CN114272902B - Composite material for removing metallic copper ions in acidic wastewater and preparation method and application thereof - Google Patents
Composite material for removing metallic copper ions in acidic wastewater and preparation method and application thereof Download PDFInfo
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- CN114272902B CN114272902B CN202111531926.XA CN202111531926A CN114272902B CN 114272902 B CN114272902 B CN 114272902B CN 202111531926 A CN202111531926 A CN 202111531926A CN 114272902 B CN114272902 B CN 114272902B
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- composite material
- copper ions
- titanium dioxide
- acidic wastewater
- phytic acid
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 56
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000227 grinding Methods 0.000 claims abstract description 32
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 31
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940068041 phytic acid Drugs 0.000 claims abstract description 31
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 31
- 239000000467 phytic acid Substances 0.000 claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 21
- 239000002184 metal Substances 0.000 abstract description 21
- 239000010949 copper Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention discloses a composite material for efficiently removing metallic copper ions in acidic wastewater, and the raw materials for preparing the composite material comprise titanium dioxide and phytic acid. The invention also discloses the composite material and a preparation method thereof: the mechanical force grinding means is adopted, the raw materials are placed into a grinding machine according to a certain proportion, the rotating speed of the grinding machine is 100-1000r/min, and the composite material is obtained through grinding. The composite material is put into copper-containing acidic wastewater to be treated, and after stirring treatment for 15-120min, the removal rate of copper ions in the acidic wastewater is over 99 percent, and meanwhile, the acid liquor in the wastewater can be recycled. The composite material has the advantages of simple preparation process, environment friendliness, capability of efficiently removing metal copper ions in acid wastewater without alkali addition for neutralization, realization of acid liquor recycling and the like, and can be widely applied to copper-containing acid wastewater treatment in the industries of chemical industry, smelting, electroplating and the like.
Description
Technical Field
The invention relates to the field of wastewater treatment, relates to a composite material for efficiently removing metal copper ions in acidic wastewater and a preparation method thereof, and further relates to application of the composite material.
Background
The industrialization process of the rapid development of China causes a large amount of heavy metal emission, and hundreds of millions of tons of harmful metal ions (mainly Cu) are emitted each year in industries such as chemical industry, smelting, electroplating and the like 2+ 、Zn 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ ，Mn 2+ Etc.). At present, the treatment methods of the copper ion-containing acidic wastewater mainly comprise a neutralization precipitation method, an ion exchange method, an adsorption method, an electrochemical method, a microorganism restoration method and the like, wherein the adsorption method has high selectivity, the adsorbent can be recycled, and the low-concentration metal ion-containing wastewater can be treatedThe acid waste water is widely used.
The existing adsorbents for removing copper ions in acid wastewater mainly comprise a high-molecular polymer adsorbent, a macromolecular organic acid adsorbent, a modified clay mineral adsorbent and the like, and basically all the adsorbents have the problems of complex preparation process, high production cost, easiness in desorbing the adsorbed copper ions in the acid wastewater again, incapability of recycling acid liquor in the wastewater and the like, so that the adsorbents are difficult to popularize and apply in industrial production on a large scale. Therefore, the development and preparation of the novel acidic wastewater copper ion adsorption material which has the advantages of simple process, low production cost and high removal rate and can realize the recycling of the acid liquor in the wastewater is significant.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a composite material for efficiently removing metal copper ions in acidic wastewater, which has the advantages of environmental protection, low cost, high copper ion removal rate in the acidic wastewater, capability of realizing the recycling of acid liquor in the wastewater, and the like.
The invention further aims to provide a preparation method of the composite material for efficiently removing the metal copper ions in the acidic wastewater, and the method has the advantage of simple preparation process. The obtained composite material can realize the efficient and low-cost removal of metal copper ions in the acidic wastewater by means of ion exchange and adsorption only by mixing and stirring with the copper-containing acidic wastewater.
It is still another object of the present invention to provide a use of the above composite material, wherein the composite material of the present invention can achieve efficient and low-cost removal of metallic copper ions in acidic wastewater by means of ion exchange and adsorption only by mixing and stirring with the copper-containing acidic wastewater.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a composite material for efficiently removing metallic copper ions in acidic wastewater is characterized in that: the raw materials for preparing the composite material comprise titanium dioxide and phytic acid, and the molar ratio of the titanium dioxide to the phytic acid is 10-100:1.
in the technical scheme of the composite material for efficiently removing the metal copper ions in the acidic wastewater, a further preferable technical scheme is as follows: the mole ratio of the titanium dioxide to the phytic acid is 40-50:1.
in the technical scheme of the composite material for efficiently removing the metal copper ions in the acidic wastewater, a further preferable technical scheme is as follows: titanium dioxide particles are adopted as raw material titanium dioxide, and TiO in the titanium dioxide particles 2 The content is more than 90 percent.
In the technical scheme of the composite material for efficiently removing the metal copper ions in the acidic wastewater, a further preferable technical scheme is as follows: the raw material phytic acid adopts phytic acid particles, and C in the phytic acid particles 6 H 18 O 24 P 6 The content is more than 90 percent.
The invention also provides a preparation method of the composite material for efficiently removing the metal copper ions in the acidic wastewater, which is characterized by comprising the following steps of: the raw materials of titanium dioxide and phytic acid are proportionally placed into a mill by adopting a mechanical grinding means, and are ground for 30-240min at the rotating speed of 100-1000r/min, so that the composite material is obtained.
Further, the mill used in the above scheme includes, but is not limited to, a planetary ball mill; the mechanical grinding means is dry ball milling.
Further, in the scheme, the mass ratio of the grinding medium to the material is controlled to be 10-50 during grinding: 1.
further, in the above scheme, the grinding medium comprises, but is not limited to, zirconia balls, and the cavity of the ball mill comprises, but is not limited to, a zirconia tank; and the particle diameter of the zirconia balls is preferably 10 to 20mm.
The invention also provides the application of the composite material for efficiently removing the metal copper ions in the acidic wastewater or the composite material prepared by the preparation method according to any one of the above, wherein the application is to use the composite material in the acidic wastewater treatment to remove the metal copper ions.
Further, when used in the above scheme, the mass ratio of the composite material to the acidic wastewater is 300-1000 g/ton.
Compared with the prior art, the invention has the beneficial effects that:
1) The raw materials adopted by the invention are common chemical raw materials, have wide sources, are nontoxic and pollution-free, and can not cause secondary pollution;
2) The preparation method adopted by the invention is dry mechanical ball milling, and has the characteristics of low cost, environmental protection, no generation of three wastes, easy industrialized popularization and the like;
3) The composite material prepared by the invention has the metal copper ion removal rate of over 99 percent on the acidic wastewater, can realize the recycling of the acid liquor in the wastewater, and has high efficiency and high economic benefit. The composite material is convenient to use, and the removal rate of copper ions in the acidic wastewater is over 99% after being put into the copper-containing acidic wastewater to be treated and stirred for 15-120 min.
4) The method takes the titanium dioxide particles and the phytic acid particles as raw materials, adopts a dry mechanical ball milling method to prepare the composite material, has the advantages of simplicity, high efficiency, low cost, environmental friendliness, no pollution and the like, and can efficiently remove metal copper ions in the acidic wastewater and realize the recycling of acid liquor in the wastewater. Can be widely applied to the treatment of copper-containing acidic wastewater produced in the industries of chemical industry, smelting, electroplating and the like.
Drawings
FIG. 1 is an XRD pattern of the composite prepared in example 3 before and after copper ion adsorption.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1, a composite material for efficiently removing metallic copper ions in acidic wastewater:
the raw materials for preparing the composite material comprise titanium dioxide and phytic acid, and the molar ratio of the titanium dioxide to the phytic acid is 10:1. titanium dioxide is adopted as raw material titanium dioxideParticles, tiO in titanium dioxide particles 2 The content was 91%. The raw material phytic acid adopts phytic acid particles, and C in the phytic acid particles 6 H 18 O 24 P 6 The content was 94%. The preparation method of the composite material for efficiently removing the metal copper ions in the acidic wastewater comprises the following steps of: and (3) adopting a mechanical force grinding means, proportionally placing the raw materials of titanium dioxide and phytic acid into a grinding machine, and grinding for 240min at the rotating speed of 100r/min to obtain the composite material. The adopted mill is a planetary ball mill; the mechanical grinding means is dry ball milling. The mass ratio of the grinding medium to the material is controlled to be 10 during grinding: 1. the ore grinding medium is zirconia balls, and the cavity of the ball mill is a zirconia tank; and the particle size of the zirconia balls was 10mm. The composite material for efficiently removing the metal copper ions in the acidic wastewater can be used in the acidic wastewater treatment to remove the metal copper ions. When in use, the mass ratio of the composite material to the acid wastewater is 300 g/ton. Directly adding and stirring.
Example 2, a composite material for efficiently removing metallic copper ions in acidic wastewater:
the raw materials for preparing the composite material comprise titanium dioxide and phytic acid, and the molar ratio of the titanium dioxide to the phytic acid is 100:1. titanium dioxide particles are adopted as raw material titanium dioxide, and TiO in the titanium dioxide particles 2 The content was 95%. The raw material phytic acid adopts phytic acid particles, and C in the phytic acid particles 6 H 18 O 24 P 6 The content was 92%. The preparation method of the composite material for efficiently removing the metal copper ions in the acidic wastewater comprises the following steps of: and (3) adopting a mechanical force grinding means, proportionally placing the raw materials of titanium dioxide and phytic acid into a grinding machine, and grinding for 30min at the rotating speed of 1000r/min to obtain the composite material. The mechanical grinding means is dry ball milling. The mass ratio of the grinding medium to the material is controlled to be 50:1. the particle size of the grinding medium is 20mm. The composite material for efficiently removing the metal copper ions in the acidic wastewater can be used in the acidic wastewater treatment to remove the metal copper ions. When in use, the mass ratio of the composite material to the acid wastewater is 1000 g/ton. Directly adding and stirring.
The equipment used in the following examples is as follows:
and (3) grinding: german Fritsch Pulverisette-7 planetary ball mill; constant temperature stirrer: shanghai Chi Co., ltd 534G; measuring the content of copper ions by adopting an atomic absorption spectrometry, wherein the AA6880 type of the Shimadzu corporation; the phase analysis is carried out by adopting an X-ray diffractometer: type D/MAX-IIIA of Rigaku corporation of Japan.
Embodiment 3, a preparation method of a composite material for efficiently removing metallic copper ions in acidic wastewater comprises the following steps:
1.20g of titanium dioxide particles and 0.66g of phytic acid particles (molar ratio 15:1) were placed in a 45cm position 3 Adding 80g of zirconia balls with the diameter of 15mm into a zirconia grinding tank, setting the rotating speed of a grinding machine to be 600rpm, and grinding for 120min to obtain the composite material (abbreviated as Ti-PA).
FIG. 1 shows XRD patterns of products obtained before and after the composite material prepared in example 3 was used for adsorbing acidic wastewater containing copper ions, respectively. As can be seen from fig. 1, anatase phase diffraction peaks and rutile phase diffraction peaks appear in the composite material after grinding, which proves that the titanium dioxide particles undergo crystal form transformation; adsorption of Cu 2+ After the ion, the diffraction peak of the crystal structure of anatase or rutile is reduced in peak form, and at the same time, the diffraction peak at 25 degrees shifts to a low angle, which means Cu 2+ The incorporation of (C) increases the interplanar spacing of the entire structure, proving Cu 2+ Has been adsorbed into the composite structure.
The composite material Ti-PA prepared in example 3 was added to acid waste water with copper ion concentration of 50mg/L and 100mg/L, respectively, the acid waste water was collected from a copper mine, the initial pH value of the acid waste water was 3.0, ca 2+ 、Mg 2+ 、Zn 2+ 、Pb 2+ The content of the plasma metal ions is less than 0.1mg/L, and the dosage of the Ti-PA composite material is 0.5g/L. The stirring speed was set at 400rpm at 25℃for 2 hours, and the pH of the solution was measured after the completion of stirring. Taking out supernatant after the solution is settled and precipitated, filtering the supernatant by using a filter membrane with the diameter of 0.45 microns, measuring the concentration of copper ions in the filtered supernatant by using an atomic absorption spectrometry, and calculating the removal rate of the copper ions, wherein the result is shown in Table 1.
TABLE 1 Effect of the composite material prepared in example 3 on removal of copper ions from acidic waste liquid
From table 1, it can be seen that the composite material Ti-PA prepared in this embodiment can efficiently remove copper ions in acidic wastewater with pH value of 3.0, the removal rate is over 99%, the pH value of the solution after copper ion removal is reduced to about 2.80, and the solution can be reused, thereby realizing recycling of acid liquor.
Example 4:
the composite material of example 4 was prepared in substantially the same manner as in example 3 except that 1.49g of titanium dioxide particles and 0.62g of phytic acid particles (molar ratio 20:1) were added to the mill at 800rpm for 180 minutes.
The effect of the composite material prepared in example 4 on removal of copper ions from the acidic waste liquid is shown in table 2.
TABLE 2 Effect of the composite material prepared in example 4 on removal of copper ions from acidic waste liquid
Example 5
The composite material of example 5 was prepared in substantially the same manner as in example 3 except that 1.57g of titanium dioxide particles and 0.52g of phytic acid particles (molar ratio 25:1) were added to the mill at 1000rpm for 240 minutes.
The effect of the composite material prepared in example 5 on removal of copper ions from the acidic waste liquid is shown in table 3.
TABLE 3 effect of the composite material prepared in example 5 on removal of copper ions from acidic waste liquid
As can be seen from examples 3-5 above: the composite material Ti-PA prepared by different preparation process parameters can effectively remove metal copper ions in the acidic waste liquid, and the removal rate is more than 99 percent; meanwhile, the pH value of the treated waste liquid is about 2.8, and the treated waste liquid can be used as acid liquor for recycling; therefore, the composite material Ti-PA has good technical effect and economic benefit in the aspect of treating the acid waste liquid containing the metal copper ions.
Claims (10)
1. A composite material for efficiently removing metallic copper ions in acidic wastewater is characterized in that: the raw materials for preparing the composite material consist of titanium dioxide and phytic acid, and the molar ratio of the titanium dioxide to the phytic acid is 10-100:1.
2. the composite material for efficiently removing metallic copper ions in acidic wastewater according to claim 1, wherein the composite material is characterized in that: the mole ratio of the titanium dioxide to the phytic acid is 40-50:1.
3. the composite material for efficiently removing metallic copper ions in acidic wastewater according to claim 1, wherein the composite material is characterized in that: titanium dioxide particles are adopted as raw material titanium dioxide, and TiO in the titanium dioxide particles 2 The content is more than 90 percent.
4. The composite material for efficiently removing metallic copper ions in acidic wastewater according to claim 1, wherein the composite material is characterized in that: the raw material phytic acid adopts phytic acid particles, and C in the phytic acid particles 6 H 18 O 24 P 6 The content is more than 90 percent.
5. A method for preparing a composite material for efficiently removing metallic copper ions in acidic wastewater according to any one of claims 1 to 4, comprising the steps of: the raw materials of titanium dioxide and phytic acid are proportionally placed into a mill by adopting a mechanical grinding means, and are ground for 30-240min at the rotating speed of 100-1000r/min, so that the composite material is obtained.
6. The method of manufacturing according to claim 5, wherein: the mills employed include, but are not limited to, planetary ball mills; the mechanical grinding means is dry ball milling.
7. The method of manufacturing according to claim 5, wherein: the mass ratio of the grinding medium to the material is controlled to be 10-50 during grinding: 1.
8. the method of manufacturing according to claim 5, wherein: grinding media including but not limited to zirconia balls, the cavities of the ball mill including but not limited to zirconia tanks; and the particle size of the zirconia balls is 10-20mm.
9. Use of a composite material for efficiently removing metallic copper ions from acidic wastewater according to any one of claims 1 to 4 or a composite material prepared by a preparation method according to any one of claims 5 to 8, characterized in that: the application is that the composite material is used in acid wastewater treatment to remove metallic copper ions.
10. Use according to claim 9, characterized in that the mass ratio of the composite material to the acidic waste water is 300-1000 g/ton in use.
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