CN113060754B - Doped cuprous dechlorinating agent and preparation method and application thereof - Google Patents
Doped cuprous dechlorinating agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a doped cuprous dechlorinating agent and a preparation method and application thereof.A precursor oxide of a doping element and a copper-containing compound are uniformly mixed and then calcined at the temperature of 250-600 ℃ to finally obtain the doped cuprous dechlorinating agent; the copper-containing compound consists of a copper simple substance and a divalent copper compound; the doping element includes a metal and/or a non-metal element. Adding the doped cuprous chloride dechlorinating agent into the wastewater containing chloride ions, stirring for precipitation reaction, carrying out solid-liquid separation after the reaction is finished, obtaining doped cuprous chloride precipitate on the solid part, and obtaining qualified wastewater with the chloride ions reaching the discharge standard on the liquid part. The preparation process of the doped cuprous dechlorinating agent is clean and environment-friendly, the operation is simple and convenient, the raw materials are low in price, the prepared doped cuprous dechlorinating agent has a good dechlorinating effect on chlorine-containing wastewater, and the doped cuprous dechlorinating agent and precipitates generated after dechlorination have good stability.
Description
Technical Field
The invention relates to the technical field of wastewater dechlorination, in particular to a doped cuprous dechlorination agent and a preparation method and application thereof.
Background
Chlorine is a widely-existing non-metallic element, is chemically active, can be combined with most metals to form compounds, and has high solubility in aqueous solution. The chlorine-containing wastewater mainly comes from industrial production, daily life of people and the like. The high-concentration chlorine-containing wastewater has strong corrosivity on metal pipelines and structures, and meanwhile, chlorine is easy to react with organic matters in water to generate carcinogens such as chloroform, trichloromethane and the like, thereby posing great threat to human health and ecological environment. Therefore, it is necessary to remove chlorine from the wastewater during the treatment of the wastewater.
At present, the methods for removing chloride ions, which are commonly used in industry, mainly include evaporation, membrane separation, ion exchange resin, chemical precipitation, and the like. The chemical precipitation method is to remove chloride ions by reacting a chlorine removing agent with the chloride ions to generate precipitates. In the traditional cuprous dechlorination method, copper powder and copper ions are added into the wastewater to generate a disproportionation reaction and a precipitation reaction so as to generate insoluble cuprous chloride precipitate, thereby achieving the purpose of removing the chloride ions in the wastewater. Zhan Yi Gem et al (chlorine removal test and research of copper slag, Gansu metallurgy, 2010) utilizes copper slag produced in the zinc hydrometallurgy cadmium production process as a chlorine removal reagent to be added into chlorine-containing wastewater, and elemental copper/divalent copper in the copper slag and chloride ions in the wastewater undergo redox reaction to generate cuprous chloride precipitate. The method has good dechlorination effect, but has long reaction time, low leaching rate of copper slag and large copper consumption, cuprous is generated by the reaction of waste copper slag and copper powder, and the ideal dechlorination effect can be achieved only by adding excessive copper and copper slag. In addition, Zjunfeng et al (CN 112028325A) selected non-ferrous smelting high-chlorine wastewater as the object of treatment, and adopted cuprous oxide to remove chlorine for the first time, and lime and sodium metaaluminate to remove chlorine for the second time. The method comprises the steps of neutral leaching zinc oxide by Shimajun et al (CN 110331282A) to obtain a zinc oxide leaching solution, adding cuprous oxide, reacting to generate cuprous chloride precipitate and dechlorinated qualified liquid, then mixing the cuprous chloride precipitate with a sodium hydroxide solution to generate cuprous oxide precipitate, mixing the cuprous oxide with waste liquid, adding hydrogen peroxide to convert the cuprous oxide into Cu2+, and generating Cu + from elemental copper in copper slag, thereby realizing regeneration and recycling of Cu +.
These methods have limited treatment effect and leave a large amount of Cu in the wastewater after dechlorination2+The subsequent water treatment cost is increased, the obtained dechlorination product cuprous chloride is unstable in property, cuprous ions in the dechlorination product cuprous chloride are easily oxidized into cupric chloride, the purity of the cuprous chloride cannot be guaranteed, and the subsequent value-added application of the cuprous chloride is influenced.
Disclosure of Invention
Aiming at solving the problems that the prior cuprous chloride has limited dechlorination effect and a great amount of Cu is remained in the wastewater after the dechlorination2+And the property of the dechlorination product cuprous chloride is unstable, and provides a doped cuprous dechlorination agent, a preparation method and application thereof. The preparation process of the doped cuprous dechlorinating agent is clean and environment-friendly,The preparation method is simple and convenient to operate, the raw materials are low in price, the prepared doped cuprous dechlorinating agent has a good dechlorinating effect on removing chloride ions in wastewater, and the doped cuprous dechlorinating agent and precipitates generated after dechlorination have good stability.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the doped cuprous dechlorinating agent comprises the following steps: uniformly mixing the precursor oxide of the doping element with a copper-containing compound, and then calcining at the temperature of 250-600 ℃ to finally obtain a doped cuprous dechlorinating agent; the copper-containing compound consists of a copper simple substance and a divalent copper compound.
Further, the doping element comprises one or more of Ca, Fe, Al, Si, B, Ag, Sn, Al, Mn, Cr, Zn, La, Mg, Co, Bi, Cs, Ni, Ti, In, Sr, Ce and Nd.
Further, the doped cuprous chloride remover comprises one or more of oxygen, hydrogen, sulfur, nitrogen and carbon besides cuprous elements and doping elements.
Furthermore, the doping amount of the doping element in the doped cuprous dechlorinating agent is 1-5 wt%.
Further, the molar ratio of the copper simple substance to the divalent copper compound is 1-1.2: 1; the calcining time is 1-4 hours.
The invention also provides the doped cuprous chloride remover prepared by the preparation method.
The last aspect of the invention provides the application of the doped cuprous dechlorinating agent prepared by the preparation method in wastewater dechlorination, and the application method comprises the following steps: and adding the doped cuprous chloride dechlorinating agent into the wastewater containing chloride ions, stirring to perform a precipitation reaction, performing solid-liquid separation after the reaction is finished, obtaining doped cuprous chloride precipitate on the solid part, and obtaining qualified wastewater with the chloride ions reaching the discharge standard on the liquid part. The doping amount of doping elements in the obtained solid part doping type cuprous chloride sediment is 0.8 wt% -4.0 wt%, and the overall purity of the doping type cuprous chloride sediment is 96% -99.2%.
Further, the content of chloride ions in the wastewater is 100 mg/L-20000 mg/L; adding the wastewater to react, wherein the pH value is 0.1-6, and the reaction temperature is 25-90 ℃; the molar ratio of cuprous ions in the doped cuprous dechlorinating agent to chloride ions in the wastewater is 0.6-1: 1.
The beneficial technical effects are as follows:
according to the method, on the basis that the cuprous dechlorinating agent is formed by high-temperature disproportionation reaction of zero-valent copper and divalent copper ions, the doped element precursor is added into the raw material, so that the element can be doped into the cuprous dechlorinating agent in the high-temperature disproportionation process to form the doped cuprous dechlorinating agent. The doping of the doping element can improve the stability of cuprous ions in the cuprous dechlorinating agent. The ion radius of the doping element is larger than or smaller than that of copper ions, so that the unit cell of the crystal of the cuprous chloride remover formed in the high-temperature disproportionation reaction process can expand or contract, and the stability of cuprous ions in the doped cuprous chloride remover can be effectively improved; in addition, the doping element can also form a relatively stable oxide in the cuprous dechlorinating agent, and the formation of the oxide contributes to the improvement of the stability of cuprous ions.
The doped cuprous chloride removal agent is added into chlorine-containing wastewater, cuprous ions are combined with chloride ions to form insoluble doped cuprous chloride precipitate, and the chloride ions dissolved in the wastewater are precipitated to remove the chloride ions; in order to allow the precipitation reaction to proceed quickly and efficiently in the dechlorination process of the chlorine-containing solution, it is necessary to adjust an appropriate reaction temperature and stir the solution for a certain period of time to allow the reaction to proceed sufficiently. The doping element in the doped cuprous dechlorinating agent basically loses very little in the dechlorinating process, and the utilization rate of cuprous ions in the dechlorinating process reaches more than 98 percent, because the doping of the doping element can improve the utilization rate of the cuprous ions and prevent the released cuprous ions from being oxidized into bivalent copper ions in the wastewater to lose the dechlorinating effect; the reaction speed of the released cuprous ions and chloride ions in the wastewater is high, the doping elements are kept in the dechlorination precipitation product in the formation process of the cuprous precipitation to form doped cuprous chloride precipitation so as to continuously maintain the stability of the cuprous chloride precipitation, the cuprous ions are prevented from being oxidized into bivalent copper ions in the dechlorination process to be released into the wastewater to a great extent, and the cost of later-stage copper removal of the wastewater is further reduced or avoided.
The doped cuprous dechlorinating agent prepared by the invention reduces the consumption of copper to a certain extent, wherein the addition of the doping element can improve the stability of the cuprous dechlorinating agent and the utilization rate of cuprous ions in the wastewater dechlorinating process, and the cuprous ions are prevented from being oxidized into cupric ions (the hydration energy of the cupric ions is higher, and the cuprous ions in water are easy to be oxidized and lose one electron to become stable cupric ions) and released into the wastewater to a great extent in the dechlorinating process; the cuprous dechlorinating agent is doped with appropriate elements, so that the stability and the dechlorinating effect of the cuprous dechlorinating agent are greatly improved, the dechlorinating process is simple to operate, and the dechlorinating effect is obvious.
The dechlorination precipitate (namely doped cuprous chloride) obtained after wastewater dechlorination by the method has stable property, and can be used as a functional material to be applied to the fields of organic synthesis, catalysis, coating, corrosion prevention and the like, for example, the dechlorination precipitate can be used as a catalyst in organic synthesis, and can be used as a raw material of an antifouling coating in the ship industry.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
(1) Preparation of Mn-doped cuprous oxide dechlorinating agent: MnO and a copper-containing compound (a mixture of elementary copper and copper oxide, the molar ratio of copper to copper oxide is 1:1) are ground in a ball mill, and after uniform mixing, the mixture is calcined at 300 ℃ for 3 hours to obtain the Mn-doped cuprous oxide dechlorinating agent with the Mn element doping amount of 1 wt%.
(2) Removing chloride ions in industrial wastewater:
obtaining industrial chlorine-containing wastewater with chloride ion concentration of 10000mg/L, adding Mn-doped cuprous oxide dechlorinating agent according to the condition that the molar ratio of cuprous ions to chloride ions in the wastewater is 1:1, adjusting the pH value of the chlorine-containing wastewater to 0.3 at 25 ℃, stirring for 30 minutes to perform precipitation reaction, performing solid-liquid separation after the reaction is finished, obtaining Mn-doped cuprous chloride precipitate from a solid part, and measuring the content of the chloride ions in a liquid part.
In the embodiment, the dechlorination efficiency of the Mn-doped cuprous oxide dechlorinating agent on industrial chlorine-containing wastewater is 99%, namely the utilization rate of cuprous ions is 99%.
Phase identification is carried out on the Mn-doped cuprous chloride precipitate at the solid part, so that the Mn-doped cuprous chloride with the main phase of 0.73 wt% can be obtained, and the overall purity of the Mn-doped cuprous chloride precipitate is 99.2%. And drying the obtained Mn-doped cuprous chloride precipitate, and then placing the precipitate in an environment with the temperature of 25 ℃ and the humidity of 50% for 1 year to obtain the product, wherein the purity of the cuprous chloride still can be maintained at 98.5%.
Example 2
(1) Preparing an Al-doped cuprous dechlorinating agent: mixing Al2O3And a copper-containing compound (a mixture of elementary copper and copper oxide, the molar ratio of copper to copper oxide is 1.2:1) are ground in a ball mill, and after uniform mixing, the mixture is calcined at 600 ℃ for 1 hour to obtain the Al-doped cuprous oxide dechlorinating agent with the Al element doping amount of 2 wt%.
(2) Removing chloride ions in industrial wastewater:
obtaining industrial chlorine-containing wastewater with chloride ion concentration of 20000mg/L, adding an Al-doped cuprous oxide dechlorinating agent according to the condition that the molar ratio of cuprous ions to chloride ions in the wastewater is 1:1, adjusting the pH value of the chlorine-containing wastewater to 3 at 50 ℃, stirring for precipitation reaction for 2000min until no precipitate is generated, then carrying out solid-liquid separation, obtaining Al-doped cuprous chloride precipitate in the solid part, and measuring the chloride ion content in the liquid part.
The dechlorination efficiency of the Al-doped cuprous oxide dechlorinating agent on the industrial chlorine-containing wastewater is 98.6 percent, namely the utilization rate of cuprous ions is 98.6 percent.
Phase identification is carried out on the Al-doped cuprous chloride precipitate at the solid part, and the cuprous chloride with the main phase of Al doping can be obtained, wherein the Al doping amount is 1.47 wt%, and the overall purity of the Al-doped cuprous chloride precipitate is 99%. And drying the obtained Al-doped cuprous chloride precipitate, and then placing the precipitate in an environment with the temperature of 25 ℃ and the humidity of 50% for 1 year to obtain the cuprous chloride with the purity of 98%.
Example 3
(1) Preparing an Ag-doped cuprous dechlorinating agent: mixing AgCO3And a copper-containing compound (a mixture of elementary copper and copper oxide, the molar ratio of copper to copper oxide is 1.1:1) are ground in a ball mill, and after uniform mixing, the mixture is calcined at 250 ℃ for 4 hours to obtain the Ag-doped cuprous oxide dechlorinating agent with the Ag doping amount of 1.5 percent.
(2) Removing chloride ions in industrial wastewater:
obtaining industrial chlorine-containing wastewater with chloride ion concentration of 100mg/L, adding an Ag-doped cuprous oxide dechlorinating agent according to the condition that the molar ratio of cuprous ions to chloride ions in the wastewater is 0.8:1, adjusting the pH value of the chlorine-containing wastewater to 6 at 30 ℃, stirring for precipitation reaction for 2880min until no precipitate is generated, then carrying out solid-liquid separation, obtaining Ag-doped cuprous chloride precipitate in the solid part, and measuring the content of the chloride ions in the liquid part.
The dechlorination efficiency of the Ag-doped cuprous oxide dechlorination agent prepared by the embodiment on industrial chlorine-containing wastewater is 99.6%, namely the utilization rate of cuprous ions is 99.6%.
Phase identification is carried out on the solid part of the Ag-doped cuprous chloride precipitate to obtain the Ag-doped cuprous chloride of which the main phase is 1.14 wt%, and the overall purity of the Ag-doped cuprous chloride precipitate is 98.8%. And drying the obtained Ag-doped cuprous chloride precipitate, and then placing the precipitate in an environment with the temperature of 25 ℃ and the humidity of 50% for 1 year to obtain the product, wherein the purity of the cuprous chloride still can be maintained at 98%.
Example 4
(1) Preparing a Ca-doped cuprous dechlorinating agent: and grinding CaO and a copper-containing compound (a mixture of elementary copper and copper oxide, wherein the molar ratio of copper to copper oxide is 1:1) in a ball mill, uniformly mixing, and calcining at 450 ℃ for 1 hour to obtain the Ca-doped cuprous oxide dechlorinating agent with the Ca doping amount of 5%.
(2) Removing chloride ions in industrial wastewater:
obtaining industrial chlorine-containing wastewater with the chloride ion concentration of 5000mg/L, adding a Ca-doped cuprous oxide dechlorinating agent according to the condition that the molar ratio of cuprous ions to chloride ions in the wastewater is 1:1, adjusting the pH value of the chlorine-containing wastewater to 1 at 70 ℃, stirring for precipitation reaction for 60min until no precipitate is generated, finishing the reaction, then carrying out solid-liquid separation, obtaining Ca-doped cuprous chloride precipitate on the solid part, and measuring the chloride ion content on the liquid part.
The dechlorination efficiency of the Ca-doped cuprous oxide dechlorinating agent prepared by the embodiment on industrial chlorine-containing wastewater is 98%, namely the utilization rate of cuprous ions is 98%.
Phase identification is carried out on the Ca-doped cuprous chloride precipitate at the solid part, and the main phase of the Ca-doped cuprous chloride precipitate can be obtained, wherein the doping amount of Ca is 3.72 wt%, and the overall purity of the Ca-doped cuprous chloride precipitate is 96%. And drying the obtained Ca-doped cuprous chloride precipitate, and then placing the precipitate in an environment with the temperature of 25 ℃ and the humidity of 50% for 1 year to obtain the product, wherein the purity of the cuprous chloride still can be kept at 96%.
Example 5
(1) Preparing a Zn-doped cuprous dechlorinating agent: ZnO and a copper-containing compound (a mixture of elementary copper and copper oxide, the molar ratio of copper to copper oxide is 1.2:1) are ground in a ball mill, uniformly mixed and calcined at 350 ℃ for 2 hours to obtain the Zn-doped cuprous oxide dechlorinating agent with the Zn doping amount of 2%.
(2) Removing chloride ions in industrial wastewater:
obtaining industrial chlorine-containing wastewater with chloride ion concentration of 3000mg/L, adding a Zn-doped cuprous oxide dechlorinating agent according to the condition that the molar ratio of cuprous ions to chloride ions in the wastewater is 0.6:1, adjusting the pH value of the chlorine-containing wastewater to 1 at 50 ℃, stirring for carrying out precipitation reaction for 30min until no precipitate is generated, then carrying out solid-liquid separation, obtaining Zn-doped cuprous chloride precipitate in a solid part, and measuring the chloride ion content in a liquid part.
The dechlorination efficiency of the Zn-doped cuprous oxide dechlorination agent prepared by the embodiment on industrial chlorine-containing wastewater is 98.2%, namely the utilization rate of cuprous ions is 98.2%.
Phase identification is carried out on the Zn-doped cuprous chloride precipitate at the solid part, so that Zn-doped cuprous chloride with the main phase, wherein the doping amount of Zn is 1.51 wt%, and the overall purity of the Zn-doped cuprous chloride precipitate is 97.2%, can be obtained. And drying the obtained Zn-doped cuprous chloride precipitate, and then placing the Zn-doped cuprous chloride precipitate for 1 year in an environment with the temperature of 25 ℃ and the humidity of 50 percent, wherein the purity of the cuprous chloride still can be kept at 96.5 percent.
Example 6
(1) Preparing a Ti-doped cuprous dechlorinating agent: adding TiO into the mixture2And a copper-containing compound (a mixture of elementary copper and copper oxide, the molar ratio of copper to copper oxide is 1.1:1) are ground in a ball mill, and after uniform mixing, the mixture is calcined at 550 ℃ for 2 hours to obtain the Ti-doped cuprous oxide dechlorinating agent with the Ti doping amount of 2%.
(2) Removing chloride ions in industrial wastewater:
obtaining industrial chlorine-containing wastewater with chloride ion concentration of 8000mg/L, adding a Ti-doped cuprous oxide dechlorinating agent according to the condition that the molar ratio of cuprous ions to chloride ions in the wastewater is 1:1, adjusting the pH value of the chlorine-containing wastewater to 0.1 at 70 ℃, stirring for carrying out precipitation reaction for 1min until no precipitate is generated, then carrying out solid-liquid separation, obtaining Ti-doped cuprous chloride precipitate in the solid part, and measuring the chloride ion content in the liquid part.
The dechlorination efficiency of the Ti-doped cuprous oxide dechlorination agent prepared by the embodiment on industrial chlorine-containing wastewater is 99.1%, namely the utilization rate of cuprous ions is 99.1%.
Phase identification is carried out on the Ti-doped cuprous chloride precipitate at the solid part, and the Ti-doped cuprous chloride which is the main phase can be obtained, wherein the doping amount of Ti is 1.47 wt%, and the overall purity of the Ti-doped cuprous chloride precipitate is 98.5%. And drying the obtained Ti-doped cuprous chloride precipitate, and then placing the precipitate in an environment with the temperature of 25 ℃ and the humidity of 50% for 1 year to obtain the cuprous chloride with the purity of 98%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. The preparation method of the doped cuprous dechlorinating agent is characterized by comprising the following steps: uniformly mixing the precursor oxide of the doping element with a copper-containing compound, and then calcining at the temperature of 250-600 ℃ to finally obtain a doped cuprous dechlorinating agent; the copper-containing compound consists of a copper simple substance and a divalent copper compound;
the doping elements comprise one or more of Ca, Fe, Si, B, Ag, Sn, Al, Mn, Cr, Zn, La, Mg, Co, Bi, Cs, Ni, Ti, In, Sr, Ce and Nd;
the doping amount of the doping element in the doped cuprous dechlorinating agent is 1-5 wt%.
2. The method for preparing the doped cuprous chloride remover as claimed in claim 1, wherein said doped cuprous chloride remover comprises one or more of oxygen, hydrogen, sulfur, nitrogen and carbon in addition to cuprous element and doping elements.
3. The preparation method of the doped cuprous dechlorinating agent according to any one of claims 1-2, wherein the molar ratio of the copper simple substance to the divalent copper compound is 1-1.2: 1; the calcining time is 1-4 hours.
4. Doped cuprous dechlorinating agent prepared by the preparation method according to any one of claims 1-2.
5. The application of the doped cuprous dechlorinating agent prepared by the preparation method according to any one of claims 1-2 in wastewater dechlorination is characterized in that the application method comprises the following steps: and adding the doped cuprous chloride dechlorinating agent into the wastewater containing chloride ions, stirring to perform a precipitation reaction, performing solid-liquid separation after the reaction is finished, obtaining doped cuprous chloride precipitate on the solid part, and obtaining qualified wastewater with the chloride ions reaching the discharge standard on the liquid part.
6. The use according to claim 5, wherein the content of chloride ions in the wastewater is 100mg/L to 20000 mg/L; adding the wastewater to react, wherein the pH value is 0.1-6, and the reaction temperature is 25-90 ℃; the molar ratio of cuprous ions in the doped cuprous dechlorinating agent to chloride ions in the wastewater is 0.6-1: 1.
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