CN116022944A - Method for simultaneously removing ruthenium and zinc in wastewater - Google Patents
Method for simultaneously removing ruthenium and zinc in wastewater Download PDFInfo
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Abstract
The invention relates to a method for simultaneously removing ruthenium and zinc in wastewater, which adjusts the pH value of the wastewater to convert the zinc into sediment; combining ruthenium-containing groups in the wastewater with the precipitate by means of a ruthenium-binding agent; the precipitate is then removed from the wastewater, and the ruthenium element is removed along with the precipitate. The invention can remove ruthenium and zinc in the wastewater through one-step precipitation, so that the concentration of ruthenium and the concentration of zinc in the wastewater after treatment are less than 2.0mg/L, the color of the wastewater is eliminated, and the requirement of direct discharge of the wastewater on ruthenium and zinc elements is met. The method of the invention is simple and convenient to operate and easy to be industrially implemented.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a method for simultaneously removing ruthenium and zinc in wastewater.
Background
In recent years, ruthenium has shown unique and stable catalytic performance in industrial catalysis and organic synthesis, so that attention of a plurality of students is drawn, and research and application layers of ruthenium-based catalysts in chemical industries such as byproduct hydrogen chloride utilization, ammonia synthesis, fischer-Tropsch synthesis, benzene selective hydrogenation and the like are endless. Because ruthenium-containing groups are generally colored, ruthenium-containing wastewater with color can be generated in the preparation process of the ruthenium-based catalyst, and ruthenium in the wastewater can be removed to eliminate the color of the wastewater, so that the direct discharge requirement of the wastewater is met. Meanwhile, the wastewater generated in the catalyst preparation process often contains not only ruthenium as a metal element but also other metal elements which need to be removed.
Taking a cyclohexene catalyst prepared by benzene selective hydrogenation as an example, the catalyst is a ruthenium and zinc bimetallic catalyst, alkaline wastewater generated in the catalyst preparation process contains ruthenium and zinc elements at the same time, and the concentration of the ruthenium and the zinc in the wastewater is lower and is respectively less than or equal to 50.0mg/L and less than or equal to 500.0mg/L. Although the ruthenium concentration in the wastewater is low, the wastewater is still obviously colored, and the color of the wastewater is changed from pale yellow to brown yellow along with the increase of the ruthenium concentration in the wastewater. The research result shows that when the ruthenium concentration is less than or equal to 2.0mg/L, the chromaticity (dilution factor) of the wastewater is less than or equal to 50, and the wastewater can be basically identified as colorless, thereby meeting the requirements of national standard GB 8978-1996 comprehensive wastewater discharge standard; when the ruthenium concentration is more than 2.0mg/L, the chromaticity (dilution multiple) of the wastewater is more than 50, and the wastewater cannot be directly discharged. Therefore, in order to meet the requirement of direct discharge of wastewater, the concentration of ruthenium in the treated wastewater is less than or equal to 2.0mg/L. Meanwhile, according to the requirements of national standard GB 8978-1996, the concentration of zinc in the treated wastewater is less than or equal to 2.0mg/L. In conclusion, the concentration of ruthenium and zinc in the treated wastewater is less than or equal to 2.0mg/L, so that the requirement of direct wastewater discharge can be met.
The research on removing zinc from zinc-containing wastewater is relatively large, but the deep removal of ruthenium from ruthenium-containing wastewater is not reported from the wastewater treatment perspective, and particularly the concentration of ruthenium in the treated wastewater is less than or equal to 2.0mg/L. The field of ruthenium recovery and purification, such as recovery of ruthenium from ruthenium-containing solutions, is relatively high, and the focus of such research is on ruthenium recovery, and the concentration of ruthenium in the treated solution is still relatively high, so that the treated solution is still colored, and direct discharge cannot be realized.
The method for recovering ruthenium or ruthenium compounds from ruthenium compound solution according to patent application CN103380219a discloses a method for recovering ruthenium from ruthenium compound solution by adding an inorganic adsorbent to ruthenium compound solution, then adding an acid to dissolve the inorganic adsorbent, then adjusting pH to 7 or more with alkali solution to precipitate the inorganic adsorbent, and adsorbing ruthenium or ruthenium compounds on the inorganic adsorbent. The inorganic adsorbent is one or a mixture of a plurality of calcium phosphate compounds, talcum powder block compounds and amorphous aluminosilicate. The examples show that the concentration of ruthenium in the pre-treatment solution is 650ppm to 810ppm and that the concentration of ruthenium in the post-treatment solution is 3.7ppm to 9.5ppm.
A method for recovering ruthenium from ruthenium-containing solutions is disclosed in patent application CN111235395a, in which the pH of the ruthenium-containing solution is adjusted to be alkaline by adding a base, then sodium hypochlorite solution is added for reaction, finally a precipitant is added, filtration is performed, the precipitate is washed until no impurity ions are present, and the filter cake is converted into a chlororuthenic acid solution by hydrochloric acid treatment. The examples show that the concentration of ruthenium in the pre-treatment solution is 0.25% and that the concentration of ruthenium in the post-treatment solution is 5ppm to 18ppm.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a treatment method of wastewater containing ruthenium and zinc, which can simultaneously treat the concentration of ruthenium and the concentration of zinc to below 2.0mg/L through one-step precipitation.
The invention provides a method for simultaneously removing ruthenium and zinc in wastewater, which comprises the following steps: adjusting the pH value of the wastewater to convert zinc into sediment; combining ruthenium-containing groups in the wastewater with the precipitate by means of a ruthenium-binding agent; removing the precipitate from the wastewater; the pH of the wastewater is > 12 and ruthenium is present in the anionic groups.
According to the method of the invention, after removing the precipitate, the wastewater from which ruthenium and zinc are removed is obtained.
According to the method of the invention, the pH value of the wastewater is regulated to be 10-11, so that zinc is converted into sediment.
According to the method of the invention, a ruthenium binder can be added to the wastewater before or after the pH of the wastewater is adjusted.
According to one embodiment of the invention, ruthenium binding agent is added to the wastewater, the pH value of the wastewater is adjusted, and after precipitation occurs, stirring is continued, and then the precipitation is separated and removed.
According to another embodiment of the invention, after adjusting the pH of the wastewater, a ruthenium binder is added to the wastewater; preferably, the ruthenium binder is added after precipitation has occurred. Preferably, after addition of the ruthenium binder, stirring is continued and the precipitate is removed again.
According to both of the foregoing embodiments, before separation and removal of the precipitate, the supernatant may be separated by standing, and then the precipitate may be removed by a conventional solid-liquid separation method, such as one or more of filtration, sedimentation or centrifugation.
According to the treatment method of the invention, ruthenium is used as or substantially used as [ RuCHO ] 3 ] - 、[RuC 2 H 3 SO 5 ] - 、[RuC 4 H 5 OCl 2 ] - And [ RuC 3 H 4 O 4 Cl] - One or more forms of the above. The term "substantially with" means, except for the term "RuCHO 3 ] - 、[RuC 2 H 3 SO 5 ] - 、[RuC 4 H 5 OCl 2 ] - And [ RuC 3 H 4 O 4 Cl] - In addition to the ruthenium in one or more forms, the total content of the ruthenium in other forms in the wastewater is less than 1.0mg/L.
According to the treatment method of the invention, the pH value of the wastewater is more than 12. In the wastewater, zinc is present in anionic groups (e.g. ZnO 2 2- )。
According to the treatment method of the present invention, the concentration of ruthenium in the wastewater before treatment is preferably not more than 50.0mg/L, more preferably 5.0mg/L to 50.0mg/L, still more preferably 5.0mg/L to 30.0mg/L, based on the mass of ruthenium element.
According to the treatment method of the present invention, the concentration of zinc in the wastewater before treatment is preferably 500.0mg/L or less, more preferably 10.0mg/L to 500.0mg/L, based on the mass of zinc element.
According to the treatment method of the present invention, the sodium concentration in the wastewater before treatment is generally 800.0mg/L to 16000.0mg/L.
According to the treatment method of the present invention, the concentration of chloride ions in the wastewater before treatment is generally 90.0mg/L to 6000.0mg/L.
According to the treatment method of the present invention, the sulfate ion concentration in the wastewater before treatment is generally 20.0mg/L to 1700.0mg/L.
According to the treatment method of the invention, the wastewater is generated in the process of preparing the benzene selective hydrogenation catalyst. The benzene selective hydrogenation catalyst is a ruthenium and zinc bimetallic catalyst. In the wastewater, the concentration of sodium is generally 800.0 mg/L-16000.0 mg/L; the concentration of chloride ions is generally 90.0 mg/L-6000.0 mg/L; the sulfate ion concentration is generally 20.0mg/L to 1700.0mg/L.
According to the treatment method of the present invention, the method is carried out at ambient temperature, for example, at 10 to 35 ℃.
According to the method of the present invention, ruthenium-containing groups in the wastewater are bound to the precipitate by a ruthenium binding agent, and then the precipitate is removed from the wastewater, so that the ruthenium-containing groups are removed with the precipitate.
According to the method of the invention, the ruthenium binder is a cationic organic polymer, preferably a cationic polyacrylamide. The cationic polyacrylamide is a water-soluble linear high molecular polymer, and the synthesis method is a mature technology. The molecular weight of the cationic polyacrylamide is not particularly limited, and can be thousands, tens of thousands, hundreds of thousands or hundreds of thousands up to tens of thousands. The cationic degree of the cationic polyacrylamide can be 10% -60% (the measuring method can be seen in GB/T31246-2014). In the invention, the ruthenium bonding agent is preferably a cationic polyacrylamide flocculant, and the molecular weight of the cationic polyacrylamide is generally 800-1200 ten thousand when the ruthenium bonding agent is used as the flocculant. The cationic polyacrylamide is conveniently available commercially; can also be synthesized according to the known method. In the invention, the cationic polyacrylamide is preferably quaternary ammonium type cationic polyacrylamide. The quaternary ammonium type cationic polyacrylamide is a quaternary ammonium type cation.
Further, the mass ratio of the ruthenium binder to the wastewater is preferably (10 -6 ～10 -5 )：1。
Further, the cationic polyacrylamide can be prepared into an aqueous solution with the mass fraction of 0.01-0.5%, and preferably prepared into an aqueous solution with the mass fraction of 0.05-0.3%.
According to the treatment method provided by the invention, the concentration of ruthenium and the concentration of zinc in the treated wastewater are less than 2.0mg/L, the color of the wastewater is eliminated, and the requirement of direct discharge of the wastewater on ruthenium and zinc elements is met.
The beneficial effects of the invention are as follows: the ruthenium and zinc in the wastewater can be removed simultaneously through one-step precipitation, so that the concentration of ruthenium and the concentration of zinc in the wastewater after treatment are less than 2.0mg/L, the color of the wastewater is eliminated, and the requirement of direct discharge of the wastewater on ruthenium and zinc elements is met. The method of the invention is simple and convenient to operate and easy to be industrially implemented.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical values disclosed in the present specification include not only the numerical values specifically disclosed in the embodiments but also the end points of each numerical value range in the specification, and any combination of these numerical values should be considered as the disclosed or described range of the present invention, unless explicitly stated otherwise.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
Numerical ranges defined in the present invention include the endpoints of the numerical ranges unless expressly stated otherwise.
It is understood that in the ruthenium and zinc-containing wastewater, the ruthenium concentration and the zinc concentration are respectively higher than 2.0mg/L based on the mass of ruthenium element and the mass of zinc element.
In the embodiment, the concentration of ruthenium and zinc elements in the wastewater containing ruthenium and zinc is measured by adopting a Baird PS-4 type ICP-AES plasma inductively coupled atomic emission spectrometer according to a standard curve method.
In the examples, the ruthenium-containing group detection was analyzed by ultra high performance liquid chromatography-quaternary column electrostatic field Orbitrap mass spectrometry (UPLC-Orbitrap) of the United states Siemens. The analysis conditions were: the mobile phase A is water, the mobile phase B is methanol, and the PDA detection wavelength is 210-800nm. The wastewater of the examples was examined for ruthenium-containing groups in the form of [ RuCHO ] 3 ] - 、[RuC 2 H 3 SO 5 ] - 、[RuC 4 H 5 OCl 2 ] - And [ RuC 3 H 4 O 4 Cl] - One or more forms of the above.
In the examples, the cationic polyacrylamides are quaternary cationic polyacrylamide flocculants, all from commercial sources.
Example 1
100g of wastewater containing ruthenium and zinc (wastewater generated in the process of preparing the benzene selective hydrogenation catalyst) is taken, the wastewater contains 5.2mg/L of ruthenium and 437.3mg/L of zinc after detection, the pH value of the wastewater is 13.2, the color of the wastewater is light yellow), the pH value of the wastewater is regulated to 10.7 by adding sulfuric acid, precipitation occurs, stirring is carried out for 10min, 0.2g of cationic polyacrylamide (with the cation degree of 12%) solution (with the mass fraction of 0.1%) is added, stirring is carried out for 1h, standing is carried out for 2h, about 70mL of supernatant is sucked out, the rest liquid is filtered, the sucked supernatant and filtrate are mixed, and the concentration of ruthenium and zinc in the detected mixed liquid is less than 1.0mg/L.
Example 2
100g of wastewater containing ruthenium and zinc (wastewater generated in the process of preparing the benzene selective hydrogenation catalyst) is taken, the wastewater contains 9.4mg/L of ruthenium and 152.2mg/L of zinc through detection, the pH value of the wastewater is 12.9, the color of the wastewater is yellow), 0.5g of cationic polyacrylamide (the cationic degree is 20%) solution (the mass fraction is 0.2%) is added, hydrochloric acid is added to adjust the pH value to 10.3, precipitation occurs, the mixture is stirred for 1h and then filtered, the concentration of ruthenium and zinc in the filtrate through detection is less than 1.0mg/L, and the filtrate is colorless.
Example 3
100g of wastewater containing ruthenium and zinc (wastewater generated in the process of preparing the benzene selective hydrogenation catalyst) is taken, the wastewater contains 32.1mg/L of ruthenium, 25.0mg/L of zinc and the pH value of the wastewater is 12.2 after detection, the pH value of the wastewater is yellow, hydrochloric acid is added to adjust the pH value of the wastewater to 10.8, precipitation occurs, stirring is carried out for 10min, 0.8g of cationic polyacrylamide (the cationic degree is 25%) solution (the mass fraction is 0.05%) is added, stirring is carried out for 1h, standing is carried out for 2h, about 70mL of supernatant is sucked out, the rest liquid is filtered, the sucked supernatant is mixed with filtrate, and the concentration of ruthenium and zinc in the detected mixed liquid is less than 1.0mg/L.
Example 4
100g of wastewater containing ruthenium and zinc (wastewater generated in the process of preparing the benzene selective hydrogenation catalyst) is taken, the wastewater contains 47.8mg/L of ruthenium, 470.7mg/L of zinc and 13.5 of pH value of the wastewater, the pH value of the wastewater is regulated to be brown yellow by adding hydrochloric acid, precipitation occurs, stirring is carried out for 10min, 0.2g of cationic polyacrylamide (the cationic degree is 60%) solution (the mass fraction is 0.3%) is added, stirring is carried out for 1h, standing is carried out for 2h, about 70mL of supernatant is sucked out, the rest liquid is filtered, the sucked supernatant is mixed with filtrate, the ruthenium concentration in the detected mixed liquid is 1.8mg/L, the zinc concentration is less than 1.0mg/L, and the mixed liquid is colorless.
Comparative example 1
100g of wastewater containing ruthenium and zinc (wastewater generated in the process of preparing the benzene selective hydrogenation catalyst, wherein the wastewater contains 5.2mg/L of ruthenium and 5.3 mg/L of zinc through detection, the pH value of the wastewater is 13.2, the color of the wastewater is light yellow), 0.2g of cationic polyacrylamide solution in the example 1 is added, stirring is carried out for 1h, no precipitation occurs, and the wastewater is still light yellow.
Comparative example 2
100g of wastewater containing ruthenium and zinc (wastewater generated in the process of preparing the benzene selective hydrogenation catalyst is detected to contain 5.2mg/L of ruthenium and 437.3mg/L of zinc, the pH value of the wastewater is 13.2, the color of the wastewater is light yellow), sulfuric acid is added to adjust the pH value of the wastewater to 10.7, precipitation occurs, stirring is carried out for 1h, filtration is carried out, the concentration of ruthenium in the filtrate detected is 5.2mg/L, the concentration of zinc is less than 1.0mg/L, and the color of the filtrate is still light yellow.
Claims (11)
1. A method for simultaneously removing ruthenium and zinc in wastewater, comprising: adjusting the pH value of the wastewater to convert zinc into sediment; combining ruthenium-containing groups in the wastewater with the precipitate by means of a ruthenium-binding agent; removing the precipitate from the wastewater; the pH of the wastewater is > 12 and ruthenium is present in the anionic groups.
2. The method according to claim 1, wherein the pH of the wastewater is adjusted to 10-11.
3. The method according to claim 1, wherein ruthenium binder is added to the wastewater, the pH of the wastewater is adjusted, and after precipitation, stirring is continued and the precipitate is separated and removed.
4. The method of claim 1, wherein the wastewater is generated during the preparation of a benzene selective hydrogenation catalyst.
5. The method according to claim 1, wherein ruthenium is present in the wastewater in or substantially in [ RuCHO ] 3 ] - 、[RuC 2 H 3 SO 5 ] - 、[RuC 4 H 5 OCl 2 ] - And [ RuC 3 H 4 O 4 Cl] - One or more forms of the above.
6. The method according to claim 1, wherein the ruthenium concentration in the wastewater is 5.0mg/L to 50.0mg/L based on the mass of ruthenium element.
7. The method according to claim 1, wherein the zinc concentration in the wastewater is 10.0mg/L to 500.0mg/L based on the mass of zinc element.
8. The method of claim 1, wherein the ruthenium binder is a cationic organic polymer.
9. The method of claim 8, wherein the ruthenium binder is a cationic polyacrylamide.
10. The method of claim 9, wherein the ruthenium binder is a quaternary cationic polyacrylamide.
11. The method according to claim 1, characterized in that the mass ratio of ruthenium binder to wastewater is (10 -6 ～10 -5 )：1。
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