time 5）, applicable pH range it is wide（pH6~10）The advantages that.Goswami etc. is in " Arsenic
adsorption using copper (II) oxide nanoparticles”（Chemical Engineering
Research and Design, 90 (2012): 1387–1396）CuO nano-particles are reported in one text to low-concentration arsenic（<
0.2 mg/L）Reach 1.09 mg/g with good absorption property, maximum adsorption capacity, there is adsorbent easily to regenerate, regenerate suction
The advantages of attached effect is good.But in the two examples nanometer CuO arsenic-removing adsorption agent exist usage amount is larger, copper ion release and
Secondary pollution problem caused by nano-particle remnants.
The content of the invention
It is an object of the invention to received in view of the shortcomings of the prior art, providing a kind of zinc zirconium mixed oxide load IB races metal
Rice corpuscles arsenic-removing adsorption agent and preparation method thereof.
To achieve the above object, the present invention adopts the following technical scheme that：
Arsenic-removing adsorption agent provided by the invention by zinc zirconium composite oxides carrier, high degree of dispersion IB races metal nanoparticle and
Interface forms between the component, and IB races metal is the one or more in gold, silver, copper.
The method that the present invention prepares above-mentioned zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent, including
Following steps：
（1）Ionized water is removed, its pH value 7 ~ 10 is adjusted using precipitant solution, alkaline deionized water is obtained, as co-precipitation
Bottom liquid, it is stand-by then with 70 DEG C of water-bath steady temperature；
（2）Zinc solution, zirconium salt solution and IB races metal salt solution are mixed, mixing is stirred at room temperature, hybrid metal is made
Salting liquid；
（3）It is being stirred vigorously, under the conditions of water bath with thermostatic control, by precipitant solution and step（2）Obtained mixed salt solution drop
Add to step（1）In obtained alkaline deionized water bottom liquid, it is co-precipitated, it is 7 ~ 10 to control final ph；
（4）After above-mentioned solution is added dropwise to complete, continue the h of stirring 1 ~ 3, carry out the heating hydrolysis of co-precipitate, generate sediment；
（5）By step（4）Obtained sediment is centrifuged and washed repeatedly with deionized water, until supernatant liquor detection is not
To Cl-Presence；
（6）By step（5）Gained sediment is dried, and at 250 ~ 500 DEG C（It is preferred that 300 ~ 350 DEG C）Lower roasting 3h is natural
Cool down and produce adsorbent.
Step（1）With（3）Described in precipitant solution be 1.0 M Na2CO3The NH of solution or 5wt%3·H2O solution.
Step（2）In, the zinc solution is 1.0 M Zn (NO3)2Solution；The zirconium salt solution is 0.25 ~ 1.0 M
ZrOCl2·8H2O solution or 0.25 ~ 1.0 M Zr (NO3)4Solution；IB races metal salt solution is 0.25 M HAuCl4Solution, 0.5
~1.0 M AgNO3Solution and 0.5 M Cu (NO3)2One or more in solution.
Step（2）Described in IB races metal salt, zinc salt and zirconates material amount ratio be 0.05 ~ 0.3:0.5~3:1
The step（3）In coprecipitation mode be following current, cocurrent or adverse current；Described following current coprecipitation mode refers to, stirring,
Under water-bath isothermal condition, precipitant solution is first added dropwise to bottom liquid, completion of dropwise addition, after bath temperature is stable, then will be mixed
Metal salt solution is closed to be added dropwise；Described parallel-flow precipitation mode refers to, under stirring, water-bath isothermal condition, will precipitate
Agent solution and mixed salt solution are added dropwise in the liquid of bottom simultaneously；Described adverse current coprecipitation mode refers to, constant in stirring, water-bath
Under temperature conditionss, mixed salt solution is first added dropwise to bottom liquid, completion of dropwise addition, after bath temperature is stable, then by precipitating reagent
Solution is added dropwise.
Step（4）Described in hydrolysis temperature be 70 DEG C, the h of hydrolysis time 1 ~ 3.
Step（5）Described in the technological parameter of centrifugal process be：Centrifugal rotational speed is 4000 rpm, and centrifugation time is 8 min.
Step（5）The Cl of clear liquid at the middle and upper levels-Detection is with 0.5 M AgNO3Solution detects.
Step（6）Described in the technological parameter of drying process be：110 DEG C of drying temperature, the h of drying time 4 ~ 12.
The beneficial effects of the present invention are：
（1）Zinc zirconium mixed oxide provided by the invention load IB races metal nanoparticle arsenic-removing adsorption agent, specific surface area is larger,
Pore-size distribution is narrow, metal nanoparticle high degree of dispersion is loaded to the composite oxide carrier of amorphous state, bigger serface, has
The features such as clearance is high, adsorption capacity is big, usage amount is few and the rate of adsorption is fast, available for low-concentration arsenic in underground water, surface water
The advanced treating of pollutant and low concentration waste water containing arsenic；
（2）This preparation method technique is simple, reaction condition is gentle, and avoiding having used has strong toxicity and volatile compound conduct
Raw material, possesses the characteristics of green, safe technology, and metal nanoparticle can not only be highly dispersed to be loaded to without fixed by this method
The composite oxide carrier of form, bigger serface, microstructure, the metallic nanoparticle of composite oxide carrier can also be regulated and controled
Interaction between the decentralization and carrier-metal nanoparticle of son, farthest realize that various ingredients are inhaled in adsorbent
The synergy of attached arsenic.
Brief description of the drawings
Fig. 1 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2The XRD spectra of arsenic-removing adsorption agent；
Fig. 2 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2The HRTEM figures of arsenic-removing adsorption agent；
Fig. 3 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2The nitrogen adsorption desorption loop line of arsenic-removing adsorption agent and aperture
Distribution curve；
Fig. 4 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2Adsorption isotherm of the arsenic-removing adsorption agent to arsenic；
Fig. 5 (a), Fig. 5 (b), Fig. 5 (c) are the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2Arsenic-removing adsorption agent is to arsenic
Isothermal adsorption matched curve：Wherein Fig. 5 (a) uses Freundlich models；Fig. 5 (b) uses Langmuir models；Fig. 5
(c) Brunauer-Emmett-Teller models are used；
Fig. 6 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2Curve of adsorption kinetics of the arsenic-removing adsorption agent to arsenic；
Fig. 7 (a), Fig. 7 (b), Fig. 7 (c) are the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2Arsenic-removing adsorption agent is to arsenic
Adsorption dynamics adsorption kinetics matched curve：Wherein Fig. 7 (a) uses pseudo-first-order model；Fig. 7 (b) uses quasi- second-level model；Fig. 7 (c) is used
Diffusion model in particle.
Fig. 8 is the Ag-Cu/ZnO-ZrO that embodiments of the invention 9 are prepared2The XRD spectra of arsenic-removing adsorption agent；
Fig. 9 is the Ag-Cu/ZnO-ZrO that embodiments of the invention 9 are prepared2The N of arsenic-removing adsorption agent2Adsorption desorption loop line and hole
Footpath distribution curve；
Figure 10 is the Ag-Cu/ZnO-ZrO that embodiments of the invention 9 are prepared2Adsorption isotherm of the arsenic-removing adsorption agent to arsenic；
Figure 11 (a), Figure 11 (b), Figure 11 (c) are the Ag-Cu/ZnO-ZrO that embodiments of the invention 9 are prepared2Arsenic removal is adsorbed
Matched curve of the agent to the isothermal adsorption of arsenic：Wherein Figure 11 (a) uses Freundlich models；Figure 11 (b) uses Langmuir
Model；Figure 11 (c) uses Brunauer-Emmett-Teller models.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1：
Using 20 mL deionized waters as co-precipitation bottom liquid, using 1.0 M Na2CO3Solution adjusts pH value to 10, then permanent with water-bath
Determine temperature 70 C.By 0.25 M HAuCl4Solution, 1.0 M Zn (NO3)2Solution and 1.0 M ZrOCl2·8H2O solution presses one
Earnest matter amount ratio (n(Au)/n(Zn)/n(Zr)= 0.05:0.5:1) mixed salt solution is prepared.Precipitating reagent uses 1.0 M
Na2CO3Solution.First 46.6 mL precipitant solutions are added dropwise in above-mentioned bottom liquid under the conditions of magnetic agitation, then by 24.5 mL
Mixed salt solution following current is added dropwise and is co-precipitated, and endpoint pH is 9 ~ 10.Completion of dropwise addition, continue to stir 1.0 h, sunk
The heating hydrolysis of starch, hydrolysis temperature are 70 DEG C, hydrolysis time 1h.Hydrolysis terminates, takes out standing and be cooled to room temperature, high speed centrifugation
Separation（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until supernatant is with 0.5
M AgNO3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, with 2.6 DEG C/min be warming up to 300 DEG C and
3.0 h are calcined in still air atmosphere at this temperature, adsorbent is prepared into stove natural cooling（Au/ZnO-ZrO2）.
Embodiment 2
Using 20 mL deionized waters as co-precipitation bottom liquid, using 1.0 M Na2CO3Solution adjusts pH value to 10, then permanent with water-bath
Determine temperature 70 C.By 0.25 M HAuCl4Solution, 1.0 M Zn (NO3)2Solution and 1.0 M ZrOCl2·8H2O solution presses one
Earnest matter amount ratio (n(Au)/n(Zn)/n(Zr)= 0.05:0.5:1) mixed salt solution is prepared.Precipitating reagent uses 1.0 M
Na2CO3Solution.First 46.6 mL precipitant solutions are added dropwise in above-mentioned bottom liquid under the conditions of magnetic agitation, then by 24.5 mL
Mixed salt solution following current is added dropwise and is co-precipitated, and endpoint pH is 9 ~ 10.Completion of dropwise addition, continue to stir 1.0 h, sunk
The heating hydrolysis of starch, hydrolysis temperature are 70 DEG C, hydrolysis time 1h.Hydrolysis terminates, takes out standing and be cooled to room temperature, high speed centrifugation
Separation（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until supernatant is with 0.5
M AgNO3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, with 2.6 DEG C/min be warming up to 350 DEG C and
3.0 h are calcined in still air atmosphere at this temperature, adsorbent is prepared into stove natural cooling（Au/ZnO-ZrO2）.
Embodiment 3
Using 20 mL deionized waters as co-precipitation bottom liquid, using 1.0 M Na2CO3Solution adjusts pH value to 10, then permanent with water-bath
Determine temperature 70 C.By 0.25 M HAuCl4Solution, 1.0 M Zn (NO3)2Solution and 1.0 M ZrOCl2·8H2O solution is distinguished
By certain material amount ratio (n(Au)/n(Zn)/n(Zr)= 0.13:3:1) preparing metal salting liquid.Precipitating reagent uses 1.0 M
Na2CO3Solution.First 46.6 mL precipitant solutions are added dropwise in above-mentioned bottom liquid under the conditions of magnetic agitation, then by 24.5 mL
Mixed salt solution following current is added dropwise and is co-precipitated, and endpoint pH is 9 ~ 10.Completion of dropwise addition, continue to stir 1.0 h, sunk
The heating hydrolysis of starch, hydrolysis temperature are 70 DEG C, hydrolysis time 1h.Hydrolysis terminates, takes out standing and be cooled to room temperature, high speed centrifugation
Separation（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until supernatant is with 0.5
M AgNO3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, with 2.6 DEG C/min be warming up to 350 DEG C and
3.0 h are calcined in still air atmosphere at this temperature, adsorbent is prepared into stove natural cooling（Au/ZnO-ZrO2）.
Embodiment 4
Using 20 mL deionized waters as co-precipitation bottom liquid, using 1.0 M Na2CO3Solution adjusts pH value to 10, then permanent with water-bath
Determine temperature 70 C.By 0.25 M HAuCl4Solution, 1.0 M Zn (NO3)2Solution and 1.0 M ZrOCl2·8H2O solution is distinguished
By certain material amount ratio (n(Au)/n(Zn)/n(Zr)= 0.07:1:1) preparing metal salting liquid.Precipitating reagent uses 1.0 M
Na2CO3Solution.First 46.6 mL precipitant solutions are added dropwise in above-mentioned bottom liquid under the conditions of magnetic agitation, then by 24.5 mL
Mixed salt solution following current is added dropwise and is co-precipitated, and endpoint pH is 9 ~ 10.Completion of dropwise addition, continue to stir 1.0 h, sunk
The heating hydrolysis of starch, hydrolysis temperature are 70 DEG C, hydrolysis time 1h.Hydrolysis terminates, takes out standing and be cooled to room temperature, high speed centrifugation
Separation（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until supernatant is with 0.5
M AgNO3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, with 2.6 DEG C/min be warming up to 350 DEG C and
3.0 h are calcined in still air atmosphere at this temperature, adsorbent is prepared into stove natural cooling（Au/ZnO-ZrO2）.
Embodiment 5：
Using 20 mL deionized waters as co-precipitation bottom liquid, using 1.0 M Na2CO3Solution adjusts pH value to 10, then permanent with water-bath
Determine temperature 70 C.By 0.25 M HAuCl4Solution, 1.0 M Zn (NO3)2Solution and 1.0 M ZrOCl2·8H2O solution presses one
Earnest matter amount ratio (n(Au)/n(Zn)/n(Zr)= 0.05:0.5:1) mixed salt solution is prepared.Precipitating reagent uses 1.0
M Na2CO3Solution.By 46.6 mL precipitant solutions and 24.5 mL mixed salt solutions and drip under the conditions of magnetic agitation
Add in above-mentioned bottom liquid and be co-precipitated, endpoint pH is 9 ~ 10.Completion of dropwise addition, continue to stir 1.0 h, carry out adding for sediment
Pyrohydrolysis, hydrolysis temperature are 70 DEG C, hydrolysis time 1h.Hydrolysis terminates, takes out standing and be cooled to room temperature, is centrifuged at a high speed（Turn
Speed 4000 rpm, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until 0.5 M AgNO of supernatant3
Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, 350 DEG C are warming up to and in the temperature with 2.6 DEG C/min
3.0 h are calcined in lower still air atmosphere, adsorbent is prepared into stove natural cooling（Au/ZnO-ZrO2）.
Embodiment 6
Using 20 mL deionized waters as co-precipitation bottom liquid, using 1.0 M Na2CO3Solution adjusts pH value to 10, then permanent with water-bath
Determine temperature 70 C.By 0.25 M HAuCl4Solution, 1.0 M Zn (NO3)2Solution and 1.0 M ZrOCl2·8H2O solution presses one
Earnest matter amount ratio (n(Au)/n(Zn)/n(Zr)= 0.05:0.5:1) mixed salt solution is prepared.Precipitating reagent uses 1.0 M
Na2CO3Solution.First 24.5 mL mixed salt solutions are added dropwise in above-mentioned bottom liquid under the conditions of magnetic agitation, then will
46.6 mL precipitant solutions adverse current, which is added dropwise, to be co-precipitated, and endpoint pH is 9 ~ 10.Completion of dropwise addition, continue to stir 1.0 h, enter
The heating hydrolysis of row sediment, hydrolysis temperature are 70 DEG C, hydrolysis time 1h.Hydrolysis terminates, takes out standing and be cooled to room temperature, high speed
Centrifuge（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until supernatant is used
0.5 M AgNO3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, 350 DEG C are warming up to 2.6 DEG C/min
And 3.0 h are calcined in still air atmosphere at such a temperature, it is prepared into adsorbent with stove natural cooling（Au/ZnO-ZrO2）
Embodiment 7：
Using 50 mL deionized waters as co-precipitation bottom liquid, using 5wt%NH3·H2O solution adjusts its pH value 8, then permanent with water-bath
Determine temperature 70 C.By 1.0 M AgNO3Solution, 0.5 M Cu (NO3)2Solution, 1.0 M Zn (NO3)2Solution and 0.25 M Zr
(NO3)4Solution respectively by certain material amount ratio (n(Ag)/n(Zn)/n(Zr)= 0.1:0.5:1) it is molten to prepare mixed nitrate
Liquid.Precipitating reagent uses 5wt% NH3·H2O solution, it is under intense agitation that 50 mL mixed nitrate solutions and precipitating reagent are molten
Liquid cocurrent is added drop-wise in above-mentioned bottom liquid.In coprecipitation process, both rate of addition of adjustment, control ph maintains 7 ~ 8.It is added dropwise
Terminate, continue to stir 3.0 h, carry out the heating hydrolysis of sediment, hydrolysis temperature is 70 DEG C, the h of hydrolysis time 3.Hydrolysis terminate,
Take out standing and be cooled to room temperature, be centrifuged at a high speed（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed with deionized water
Wash, centrifuge, until 0.5 M AgNO of supernatant3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h,
It is warming up to 3.3 DEG C/min in 300 DEG C and at such a temperature still air atmosphere and is calcined 3.0 h, is produced with stove natural cooling
Adsorbent（Ag /ZnO-ZrO2）.
Embodiment 8
Using 50 mL deionized waters as co-precipitation bottom liquid, using 5wt%NH3·H2O solution adjusts its pH value 8, then permanent with water-bath
Determine temperature 70 C.By 0.5 M Cu (NO3)2Solution, 1.0 M Zn (NO3)2Solution and 0.25 M Zr (NO3)4Solution is by certain
Material amount ratio (n(Cu)/n(Zn)/n(Zr)= 0.2:0.5:1) mixed nitrate solution is prepared.Precipitating reagent uses 5% NH3·
H2O solution, 50 mL mixed nitrate solutions and precipitant solution cocurrent are added drop-wise to above-mentioned bottom liquid under intense agitation
In.In coprecipitation process, both rate of addition of adjustment, control ph maintains 7 ~ 8.Completion of dropwise addition, continue to stir 3.0 h,
The heating hydrolysis of sediment is carried out, hydrolysis temperature is 70 DEG C, the h of hydrolysis time 3.Hydrolysis terminates, takes out standing and be cooled to room temperature,
It is centrifuged at a high speed（The rpm of rotating speed 4000, the min of time 8）.Then repeatedly washed, centrifuged with deionized water, until supernatant
0.5 M AgNO of liquid3Solution is detected without Cl-In the presence of untill.Finally in 110 DEG C of dry 12 h, it is warming up to 3.3 DEG C/min
300 DEG C and 3.0 h are calcined in still air atmosphere at such a temperature, adsorbent is produced with stove natural cooling（Cu/ZnO-
ZrO2）.
Embodiment 9
Using 50 mL deionized waters as co-precipitation bottom liquid, using 5wt%NH3·H2O solution adjusts its pH value 8, then permanent with water-bath
Determine temperature 70 C.By 1.0 M AgNO3Solution, 0.5 M Cu (NO3)2Solution, 1.0 M Zn (NO3)2Solution and 0.25 M Zr
(NO3)4Solution respectively by certain material amount ratio (n(Ag)/n(Cu)/n(Zn)/n(Zr)= 0.1:0.2:0.5:1) mixing is prepared
Nitrate solution.Precipitating reagent uses 5wt% NH3·H2O solution, under intense agitation by 50 mL mixed nitrate solutions and
Precipitant solution cocurrent is added drop-wise in above-mentioned bottom liquid.In coprecipitation process, both rate of addition of adjustment, control ph maintains
7~8.Completion of dropwise addition, continue to stir 3.0 h, carry out the heating hydrolysis of sediment, hydrolysis temperature is 70 DEG C, hydrolysis time 3h.Water
Solution, which terminates, takes out standing is cooled to room temperature, is centrifuged at a high speed（The rpm of rotating speed 4000, the min of time 8）.Then deionized water is used
Repeatedly washing, centrifugation, until 0.5 M AgNO of supernatant3Solution is detected without Cl-In the presence of untill.It is finally dry at 110 DEG C
Dry 12 h, it is warming up to 3.3 DEG C/min in 300 DEG C and at such a temperature still air atmosphere and is calcined 3.0 h, it is naturally cold with stove
But adsorbent is produced（Ag-Cu/ZnO-ZrO2）.
The gained adsorbent of embodiment 1 ~ 9 is determined to the clearance and adsorption capacity of arsenic using interval static adsorptive method, will be inhaled
Attached dose is ground using agate mortar, crosses 200 mesh sieves, the mg of precise 10.Measure the arsenic-containing water that 70 mL arsenic concentrations are 5 mg/L
Solution, with 25 DEG C of water-bath steady temperature.Under the conditions of magnetic agitation, the sample of sorbent accurately weighed is added, stirs 40 min
After take out, 4000 r/min rotating speeds centrifuge 8 min under the conditions of carry out separation of solid and liquid.The mL of supernatant liquor 50 is taken, using diethyl
The concentration of arsenic in aminodithioformic acid silver spectrophotometry solution, calculate the clearance of arsenicR(%) and arsenic adsorbanceq
(mg/g), as a result such as table 1.
The zinc zirconium mixed oxide of table 1 loads IB race's metal nanoparticle arsenic-removing adsorption agents and its absorption arsenic removal example performance
From table 1, embodiment 1 ~ 4 and embodiment 8,9 preparation-obtained adsorbents are respectively provided with good effect of removing arsenic, wherein
Embodiment 9 is optimum embodiment of the present invention.Good synergy be present between this explanation Liang Zhong IB races metal.Embodiment 1 is bright
It is aobvious to be substantially better than embodiment 7 better than embodiment 5 and 6, embodiment 8.When this all illustrates to use single IB races metal, coprecipitation mode and
The arsenic removal performance to adsorbent of the present invention such as IB races metal species has significant impact effect.
By sample made from embodiment 2（350 DEG C of roastings）X-ray diffraction is carried out respectively（XRD）Analysis, high-resolution are saturating
Radio mirror（HRTEM）Observation, N2Adsorption and desorption isotherms, adsorption isotherm and curve of adsorption kinetics to arsenic determine, and as a result divide
Not as shown in Figure 1, Figure 2, Fig. 3, Fig. 4 and Fig. 5（a）, Fig. 5（b）, Fig. 5（c）It is shown.Determine the adsorption isothermal curve use of adsorbent
Initial arsenic concentration is respectively 0.5,3,5,7,9,11,13 mg/L arsenic-containing water solution, and remaining experiment condition is the same as interval Static Adsorption
Method.Experiment condition is used by determining the curve of adsorption kinetics of adsorbent：Initial arsenic concentration is used to contain arsenic for 5 mg/L
The aqueous solution, mixing time are respectively 5,10,20,30,40,50,60,70,80,90 min, and remaining experiment condition is static with interval
Absorption method.
Fig. 1 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2The XRD spectra of arsenic-removing adsorption agent.Can by Fig. 1
Know faint tetragonal phase, monocline crystalline phase ZrO only occur2Diffraction maximum and elemental gold diffraction maximum, illustrate Zr in composite oxygen
Then exist in compound with amorphous state, Zn is not substantially separated out from composite oxides, and gold is in high degree of dispersion state.
Fig. 2 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2The HRTEM figures of arsenic-removing adsorption agent.Can by Fig. 2
See, nanometer grade gold particle is highly dispersed at ZnO-ZrO2Composite oxide carrier surface.
Fig. 3 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2The N of arsenic-removing adsorption agent2Adsorption desorption loop line and hole
Footpath distribution curve.From the figure 3, it may be seen that IV types, Hysteresis loop that the adsorption isotherm of the adsorbent belongs in IUPAC classification belong to H4
Type.This illustrates that the adsorbent has the pore property of micropore and mesopore " mixing ".In addition, instruction single molecular layer saturated absorption
Flex point unobvious, this is the result that a small amount of micropore of adsorbent is filled with；Continue to increase with relative pressure, start multilayer
Absorption；In medium relative pressure, capillary condensation takes place；But after mesopore capillary condensation is filled up, on adsorption isotherm continues
Rise, illustrate that the adsorbent also has the hole of large aperture or adsorption molecule interaction strong, continue absorption and form polymolecular layer.By
Adsorption and desorption isotherms calculate the texture parameter for obtaining the adsorbent：The m of BET specific surface area 115.032/ g, average pore size 5.36
Nm, the nm of most probable pore size 3.70, the cm of specific pore volume 0.153/g。
Fig. 4 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2Adsorption isotherm of the arsenic-removing adsorption agent to arsenic.
Using conventional Freundlich, Langmuir and Brunauer-Emmett-Teller adsorption isotherm line model to the adsorbent
The isothermal adsorption process of arsenic-adsorbing is fitted, Fig. 5（a）, Fig. 5（b）, Fig. 5（c）For fitting result.As a result find, compare
The coefficient correlation of Freundlich models（R 2= 0.9222）, Au/ZnO-ZrO2Adsorbent is more suitable for using to the adsorption process of arsenic
Langmuir and Brunauer-Emmett-Teller Tellurium determinations are described（R 2= 0.9992, 0.9992）；Say
Absorption of the bright adsorbent to arsenic be not limited to monolayer adsorption can also be multilayer absorption, adsorb the superiors arsenic species and solution
In arsenic species be in kinetic balance, its maximum adsorption capacity is 33.56 mg/g.
Fig. 6 is the Au/ZnO-ZrO that embodiments of the invention 2 are prepared2Arsenic-removing adsorption agent is bent to the adsorption dynamics adsorption kinetics of arsenic
Line, by 40 min, absorption basically reaches balance, and adsorption efficiency reaches 83.16%.Using expanding in pseudo-first-order, quasi- two level and particle
Kinetic model is dissipated to be fitted the adsorption dynamics adsorption kinetics process of arsenic in the adsorbent.Such as Fig. 7（a）, Fig. 7（b）, Fig. 7（c）Can
Know, compare pseudo-first-order dynamics coefficient correlation（R 2= 0.8053）, the coefficient correlation of kinetics of diffusion in quasi- two level and particle
（R 2= 0.9977, 0.9892）Do not pass through original closer to kinetics of diffusion piecewise fitting straight line in 1.000, particle
Point, illustrate that kinetics of diffusion model may be applicable to describe absorption of the adsorbent to arsenic, and the absorption in quasi- two level and particle
Process initial period controlled by membrane diffusion, after by chemisorbed and intra-particle diffusion co- controlling.
By Ag-Cu/ZnO-ZrO made from embodiment 92Sample carries out X-ray diffraction respectively（XRD）Analysis, N2Adsorption desorption etc.
Warm line and the adsorption isotherm measure to arsenic, as a result respectively such as Fig. 8, Fig. 9, Figure 10 and Figure 11（a）, Figure 11（b）, Figure 11（c）Institute
Show.
Fig. 8 is the Ag-Cu/ZnO-ZrO that embodiments of the invention 9 are prepared2The XRD spectra of arsenic-removing adsorption agent.By dividing
Analyse Fig. 8 to understand, hence it is evident that multiple ZnO diffraction maximum occur, wherein 1 Cu may be included2O diffraction maximum, and appearance 1 are faint
Ag2O diffraction maximum.Using identical Zn/Zr ratios, when loading silver-bearing copper component, part Zn, a small amount of Cu and Ag will be from combined oxidations
Separated out in thing, form corresponding nanometer oxide particle；And Zr then exists in composite oxides with amorphous state.
Fig. 9 is the Ag-Cu/ZnO-ZrO that embodiments of the invention 9 are prepared2The N of arsenic-removing adsorption agent2Adsorption desorption loop line and
Pore size distribution curve.As shown in Figure 9, the adsorption isotherm of the adsorbent belongs in IUPAC classification IV types, Hysteresis loop belongs to
H4 types.This illustrates that the adsorbent has the pore property of micropore and mesopore " mixing ".In addition, instruction monolayer saturation absorption
The flex point unobvious of amount, this is the result that a small amount of micropore of adsorbent is filled with；Continue to increase with relative pressure, start more
Layer absorption；In medium relative pressure, capillary condensation takes place；But after mesopore capillary condensation is filled up, adsorption isotherm continues
Rise, illustrate that the adsorbent also has the hole of large aperture or adsorption molecule interaction strong, continue absorption and form polymolecular layer.
The texture parameter for obtaining the adsorbent is calculated by Adsorption and desorption isotherms：The m of BET specific surface area 1192/ g, the nm of average pore size 5.68,
The nm of most probable pore size 3.70, the cm of specific pore volume 0.163/g。
Figure 10 is Ag-Cu/ZnO-ZrO prepared by the embodiment of the present invention 92Adsorption isotherm of the arsenic-removing adsorption agent to arsenic.Adopt
The adsorbent is inhaled with conventional Freundlich, Langmuir and Brunauer-Emmett-Teller adsorption isotherm line model
The isothermal adsorption process of attached arsenic is fitted, Figure 11（a）, Figure 11（b）, Figure 11（c）For fitting result.As a result find, compare
The coefficient correlation of Freundlich models（R 2= 0.7316）, Ag-Cu/ZnO-ZrO2Adsorbent is more suitable for the adsorption process of arsenic
It is described with Langmuir and Brunauer-Emmett-Teller Tellurium determinations（R 2= 0.9991, 0.9991）；
Illustrate absorption of the adsorbent to arsenic be not limited to monolayer adsorption can also be multilayer absorption, adsorb the superiors arsenic species with it is molten
Arsenic species in liquid are in kinetic balance, and its maximum adsorption capacity is 40.65 mg/g.
Above example is that right will appended by use in exemplary and nonrestrictive, of the invention components system
The arsenic-removing adsorption agent and technical scheme that all Parameters variations for the preparation method asked or optimization are obtained, it is all contained in the present invention's
In protection domain.
Claims (10)
- A kind of 1. zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent, it is characterised in that：The adsorbent Be made up of interface between zinc zirconium composite oxides carrier, IB races metal nanoparticle and component, IB races metal be gold, silver and One or more in copper.
- A kind of 2. zinc zirconium mixed oxide as claimed in claim 1 load IB races metal nanoparticle arsenic-removing adsorption agent of preparing Method, it is characterised in that：Specifically include following steps：（1）Ionized water is removed, its pH value 7 ~ 10 is adjusted using precipitant solution, alkaline deionized water is obtained, as co-precipitation Bottom liquid, it is stand-by then with 70 DEG C of water-bath steady temperature；（2）Zinc solution, zirconium salt solution and IB races metal salt solution are mixed, mixing is stirred at room temperature, hybrid metal is made Salting liquid；（3）It is being stirred vigorously, under the conditions of water bath with thermostatic control, by precipitant solution and step（2）Obtained mixed salt solution drop Add to step（1）In obtained alkaline deionized water bottom liquid, it is co-precipitated, it is 7 ~ 10 to control final ph；（4）After above-mentioned solution is added dropwise to complete, continue the h of stirring 1 ~ 3, carry out the heating hydrolysis of co-precipitate, generate sediment；（5）By step（4）Obtained sediment is centrifuged and washed repeatedly with deionized water, until supernatant liquor can't detect Cl-Presence；（6）By step（5）Gained sediment is dried, and 3h is calcined at 250 ~ 500 DEG C, and natural cooling produces adsorbent.
- 3. the preparation of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（1）With（3）Described in precipitant solution be 1.0 M Na2CO3The NH of solution or 5wt%3· H2O solution.
- 4. the preparation of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（2）In, the zinc solution is 1.0 M Zn (NO3)2Solution；The zirconium salt solution be 0.25 ~ 1.0 M ZrOCl2·8H2O solution or 0.25 ~ 1.0 M Zr (NO3)4Solution；IB races metal salt solution is 0.25 M HAuCl4It is molten Liquid, 0.5 ~ 1.0 M AgNO3Solution and 0.5 M Cu (NO3)2One or more in solution.
- 5. the preparation side of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（2）Described in IB races metal salt, zinc salt and zirconates material amount ratio be 0.05 ~ 0.3:0.5~ 3:1。
- 6. the preparation side of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：The step（3）In coprecipitation mode be following current, cocurrent or adverse current；Described following current coprecipitation mode is Refer to, under stirring, water-bath isothermal condition, precipitant solution is first added dropwise to bottom liquid, completion of dropwise addition, treats that bath temperature is stable Afterwards, then by mixed salt solution it is added dropwise；Described parallel-flow precipitation mode refers to, in stirring, water-bath isothermal condition Under, precipitant solution and mixed salt solution are added dropwise in the liquid of bottom simultaneously；Described adverse current coprecipitation mode refers to, is stirring Mix, under water-bath isothermal condition, mixed salt solution is first added dropwise to bottom liquid, completion of dropwise addition, after bath temperature is stable, Precipitant solution is added dropwise again.
- 7. the preparation of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（4）Described in hydrolysis temperature be 70 DEG C, the h of hydrolysis time 1 ~ 3.
- 8. the preparation of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（5）Described in the technological parameter of centrifugal process be：Centrifugal rotational speed is 4000 rpm, centrifugation time For 8 min.
- 9. the preparation of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（5）The Cl of clear liquid at the middle and upper levels-Detection is with 0.5 M AgNO3Solution detects.
- 10. the preparation of zinc zirconium mixed oxide load IB races metal nanoparticle arsenic-removing adsorption agent according to claim 2 Method, it is characterised in that：Step（6）Described in the technological parameter of drying process be：110 DEG C of drying temperature, drying time 4 ~ 12 h。
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| CN113842875A (en) * | 2021-10-15 | 2021-12-28 | 内蒙古工业大学 | Preparation method of halloysite-loaded zirconium oxide nanocomposite |
| CN115501852A (en) * | 2022-09-01 | 2022-12-23 | 广州大学 | Preparation method and application of metal-doped alumina hydrate with high adsorption performance |
| CN116586028A (en) * | 2023-05-04 | 2023-08-15 | 生态环境部南京环境科学研究所 | Fe (Fe) 3+ -Ti 4+ -Zr 4+ Preparation method and application of LDH (layered double hydroxides) -type adsorbent |
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| CN110237845B (en) * | 2018-03-07 | 2020-09-01 | 浙江大学 | Method for preparing Cu-ZnO catalyst by using microreactor |
| CN108295805A (en) * | 2018-04-20 | 2018-07-20 | 福州大学 | Active metal composite oxide load micro-nano adsorbent of modified by silver iron-series metal oxide arsenic removal and preparation method thereof |
| CN113842875A (en) * | 2021-10-15 | 2021-12-28 | 内蒙古工业大学 | Preparation method of halloysite-loaded zirconium oxide nanocomposite |
| CN115501852A (en) * | 2022-09-01 | 2022-12-23 | 广州大学 | Preparation method and application of metal-doped alumina hydrate with high adsorption performance |
| CN116586028A (en) * | 2023-05-04 | 2023-08-15 | 生态环境部南京环境科学研究所 | Fe (Fe) 3+ -Ti 4+ -Zr 4+ Preparation method and application of LDH (layered double hydroxides) -type adsorbent |
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