CN109174903A - A method of utilizing alumina stable cadmium - Google Patents
A method of utilizing alumina stable cadmium Download PDFInfo
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- CN109174903A CN109174903A CN201810875854.2A CN201810875854A CN109174903A CN 109174903 A CN109174903 A CN 109174903A CN 201810875854 A CN201810875854 A CN 201810875854A CN 109174903 A CN109174903 A CN 109174903A
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- cadmium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
Abstract
The invention discloses a kind of methods using alumina stable cadmium, comprising the following steps: 1) by CdO and γ-Al2O3Precursor mixing, wherein Cd/Al molar ratio is 0.25；2) it by mixture in step 1) in aqueous slurry environment after ball milling 18~for 24 hours, send to baking oven 18 at 100~105 DEG C~is dried for 24 hours；3) dry mixture is further homogenized with mortar grinder, the pellet of 10~20mm of Φ is then granulated at 150~250MPa；4) time of 0.25~18h is kept to be used for subsequent heat treatment at 800~1000 DEG C；The present invention is by CdO to CdAl4O7Monocline transformation, passes through monoclinic system CdAl4O7Structure formed can significant reduction cadmium leaching rate, thus harmful cadmium in effectively stable waste stream；Present invention process is simple, it is only necessary to use a kind of common inexpensive industrial materials γ-Al abundant in the natural environment2O3, by simple sintering method, cadmium effectively can be included in CdAl4O7Structure significantly reduces the danger that can be discharged into environment cadmium metal.
Description
Technical field
The present invention relates to solid waste harmless treatment and application technology as the second resource fields, it particularly relates to a kind of benefit
With the method for alumina stable cadmium.
Background technique
Metallic pollution has become many areas in world problem of interest, and cadmium is due to its serious acute and chronic toxicity
Effect, cadmium is considered as one of maximum metal of toxicity, and cadmium pollution is number two in heavy metal pollution.2014, the whole world
The production and consumption amount of cadmium be 22200 tons, industrial activity (as be electroplated, smelt, alloy manufacture, pigment, plastics, battery, mining and
Refinery practice) material risk is constituted to publilc health and the ecosystem.It is reported that 1979, Japan is in the bank reparation of Jinin river bank
Being expended totle drilling cost by the project in the farmland of cadmium pollution is 4.96 hundred million dollars.2009, cadmium pollution occurred for liuyang hunan town head town,
Thing source Changsha Hunan and chemical plant production secondary zinc oxide, zinc sulfate and indium metal.Since Environment Protection and Drainage of Pulled Water facility is not complete, cadmium is direct
It is discharged into water body and soil, leads to soil pollution in wide area.There are within 2012 20 tons of cadmiums to be discharged into Longjiang (Guangxi China), causes hundreds of
Ten thousand fish are dead, affect the water supply of up to 4,000,000 people.Most of cadmium ion passes through precipitation process from dirt in the form of cadmium hydroxide
It is removed in the waste water of dye.Environmental Protection Department of Denmark points out that the 11-59% of the cadmium in municipal wastewater may be with waste sludge shape
Formula exists.In general, solidify and stable sludge containing cadmium is eventually processed in landfill field.But since it can not
Degradability and high fluidity, cadmium are easy to be leached in acid condition, and pass through food chain (soil-plant-animal-human)
The biological accumulation in human organ.
Mainly there are two approach of stabilisation/curing process and resource utilization to the processing containing heavy metal waste slag.It is Chinese special
Sharp publication number CN105801046A has invented one kind and has formed processing by cement hardener, stabilizing additive, adsorbent, stabilizer
Agent will contain cadmium waste residue stable curing into the body of residue stabilization containing cadmium, then will contain cadmium residue stabilization body landfill, but its solidification uses medicine
Agent product is more, complex treatment process；China Patent Publication No. CN102560124 describes a kind of rotary kiln progress solid waste of heavy metal
Harmless resource utilization, which realizes the zero-emission of waste water, waste residue, the circulation and comprehensive utilization of resource, but its technical process is easy
Generate secondary pollution；China Patent Publication No. CN104475431A describes a kind of stabilisation curing method of high poison waste residue, should
Method chemical stabilization and cladding, solidification etc. stabilize to mercury, arsenic, chromium, cadmium, cyanide high poison hazardous waste solid
Change.But it needs to carry out repeatedly cladding solidification, cumbersome and is difficult to be widely used in engineering reality.In addition, this method may
It is corroded in acid condition by percolate, there are the risks of secondary pollution.China Patent Publication No. CN101824543 introduces a huge sum of money
Belong to the vulcanizing treatment of waste and wherein the method for valuable metal recovery, the method use vulcanization combination high pressure, high temperature, flotation etc.
Technique carries out vulcanization recycling to valuable metal, is also used for the vulcanization stabilization processes of heavy metal waste slag, realizes heavy metal waste slag
Innoxious, disposal of resources, but there are heavy metal recovery not exclusively, cost is too high the problems such as.Since waste residue phase structure is multiple
It is miscellaneous, valuable metal content is relatively low, the technical difficulty of synthetical recovery and resource utilization is larger, so at common stabilisation/solidification
Reason.Solidified body will cause inclusion body rupture after being influenced by extraneous unstable factor, noxious material in waste is caused to be percolated again
Out.
In the fast development process of changing rejected material to useful resource strategy, discarded dirt is managed with needing a kind of novel economic and reliable
The technology of mud.As substitution waste management technology, heat treatment provides fixed and a possibility that stablize poisonous metal and feasible
Property.In the case where controlling good heat-treatment protocol, rich aluminum material is added to containing in metal waste, metal can be by specific brilliant
Body stable structure is got off, and a large amount of reductions of the solubility in acidic environment.For Cd-Al-O system, CdAl is had reported2O4
And CdAl4O7For aluminic acid cadmium, the chance for stablizing cadmium may be provided by heat treatment.CdAl2O4Formation be by two step (colloidal sols-
Gel and sintering) synthesis process.Aluminium oxide (Al2O3) it is a kind of common industrial material abundant in the natural environment.Share 7 kinds
Aluminium oxide phase, including metastable state γ, η, δ, θ, κ, χ-aluminium oxide and stable Alpha-alumina in being widely applied it is reported that show
Technical significance is shown.In these aluminium oxide phases, γ-Al2O3It is a kind of precursor material of low cost, due to its unique crystalline substance
Body structure and high response.
Based on above-mentioned thinking, the present invention provides a kind of stabilizes heavy metal cadmium using gama-alumina under heat condition
Method, has found a kind of promising stable strategy in the advantageous applications of the product containing cadmium, realistic price with higher and
Wide application prospect.
Summary of the invention
In place of overcoming the shortcomings of the prior art, the present invention provides one kind efficiently, steadily
Cadmium is included in CdAl4O7Method in structure.Aluminic acid cadmium pair generated is proved by the toxic characteristic leaching experiment of constant pH
Acid erosion has high resistance, significantly reduces the danger that cadmium metal can be discharged into environment.
To achieve the above object, the technical solution taken:
A method of utilizing alumina stable cadmium, which comprises the following steps:
It 1) is 0.25 by Cd/Al molar ratio, by CdO and γ-Al2O3Precursor mixing；
2) mixture in step 1) is dispersed in aqueous slurry environment, then be dried；
3) kept for the time of 0.25~18h be used for subsequent heat treatment at 800~1000 DEG C the product in step 2).
The present invention is only needed using a kind of common inexpensive industrial materials γ-Al abundant in the natural environment2O3(one
The typical rich aluminum material of kind), by simple sintering method, cadmium effectively can be included in CdAl4O7Structure, significantly reducing will
The danger that cadmium metal can be discharged into environment；The leaching result of CPLT technique clearly illustrates CdAl4O7With very strong anti-leaching
Can, and a kind of promising stable strategy is had found in the advantageous applications of the product containing cadmium.
Preferably, further include that the mixture that will be dried further homogenizes, be then granulated into pellet；
Preferably, the temperature in the step 3) is 900~1000 DEG C.When Cd/Al molar ratio is 1/4, at 900 DEG C
Form a large amount of CdAl4O7, in 950 DEG C of processing 3h, cadmium height mixes monoclinic system CdAl4O7In structure, higher temperature is logical
Often to overcome energy barrier present in solid-state reaction to provide bigger driving force.1000 DEG C are raised the temperature to further to be promoted
CdAl4O7Crystallinity and the CdAl for harvesting 83wt%4O7, and mix CdAl4O7The conversion ratio of cadmium in monoclinic structure reaches substantially
To 100%.
Preferably, the time in the step 3) is 3~18h.Extending sintering time is one of factor of most critical, can be with
Homogenizing and crystallizing for product is improved simultaneously.A large amount of CdAl is formd within 950 DEG C very short of processing times (0.25h)4O7
(55wt%).The processing time extends to 3h, observes CdAl4O7The slight increase of phase simultaneously approaches balance；By the processing of 9h,
CdAl is observed in the sample of processing4O7For 82wt%, and generate by the heat treatment of 18h 90wt%'s in product
CdAl4O7。
Preferably, being separated under ball milling 300~500r/min speed in the step 2), ball milling 18~for 24 hours.
Preferably, the drying in step 2) be send to baking oven 18 at 100~105 DEG C~for 24 hours.
Preferably, it is further homogenized in the step 3) using mortar grinder, is then granulated at 150~300MPa
The pellet of 10~20mm of Φ.
Preferably, the pellet in the step 3) is in 950 DEG C of holding 3h.In 950 DEG C very short of processing time (0.25h)
Inside form a large amount of CdAl4O7(55wt%).The processing time extends to 3h, observes CdAl4O7Phase slightly increases and approaches
Balance；Leach experiments have shown that, at the end of leaching test (120 minutes), the maximum cadmium concentration observed in CdO percolate is
691.2mg/L, after surface area normalization, it compares CdAl4O7Sample is higher by 2 orders of magnitude or more, CdAl4O7Erosion to strong acid
There is higher plant resistance than CdO phase.
The present invention also provides to CdAl4The method that O carries out leaching experiment, the leaching experiment method used are constant pH
Leaching experiment method.Non-constant pH value may delay leaching process or lead to the reprecipitation of metallic compound, and the present invention uses
Constant pH leaching test (CPLT) can overcome these disadvantages, this is to have very much for the leachability and leaching behavior that disclose waste
Benefit.
The utility model has the advantages that
1, the present invention is a kind of method using alumina stable cadmium, and this method is by CdO to CdAl4O7Monocline turns
Become, passes through monoclinic system CdAl4O7Structure formed can significant reduction cadmium leaching rate, thus the nocuousness in effectively stable waste stream
Cadmium.
2, present invention process is simple, it is only necessary to use a kind of common inexpensive industrial materials abundant in the natural environment
γ-Al2O3(a kind of typical rich aluminum material), by simple sintering method, effectively can be included in CdAl for cadmium4O7Structure,
Significantly reduce the danger that can be discharged into environment cadmium metal.
3, CdAl of the present invention4O7The fixed cadmium metal effect of monocline is obvious, and only needs 15 minutes (0.25h) to can reach
It essentially forms, while secondary residue, waste water and exhaust gas will not be generated in the curing process, it is environmentally friendly and more safe and effective, pass through
Stable product can also be advantageously used for construction material.
4, the leaching result of CPLT technique clearly illustrates CdAl4O7With very strong anti-leaching performance, and in product containing cadmium
Advantageous applications in have found a kind of promising stable strategy.
5, the present invention also depth inquires into influence reaction path and passes through CdAl4O7The processing parameter of the levels of incorporation of crystallization, such as
Cd/Al molar ratio, treatment temperature and time.The mixture that Cd/Al molar ratio is 1/4 is explored, preferred treatment temperature is 950
DEG C, TR value shows that cadmium incorporation is nearly completed after 3h processing scheme.
Detailed description of the invention
Fig. 1 is the schematic diagram of cadmium stabilization reactions approach and heat treatment of the present invention；
Fig. 2 is that embodiment 1 to 5 uses TOPAS V4.0 program analysis incorporation CdAl4O7The conversion of cadmium in monoclinic structure
Rate figure；
Fig. 3 is the X-ray diffracting spectrum of the sample of the preparation of embodiment 1 to 5；
Fig. 4 is that embodiment 6 to 12 uses TOPAS V4.0 program analysis incorporation CdAl4O7Turn of cadmium in monoclinic structure
Rate figure；
Fig. 5 is CdO and CdAl4O7Leaching cadmium content figure in phase；
Fig. 6 is the X-ray diffracting spectrum of the sample of comparative example 1 to 2；
Fig. 7 is the X-ray diffracting spectrum of the sample of comparative example 3.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following embodiment is merely to illustrate this
Invention is not for limiting the scope of the invention.Therefore it is all specific as follows according to method described in present patent application range:
Embodiment 1
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) mixture in step 1) is used to ball milling in aqueous slurry environment, under 400r/min speed, after ball milling 18h, then
It send to baking oven and is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 800 DEG C of holding 3h is used for subsequent heat treatment under different target temperatures；
5) using the XRD diagram of x-ray powder diffraction instrument record powder sample, and the analysis incorporation of TOPAS V4.0 program is used
CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 2
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) mixture in step 1) is used to ball milling in aqueous slurry environment, under 350r/min speed, after ball milling 20h, then
Send that 20h is dried at 100 DEG C to baking oven；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 15mm is then granulated at 150MPa
Material.
4) time of 850 DEG C of holding 3h is used for subsequent heat treatment under different target temperatures；
5) using the XRD diagram of x-ray powder diffraction instrument record powder sample, and the analysis incorporation of TOPAS V4.0 program is used
CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 3
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 300r/min speed, ball milling for 24 hours after, then send
To baking oven, 18h is dried at 102 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 15mm is then granulated at 200MPa
Material.
4) time of 900 DEG C of holding 3h is used for subsequent heat treatment under different target temperatures；
5) using the XRD diagram of x-ray powder diffraction instrument record powder sample, and the analysis incorporation of TOPAS V4.0 program is used
CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 4
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1), ball milling after ball milling 18h, then is sent under 500r/min speed in aqueous slurry environment
It is dried for 24 hours at 105 DEG C to baking oven；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 3h is used for subsequent heat treatment under different target temperatures；
5) using the XRD diagram of x-ray powder diffraction instrument record powder sample, and the analysis incorporation of TOPAS V4.0 program is used
CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 5
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1), ball milling after ball milling 18h, then is sent under 400r/min speed in aqueous slurry environment
It is dried for 24 hours at 105 DEG C to baking oven；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 1000 DEG C of holding 3h is used for subsequent heat treatment under different target temperatures；
5) using the XRD diagram of x-ray powder diffraction instrument record powder sample, and the analysis incorporation of TOPAS V4.0 program is used
CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 6
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1), ball milling after ball milling 20h, then is sent under 350r/min speed in aqueous slurry environment
It is dried for 24 hours at 105 DEG C to baking oven；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 0.25h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 7
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 400r/min speed, ball milling 18h, then send to
Baking oven is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 0.5h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 7
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 400r/min speed, ball milling 18h, then send to
Baking oven is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 300MPa
Material.
4) time of 950 DEG C of holding 1h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 8
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 300r/min speed, ball milling 18h, then send to
Baking oven is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 10mm is then granulated at 100MPa
Material.
4) time of 950 DEG C of holding 2h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 9
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1), ball milling after ball milling 18h, then is sent under 400r/min speed in aqueous slurry environment
It is dried for 24 hours at 105 DEG C to baking oven；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 3h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 10
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 400r/min speed, after ball milling 18h, send to
Baking oven is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 5h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 11
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 450r/min speed, after ball milling 18h, send to
Baking oven is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 9h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Embodiment 12
A kind of method using alumina stable cadmium of the present embodiment, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 0.25；
2) by mixture in step 1) in aqueous slurry environment ball milling, under 400r/min speed, after ball milling 18h, send to
Baking oven is dried for 24 hours at 105 DEG C；
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) time of 950 DEG C of holding 18h is used for subsequent heat treatment under different target temperatures；
5) using TOPAS V4.0 program analysis incorporation CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic structure.
Comparative example 1
A kind of method using alumina stable cadmium of this comparative example 1, comprising the following steps:
1) by CdO and γ-Al2O3Precursor is mixed into gross dry weight 60g, and wherein Cd/Al molar ratio is 3/4.
2) by mixture, ball milling after ball milling 18h, is sent to baking oven 105 under 400r/min speed in aqueous slurry environment
It is dried for 24 hours at DEG C.
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) 1000 DEG C of times kept for 24 hours are used for subsequent heat treatment under different target temperatures.
5) XRD diagram of each powder sample is recorded using x-ray powder diffraction instrument, structure is as shown in Figure 4.
Comparative example 2
A kind of method using alumina stable cadmium of this comparative example 2, comprising the following steps:
1) cadmium oxide (CdO) and gama-alumina (γ-Al2O3) precursor are mixed into gross dry weight 60g, wherein Cd/Al moles
Than being 2/1.
2) by mixture, ball milling after ball milling 18h, is sent to baking oven 105 under 400r/min speed in aqueous slurry environment
It is dried for 24 hours at DEG C.
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) 1000 DEG C of times kept for 24 hours are used for subsequent heat treatment under different target temperatures.
5) XRD diagram that each powder sample is recorded using x-ray powder diffraction instrument, shown in result figure 4.
Comparative example 3
A kind of method using alumina stable cadmium of this comparative example 3, comprising the following steps:
1) by cadmium oxide (CdO) and gama-alumina (γ-Al2O3) precursor is mixed into gross dry weight 60g, wherein Cd/Al moles
Than being 1/2.
2) by mixture, ball milling after ball milling 18h, is sent to baking oven 105 under 400r/min speed in aqueous slurry environment
It is dried for 24 hours at DEG C.
3) dry mixture is further homogenized with mortar grinder, the grain of Φ 20mm is then granulated at 250MPa
Material.
4) 1000 DEG C of times kept for 24 hours are used for subsequent heat treatment under different target temperatures.
5) XRD diagram that each powder sample is recorded using x-ray powder diffraction instrument, shown in result figure 5.
It can be seen that from Fig. 6, Fig. 7, in the CdO excess system that Cd/Al ratio is 3/4 or 2/1 in comparative example 1, comparative example 2
It observes even if under maximum processing temperature (1000 DEG C), for all Cd/Al=1/2 samples of comparative example 3 (for CdAl4O7Phase
For all have excessive cadmium), all observe CdO signal, therefore high proportion cadmium should be selected as reaction condition.
Effect example 1
The XRD diagram of each powder sample is recorded using x-ray powder diffraction instrument to powder prepared by embodiment 1 to 5, and is made
Incorporation CdAl is analyzed with TOPAS V4.0 program4O7The conversion ratio (TR, %) of cadmium in monoclinic structure, as a result such as the institute of Fig. 2 to 3
Show, due to CdAl4O7Mutually prevailing Cd/Al rate system, CdAl4O7Formation be CdO and γ-Al2O3In 800-
Preferred reaction between 1000 DEG C；When Cd/Al molar ratio is 1/4, a large amount of CdAl is formd at 900 DEG C4O7；At 950 DEG C
3h is handled, cadmium height mixes monoclinic system CdAl4O7In structure；Higher temperature is usually to overcome energy present in solid-state reaction
It builds and bigger driving force is provided, raise the temperature to 1000 DEG C and further promote CdAl4O7Crystallinity simultaneously harvests 83wt%'s
CdAl4O7, and mix CdAl4O7The conversion ratio of cadmium in monoclinic structure basically reaches 100%.
Effect example 2
To powder prepared by embodiment 6 to 12, the mixture that Cd/Al molar ratio is 1/4 is handled under the conditions of 950 DEG C
0.25-9h mixes CdAl4O7The conversion ratio (TR, %) of cadmium in monoclinic crystal structure, as a result as shown in figure 4, when extending sintering
Between be one of factor of most critical, homogenizing and crystallizing for product can be improved simultaneously.In 950 DEG C very short of processing time
A large amount of CdAl is formd in (0.25h)4O7(55wt%)；The processing time extends to 3h, observes CdAl4O7The slight increasing of phase
The close balance of adduction.By the processing of 9h, CdAl is observed in the sample of processing4O7For 82wt%, and the heat for passing through 18h
Processing generates the CdAl of the 90wt% in product4O7。
Effect example 3
CdAl prepared by CdO and the present embodiment 94O7Leaching cadmium content measurement in phase, measuring method includes following step
It is rapid:
1) HNO that initial leachate is pH 4.0 is configured3Aqueous solution.
2) 0.5g test powders are added in the tank filled with 500mL leachate to be tested, in magnetic agitation
Keep mixture uniform in entire leaching process under (200rpm).
3) the 1M HNO3 aqueous solution of about 20 μ L is added once the pH in leachate reaches 4.2 to incite somebody to action in real-time monitoring pH value
PH is adjusted to 4.0.
4) within every 10 minutes interval times, the 5mL leachate mixed with corresponding solid sample is extracted out and is filtered and (is used
0.2 μm of syringe filter).
5) solution measures cadmium concentration by ICP-OES 800 (PerkinElmer), analyzes it and leaches cadmium effect.
Measurement result is as shown in Figure 5:
The result shows that with the extension of leaching process, CdO and CdAl4O7Leaching cadmium in phase gradually increases, and tries leaching
At the end of testing (120 minutes), the maximum cadmium concentration observed in CdO percolate is 691.2mg/L.After surface area normalization, it
Compare CdAl4O7Sample is higher by 2 orders of magnitude or more.This significant difference shows CdAl4O7Have to the erosion ratio CdO phase of strong acid
Higher plant resistance；Leach the result shows that, to CdAl4O7Monocline transformation is a kind of efficient cadmium stable strategy.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (10)
1. a kind of method using alumina stable cadmium, which comprises the following steps:
It 1) is 0.25 by Cd/Al molar ratio, by CdO and γ-Al2O3Precursor mixing；
2) mixture in step 1) is dispersed in aqueous slurry environment, then be dried；
3) kept for the time of 0.25~18h be used for subsequent heat treatment at 800~1000 DEG C the product after drying.
In step 2) and 3) 2. the method for alumina stable cadmium according to claim 1, which is characterized in that also wrapped between
It includes and further homogenizes dry mixture, be then granulated into pellet.
3. the method for alumina stable cadmium according to claim 1, which is characterized in that the temperature in the step 3) is
900~1000 DEG C.
4. the method for alumina stable cadmium according to claim 1, which is characterized in that the time in the step 3) is
3~18h.
5. the method for alumina stable cadmium according to claim 1, which is characterized in that being separated into the step 2)
Ball milling 18~for 24 hours.
6. the method for alumina stable cadmium according to claim 5, which is characterized in that the ball milling speed be 300~
500r/min。
7. the method for alumina stable cadmium according to claim 1, which is characterized in that drying in step 2) be send to
Baking oven 18 at 100~105 DEG C~for 24 hours.
8. the method for alumina stable cadmium according to claim 2, which is characterized in that described to use mortar grinder into one
Step homogenization, is then granulated into the pellet of 10~20mm of Φ at 150~300MPa.
9. the method for alumina stable cadmium according to claim 1, which is characterized in that the product in the step 3) exists
950 DEG C of processing.
10. the product of the described in any item method preparations of a kind of pair of claim 1 to 9 carries out method used in leaching experiment,
It is characterized in that, the leaching experiment method is constant pH leaching experiment method.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105050A (en) * | 2019-05-24 | 2019-08-09 | 广州大学 | A method of cadmium in trade waste is stabilized using kaolin |
| CN110170503A (en) * | 2019-05-24 | 2019-08-27 | 广州大学 | A method of cadmium in trade waste is stabilized using mullite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100342A (en) * | 2007-06-29 | 2008-01-09 | 上海大学 | Heavy metal heat stabilizer and method for stabilizing heavy metal in heavy metal pollutant by the same |
-
2018
- 2018-08-03 CN CN201810875854.2A patent/CN109174903A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100342A (en) * | 2007-06-29 | 2008-01-09 | 上海大学 | Heavy metal heat stabilizer and method for stabilizing heavy metal in heavy metal pollutant by the same |
Non-Patent Citations (1)
| Title |
|---|
| MINHUA SU ET AL.: "Stabilizing cadmium into aluminate and ferrite structures:", 《JOURNAL OF ENVIRONMENTAL MANAGEMENT》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105050A (en) * | 2019-05-24 | 2019-08-09 | 广州大学 | A method of cadmium in trade waste is stabilized using kaolin |
| CN110170503A (en) * | 2019-05-24 | 2019-08-27 | 广州大学 | A method of cadmium in trade waste is stabilized using mullite |
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