CN111018081B - Combined degradation treatment method for high-concentration high-polymerization-degree polyvinyl alcohol wastewater - Google Patents
Combined degradation treatment method for high-concentration high-polymerization-degree polyvinyl alcohol wastewater Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater, which combines a pre-oxidation-catalytic oxidation two-stage oxidation method, firstly reduces the polymerization degree of polyvinyl alcohol in the wastewater to below 200 through a pre-oxidation stage, and then further degrades the polyvinyl alcohol with ultralow polymerization degree and high concentration in the wastewater through catalytic oxidation, thereby achieving the best degradation treatment effect. The combined degradation treatment method mainly aims at the wastewater with the polymerization degree of at least 500, the concentration of 10-45 wt% and the complete dissolution of polyvinyl alcohol to carry out degradation treatment, the COD value of the wastewater is reduced to be below 100mg/L in a short time, and the removal rate of the COD value is as high as 99.95%; and the combined degradation treatment method has lower cost and is suitable for popularization and use.
Description
Technical Field
The invention belongs to the technical field of degradation treatment of polyvinyl alcohol wastewater, and particularly relates to a combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater, which is particularly used for degrading high-concentration high-polymerization-degree polyvinyl alcohol wastewater in nuclear power industry, paper-making industry, textile and printing and dyeing desizing industry.
Background
Polyvinyl alcohol (PVA) is a water-soluble high molecular polymer with wide application, and is used as one of three sizing agents for sizing warp yarns. It has stable slurry viscosity and slurry filmHigh strength, high antiwear performance and high anti-bending strength, and excellent adhesion to various kinds of fiber or blended fiber. It is widely used in chemical industry, textile industry and printing and dyeing industry. PVA is a slurry with poor biochemical properties, however, its BOD5The COD value is only 0.064, which belongs to the refractory organic matter. After PVA is discharged into the water body, the PVA can not be oxidized and degraded in time and can exist in the environment for a long time, the accumulated PVA can not only increase the viscosity of water and increase foams, but also influence the decomposition of aerobic microorganisms on organic matters, can also enhance the activity of heavy metals in the water body, accelerate the migration speed of the heavy metals and cause more serious environmental problems. Therefore, how to treat desizing wastewater containing high concentration PVA is always a problem for environmental protection workers.
At present, the treatment methods of polyvinyl alcohol wastewater are many, and there are biochemical methods, adsorption methods, salting-out methods, wet catalytic oxidation methods, photocatalytic oxidation methods, Fenton oxidation methods, microwave radiation methods, ozone oxidation, supercritical water oxidation methods, electrochemical methods, and the like, but there are few systems and methods for treating polyvinyl alcohol wastewater in practical engineering implementation, and particularly, there is a shortage of treatment technologies for polyvinyl alcohol wastewater with high concentration (concentration of at least 10 wt.%) and high degree of polymerization, and in the existing publications, there are many treatment technologies for PVA with low concentration (0.03g/L to 2 g/L).
The related literature reports about the treatment of wastewater containing polyvinyl alcohol disclosed in the prior art, for example, patent publication No. CN108503010A discloses a method for treating wastewater containing polyvinyl alcohol, which is mainly characterized in that Fe with a molar ratio of 1:2 is added2+And Fe3+And after the mixture is uniformly stirred, the pH is adjusted to be alkaline, iron mud is precipitated, and then solid-liquid separation is carried out. The invention patent with publication number CN 102757144A discloses a photo/electric Fenton treatment process for polyvinyl alcohol desizing wastewater, which combines Fenton oxidation and ultraviolet to improve the oxidation efficiency of Fenton reagent, then further makes PVA oxidized and degraded by an electrolytic device, and finally uses a biochemical pool for treatment, wherein the method adopts the following steps ofThe PVA degradation efficiency is higher than that of the traditional Fenton oxidation by introducing light/electricity, the cost of the reagent is relatively saved, but a large amount of reagent is still needed to adjust the pH value to be alkaline, the problem of iron mud exists, the cost of electricity/light for long-term operation is higher, and the real industrialization is difficult to realize. The invention patent with publication number CN106311125A discloses the use of a manganese oxide/alumina composite material in polyvinyl alcohol treatment by MnxOy/γAl203The composite material is used for carrying out adsorption treatment or catalytic degradation treatment on a polyvinyl alcohol aqueous solution, so that the adsorption treatment and the catalytic degradation treatment of polyvinyl alcohol are synchronously realized, but the method is an adsorption catalytic reaction, the catalyst needs to be continuously regenerated when being used, the requirements on equipment and operators are high, the cost is high, and the industrial production and popularization are difficult to realize. The invention patent with publication number CN105540818A discloses a method for treating polyvinyl alcohol wastewater by hydrogen peroxide catalytic oxidation, which comprises adding hydrogen peroxide and a catalyst under acidic condition, and degrading polyvinyl alcohol wastewater under stirring condition, thereby realizing treatment of polyvinyl alcohol wastewater; the treatment process is carried out at normal pressure, the reaction temperature is 50-80 ℃, the reaction condition is mild, the removal rate of COD in the wastewater reaches more than 90%, most of polyvinyl alcohol can be removed, but the method can not well treat the high-concentration polyvinyl alcohol wastewater with COD of more than 5000-10000ppm formed by polyvinyl alcohol.
Therefore, the prior art can only treat low-concentration polyvinyl alcohol wastewater generally, and a proper treatment method suitable for high-concentration high-polymerization-degree polyvinyl alcohol wastewater does not exist, so that the method is low in cost and efficient in treatment process lack for the high-concentration high-polymerization-degree polyvinyl alcohol wastewater generated in the fields of nuclear power industry, paper making industry, textile and printing and dyeing desizing industry and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a combined degradation treatment method for high-concentration high-polymerization degree polyvinyl alcohol wastewater, which mainly aims at the wastewater with the polymerization degree of at least 500 and the concentration of 10-45 wt% and completely dissolved polyvinyl alcohol to carry out degradation treatment, the COD value of the wastewater is reduced to be below 100mg/L in a short time, and the removal rate of the COD value is as high as 99.95%; and the combined degradation treatment method has lower cost and is suitable for popularization and use.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater comprises the following steps:
(1) adding a strong oxidant into wastewater with the polymerization degree of at least 500 and the concentration of 10-45 wt% and completely dissolved polyvinyl alcohol for pre-oxidation degradation, and stirring for reaction until the polymerization degree of the polyvinyl alcohol is not higher than 200 to obtain a solution B after pre-oxidation treatment;
(2) adding a hydrogen peroxide solution and a transition metal catalyst into the solution B obtained in the step (1), performing catalytic oxidation degradation by an advanced oxidation method, stirring for reaction for 10-60 min, and performing solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment.
Wherein, the wastewater with the polymerization degree of at least 500 and the concentration of 10 wt.% to 45wt.% and completely dissolved polyvinyl alcohol in the step (1) is polyvinyl alcohol wastewater which is usually directly discharged in an industrial link, or polyvinyl alcohol wastewater which is subjected to pretreatment to dilute/concentrate the concentration of polyvinyl alcohol to the above concentration range, or polyvinyl alcohol wastewater which is subjected to pretreatment (such as pressurization treatment) to improve the solubility of polyvinyl alcohol. Generally, the direct discharging or pre-treating is to select proper direct discharging wastewater collecting or pre-treating process according to the prior art by those skilled in the art according to different industrial fields, and limit the polyvinyl alcohol in the wastewater to be completely dissolved to achieve the best degradation treatment effect.
It is worth mentioning that the person skilled in the art knows, on the basis of his general knowledge, that the polyvinyl alcohol waste water produced in the industrial sector at present has a degree of polymerization of polyvinyl alcohol generally not exceeding 2600. Under normal pressure, polyvinyl alcohol wastewater with high polymerization degree is limited by solubility, and the mass concentration of the polyvinyl alcohol wastewater has an upper limit under the precondition that the polyvinyl alcohol is completely dissolved, and the specific upper limit can be known by looking up the prior art documents according to the polymerization degree of the polyvinyl alcohol in the actual wastewater, for example, the highest dissolution concentration of the polyvinyl alcohol wastewater with the polymerization degree of about 1700 is 15 wt.% to 20 wt.% under the normal pressure, and the polyvinyl alcohol wastewater with the concentration higher than the highest dissolution concentration cannot form a homogeneous solution under the normal pressure, so that the optimal degradation treatment effect cannot be achieved. However, it is known from the common knowledge in the art that the solubility of polyvinyl alcohol under pressurized conditions is further improved, for example, the above-mentioned polyvinyl alcohol wastewater with a polymerization degree of about 1700 is dissolved at a concentration of 33 wt.% under pressure, which is suitable for the degradation treatment in the technical solution of the present invention, and the optimal degradation treatment effect can be achieved. In addition, the highest solubility of the polyvinyl alcohol wastewater with a relatively low degree of polymerization (the degree of polymerization is about 500) is 30 wt.% under normal pressure, and the highest solubility can reach 45wt.% under pressure, so that the method is also suitable for the technical scheme of the invention to carry out degradation treatment, and the optimal degradation treatment effect can be achieved.
Comprehensively, namely, the polymerization degree of polyvinyl alcohol of the wastewater is at least 500 and the concentration is 10-30 wt% under the normal pressure condition, and the wastewater is suitable for degradation treatment in the technical scheme of the invention under the condition of meeting the requirement of complete dissolution of the polyvinyl alcohol, and can achieve the optimal degradation treatment effect;
under the pressurization condition, the polymerization degree of the polyvinyl alcohol is at least 500, and the concentration is 10-45 wt.%, so that the method is suitable for the technical scheme of the invention to carry out degradation treatment under the condition of meeting the requirement of completely dissolving the polyvinyl alcohol, and the optimal degradation treatment effect can be achieved.
In addition, for the polyvinyl alcohol wastewater with the polymerization degree and the concentration lower than the protection range, the catalytic oxidation degradation is directly carried out for treatment according to the step (2) without the pre-oxidation stage of the method, and a good removal effect can also be obtained.
Wherein, said step (1) of adding strong oxidant to carry out pre-oxidation degradation, stirring to make polyvinyl alcohol polymerization degree not higher than 200, generally speaking, said strong oxidant meeting the above condition can be all, such as sodium periodate, sodium hypochlorite, hypochlorous acid, chlorine dioxide, sodium ferrate, sodium permanganate or combination of at least two of the above strong oxidants, but it is found by the inventor of the present invention in the implementation process that the effect of using the combination of strong oxidant is actually inferior to using single strong oxidant, in order to better illustrate the present invention, and provide a preferable technical solution, said strong oxidant in step (1) is sodium hypochlorite.
More preferably, the strong oxidant is added in a molar ratio of (1-4): addition was carried out in the manner of 1. More preferably, the strong oxidant is added in a molar ratio of (2.5-4): addition was carried out in the manner of 1.
It should be noted that, during the pre-oxidation degradation process of the strong oxidant and the polyvinyl alcohol, high-concentration ionic contaminants, such as iodide ions and sodium ions corresponding to sodium periodate and chloride ions and sodium ions corresponding to sodium hypochlorite, are inevitably introduced, but the treatment process of the above high-concentration ionic contaminants in the prior art is mature, and the treatment cost is almost negligible compared with the treatment cost of the high-concentration polyvinyl alcohol wastewater in the prior art, so that the obvious defect of the present invention is not implied, but it should be pointed out that the technical content of the present invention is to perform post-treatment on the finally obtained wastewater after the degradation treatment of the polyvinyl alcohol in the implementation process to remove the ionic contaminants in the wastewater.
Wherein, the stirring reaction is carried out until the polymerization degree of the polyvinyl alcohol is not higher than 200, generally speaking, appropriate stirring process parameters are selected according to the weight of the wastewater to be implemented, and a person skilled in the art can determine appropriate mechanical stirring rotation speed and stirring time according to a sample, and the stirring reaction time is usually not more than 2 h. In order to better illustrate the invention and provide a reference technical scheme, when the polyvinyl alcohol wastewater is 1kg, the corresponding stirring process parameters are as follows: the mechanical stirring speed is 300-1200 r/min, the stirring reaction time is 1-2 h, and the reaction temperature is 25-90 ℃.
The hydrogen peroxide solution in the step (2) and a transition metal catalyst, wherein the transition metal catalyst is preferably one of a copper-based catalyst, an iron-based catalyst, a manganese-based catalyst and a cobalt-based catalyst or a composite catalyst thereof. The concentration and addition amount of the hydrogen peroxide solution and the addition amount of the transition metal catalyst can be determined by the prior art Fenton oxidation method.
In the implementation process, the inventor of the invention finds that if a single catalyst is adopted, the catalyst is most preferably a copper-based catalyst, and then a cobalt-based catalyst; if a composite catalyst is used, a copper-cobalt or copper-manganese catalyst is preferred.
In addition, the Fenton reagent in the Fenton oxidation method in the prior art can also be adopted, but after the Fenton reagent is added and used, the pH needs to be adjusted to be alkaline, a large amount of iron mud is generated, the subsequent treatment cost is high, and the Fenton reagent cannot be reused, so the invention further provides the following technical scheme:
further, the transition metal catalyst is a supported metal catalyst; the supported metal catalyst is a carrier type catalyst loaded with transition/composite metal and/or transition/composite metal oxide, the composite/transition metal is consistent with the transition metal catalyst, the carrier is a porous carrier, preferably activated carbon, and the selected activated carbon has a particle size of 6-50 meshes. Generally, the supported metal catalyst can be collected by solid-liquid separation in step (2) and reused.
In order to better illustrate the invention and provide a preferable technical scheme, the hydrogen peroxide solution and the transition metal catalyst are characterized in that the mass concentration of the hydrogen peroxide solution is 10-50%, and the addition amount of the hydrogen peroxide solution is that the molar ratio of hydrogen peroxide to polyvinyl alcohol is (5-15): 1; the transition metal catalyst is a carrier type catalyst loaded with composite metal and/or composite metal oxide, the mass content of the composite metal and/or the composite metal oxide in the carrier type catalyst is 2-15%, wherein the composite metal is preferably one of copper-cobalt metal (or metal oxide thereof) composite and copper-manganese metal (or metal oxide thereof), and the mass ratio of the copper to the cobalt metal is (1-9): 1, the mass ratio of copper to manganese metal is (1-9): 1, and more preferably the mass ratio is (1-4): 1. The amount of the supported catalyst added is 0.048 g/mL-0.144 g/mL (calculated as the volume of the solution B).
It should be noted that, in the step (2), the hydrogen peroxide solution is added according to a conventional adding manner of the hydrogen peroxide solution, and it should be noted that the time of the hydrogen peroxide solution during the adding process is not counted into the subsequent stirring reaction time. In order to better illustrate the invention and provide a reference technical scheme, when the addition amount of the hydrogen peroxide solution is 1-10L, the hydrogen peroxide solution is dripped at a constant speed of 150 mu L/min by a peristaltic pump (the size of the peristaltic tube is 5mmx8 mm).
Wherein, the catalytic oxidation degradation is carried out by the advanced oxidation method in the step (2), the stirring reaction is carried out for 10min to 60min, generally speaking, appropriate catalytic oxidation degradation process parameters are selected according to the weight of the solution B to be implemented, and a person skilled in the art can determine appropriate mechanical stirring rotation speed and stirring time according to a sample, but generally, the degradation effect is not further improved after the stirring reaction exceeds 60 min. It should be noted that the inventor of the present invention finds that the advanced oxidation method cannot represent a significant reaction ending endpoint in the implementation process, so the stirring reaction time generally needs to be confirmed by sample detection in the implementation process of the technical solution of the present invention, and the stirring reaction time is in the range of 10min to 60 min. In order to better illustrate the invention and provide a reference technical scheme, when the solution B is 1kg, the corresponding catalytic oxidative degradation process parameters are as follows: the mechanical stirring speed is 300-1200 r/min, the reaction time is 10-60 min, the reaction temperature is 25-90 ℃, and the further optimization is 40 ℃.
In the step (2), the catalytic oxidation degradation is performed by an advanced oxidation method, in order to perform the catalytic oxidation degradation by using an oxidation mechanism of the advanced oxidation method, generally speaking, the pH value needs to be adjusted to 2-5 before adding a hydrogen peroxide solution and a transition metal catalyst, and generally, an industrially conventional strong acid solvent, such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid or solid acid, can be selected.
Wherein, the solid-liquid separation in the step (2) can be realized by one or more of the processes selected by the person skilled in the art according to the actual situation, such as gravity settling, filtration separation and centrifugal separation.
It should be noted that mechanical stirring is usually selected for the stirring in the technical scheme of the present invention, and those skilled in the art can select a suitable stirring manner according to actual conditions.
The above-mentioned contents provide some preferred technical solutions for the present invention, and in order to facilitate the understanding of those skilled in the art, and provide a group of preferred technical solutions for reference, the method for the combined degradation treatment of high-concentration and high-polymerization degree polyvinyl alcohol wastewater comprises the following steps in parts by weight:
(1) adding 37.5-60 parts of strong oxidant into 100 parts of polyvinyl alcohol wastewater with the polymerization degree of 1700-2600 and the concentration of 10-15 wt.% to perform pre-oxidation degradation through stirring reaction, so as to obtain a pre-oxidized solution B; the stirring process parameters are as follows: the mechanical stirring speed is 300-600 r/min, the stirring reaction time is 1-2 h, and the reaction temperature is 25-50 ℃;
(2) adjusting the pH value of the solution B obtained in the step (1) to 2-5, adding 150-225 parts of hydrogen peroxide solution with the mass concentration of 10% -50% and 4.8-14.4 parts of activated carbon carrier type catalyst loaded with composite metal and/or composite metal oxide, carrying out catalytic oxidation degradation through stirring reaction, and finally carrying out solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment; the stirring process parameters are as follows: the mechanical stirring speed is 300-600 r/min, the stirring reaction time is 30-50 min, and the reaction temperature is 25-50 ℃;
wherein the mass content of the composite metal and/or the composite metal oxide in the activated carbon carrier type catalyst is 10-15%; wherein the composite metal is a copper-cobalt composite metal/composite metal oxide or a copper-manganese composite metal/composite metal oxide, and the mass ratio of the copper to the cobalt is (1-4): 1, the mass ratio of copper to manganese metal is (1-4): 1.
according to the technical scheme, the high-efficiency degradation of the high-concentration high-polymerization-degree polyvinyl alcohol is realized. By implementing the method, the COD value in the polyvinyl alcohol wastewater is reduced to be below 100mg/L from 20 ten thousand mg/L initially in the implementation process of the technical scheme, and the removal rate of the COD value is as high as 99.95%.
The invention has the following beneficial effects:
(1) the invention combines the pre-oxidation and catalytic oxidation two-stage oxidation method, firstly reduces the polymerization degree of polyvinyl alcohol in the wastewater to below 200 through the pre-oxidation stage, reduces difficulty and cost for the catalytic oxidation of the later stage, and then degrades the polyvinyl alcohol with ultra-low polymerization degree and high concentration in the wastewater through the catalytic oxidation, thereby achieving the best degradation treatment effect.
(2) The invention combines the pre-oxidation and catalytic oxidation two-stage oxidation method, the whole process can be carried out in a lower temperature range and under the normal pressure/pressurization environment, the COD value of the polyvinyl alcohol wastewater with high concentration can be reduced to be less than 100mg/L from 20 ten thousand mg/L within hours in the implementation process, and the removal rate of the COD value is as high as 99.95%.
(3) Compared with the common process for degrading polyvinyl alcohol by a Fenton method, the technical scheme of the invention belongs to heterogeneous reaction, when the preferable technical scheme of the supported metal catalyst is adopted, the pH is not required to be adjusted in the implementation process to precipitate iron ions, no new solid waste is generated, the catalyst is recovered by solid-liquid separation, and the catalyst can be repeatedly used.
(4) The pre-oxidation-catalytic oxidation two-stage oxidation method provided by the invention is a new way for treating the high-polymerization-degree and high-concentration polyvinyl alcohol wastewater, has a guiding function on the treatment process technology of the high-polymerization-degree and high-concentration polyvinyl alcohol wastewater in the future, and has excellent industrial implementation value.
(5) The invention is widely suitable for the degradation of the high-concentration and high-polymerization degree polyvinyl alcohol wastewater generated in various industrial systems, in particular to the degradation of the high-concentration and high-polymerization degree polyvinyl alcohol wastewater in the nuclear power industry, the paper industry, the textile industry, the printing and dyeing desizing industry.
Detailed Description
The invention is further illustrated by the following examples. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
In the following examples, the COD value of the wastewater was determined by the potassium dichromate method of GB 11914-89. Adding a known amount of potassium dichromate solution into a water sample, taking a silver salt as a catalyst under a strong acid (sulfuric acid) medium, boiling and refluxing, taking resorufin (phenanthroline) as an indicator, and titrating the unreduced potassium dichromate in the water sample by using ammonium ferrous sulfate, wherein the mass concentration of consumed oxygen is converted from the amount of consumed ammonium ferrous sulfate.
The COD value was calculated as follows:
wherein C is the concentration of standard titration solution of ferrous ammonium sulfate (measured before daily use), mol/L; v1The volume of the standard titration solution of ferrous ammonium sulfate consumed for the blank test (deionized water), mL; v2The volume of the standard titration solution of consumed ammonium ferrous sulfate consumed by the test sample is mL; v0Volume of sample, mL; 8000 is 1/4O2The molar mass of (b) is expressed in mg/L.
It is to be noted that, in the following examples, the hydrogen peroxide solution was added dropwise at a constant rate of 150. mu.L/min by means of a peristaltic pump (peristaltic tube size: 5mmX8 mm).
Example 1
A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater comprises the following steps:
(1) adding 0.92L of sodium hypochlorite solution (commercially available analytically pure sodium hypochlorite solution) into 1L of polyvinyl alcohol wastewater with the polymerization degree of 2400 and the concentration of 15 wt.% to perform pre-oxidation degradation through stirring reaction to obtain solution B after pre-oxidation treatment; the stirring process parameters are as follows: the mechanical stirring speed is 375r/min, the stirring reaction time is 2h, and the reaction temperature is 40 ℃;
(2) regulating the pH value of the solution B obtained in the step (1) to 3 by adopting 50 wt.% sulfuric acid solution, then adding 5.12L of hydrogen peroxide solution with the mass concentration of 30% and 351.57g of copper-cobalt composite-activated carbon carrier type catalyst, carrying out catalytic oxidation degradation by stirring reaction, wherein the stirring reaction time is 40min, the reaction temperature is 40 ℃, the mechanical stirring rotation speed is 375r/min, and carrying out solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment; the copper-cobalt composite-activated carbon carrier catalyst is produced by Chengdouqi environmental science and technology limited company, wherein the mass content of the active metal component is 10%, the mass ratio of copper to cobalt is 4:1, and the activated carbon carrier is 4mm columnar carbon.
The COD value of the polyvinyl alcohol in the wastewater subjected to degradation treatment by the polyvinyl alcohol of the embodiment is reduced from about 20 ten thousand mg/L to about 100mg/L, and the removal rate of the COD is 99.95%.
Example 2
A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater comprises the following steps:
(1) adding 0.92L of sodium hypochlorite solution (commercially available analytically pure sodium hypochlorite solution) into 1L of polyvinyl alcohol wastewater with the polymerization degree of 2600 and the concentration of 15 wt.% to perform pre-oxidation degradation through stirring reaction to obtain solution B after pre-oxidation treatment; the stirring process parameters are as follows: the mechanical stirring speed is 600r/min, the stirring reaction time is 2h, and the reaction temperature is 90 ℃;
(2) regulating the pH value of the solution B obtained in the step (1) to 3 by adopting 50 wt.% sulfuric acid solution, then adding 5.12L of hydrogen peroxide solution with the mass concentration of 50% and 527.35g of copper-activated carbon carrier type catalyst, carrying out catalytic oxidation degradation by stirring reaction, wherein the stirring reaction time is 60min, the reaction temperature is 40 ℃, the mechanical stirring rotation speed is 600r/min, and carrying out solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment; the copper-activated carbon carrier catalyst is produced by Chengduda environmental science and technology limited company, wherein the mass content of the active metal component is 15%, and the activated carbon carrier is 4mm columnar carbon.
The COD value of the polyvinyl alcohol in the wastewater subjected to degradation treatment by the polyvinyl alcohol of the embodiment is reduced from about 20 ten thousand mg/L to about 500mg/L, and the removal rate of the COD is 99.75%.
Example 3
A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater comprises the following steps:
(1) adding 0.58L of sodium hypochlorite solution (commercially available analytically pure sodium hypochlorite solution) into 1L of polyvinyl alcohol wastewater with the polymerization degree of 500 and the concentration of 30 wt.% to perform pre-oxidation degradation through stirring reaction to obtain solution B after pre-oxidation treatment; the stirring process parameters are as follows: the mechanical stirring speed is 300r/min, the stirring reaction time is 1h, and the reaction temperature is 40 ℃;
(2) regulating the pH value of the solution B obtained in the step (1) to 3 by adopting 50 wt.% sulfuric acid solution, then adding 1.74L of hydrogen peroxide solution with the mass concentration of 30% and 175.78g of cobalt-activated carbon carrier type catalyst, carrying out catalytic oxidation degradation by stirring reaction, wherein the stirring reaction time is 30min, the reaction temperature is 40 ℃, the mechanical stirring rotation speed is 300r/min, and carrying out solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment; the cobalt-activated carbon carrier catalyst is produced by Chengduda environmental science and technology limited company, wherein the mass content of the active metal component is 10%, and the activated carbon carrier is 4mm columnar carbon.
The COD value of the polyvinyl alcohol in the wastewater subjected to degradation treatment by the polyvinyl alcohol of the embodiment is reduced from about 20 ten thousand mg/L to about 900mg/L, and the removal rate of the COD is 99.55%.
Example 4
A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater comprises the following steps:
(1) adding 0.69L of sodium hypochlorite solution (commercially available analytically pure sodium hypochlorite solution) into 1L of polyvinyl alcohol wastewater with the polymerization degree of 1700 and the concentration of 20 wt.% to perform pre-oxidation degradation through stirring reaction to obtain a pre-oxidized solution B; the stirring process parameters are as follows: the mechanical stirring speed is 400r/min, the stirring reaction time is 1.5h, and the reaction temperature is 50 ℃;
(2) regulating the pH value of the solution B obtained in the step (1) to 3 by adopting 50 wt.% sulfuric acid solution, then adding 3.48L of hydrogen peroxide solution with the mass concentration of 40% and 439.46g of copper-manganese composite-activated carbon carrier type catalyst, carrying out catalytic oxidation degradation by stirring reaction, wherein the stirring reaction time is 40min, the reaction temperature is 40 ℃, the mechanical stirring rotation speed is 400r/min, and carrying out solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment; the copper-manganese composite-activated carbon carrier catalyst is produced by Chengdu Daqi environmental science and technology limited company, wherein the mass content of active metal components is 10%, the mass ratio of copper to manganese is 1:1, and the activated carbon carrier is 4mm columnar carbon.
The COD value of the polyvinyl alcohol in the wastewater subjected to degradation treatment by the polyvinyl alcohol of the embodiment is reduced from about 20 ten thousand mg/L to about 700mg/L, and the removal rate of the COD is 99.65%.
Example 5
A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater comprises the following steps:
(1) adding 0.92L of sodium hypochlorite solution (commercially available analytically pure sodium hypochlorite solution) into 1L of polyvinyl alcohol wastewater with the polymerization degree of 2400 and the concentration of 15 wt.% to perform pre-oxidation degradation through stirring reaction to obtain solution B after pre-oxidation treatment; the stirring process parameters are as follows: the mechanical stirring speed is 375r/min, the stirring reaction time is 2h, and the reaction temperature is 40 ℃;
(2) adjusting the pH value of the solution B obtained in the step (1) to 3 by adopting 50 wt.% sulfuric acid solution, and then adding 1420g FeSO4·7H2O and 5.12L of hydrogen peroxide solution with the mass concentration of 30 percent are subjected to Fenton oxidation through stirring reaction, the stirring reaction time is 40min, the reaction temperature is 40 ℃, the mechanical stirring rotation speed is 375r/min, the pH is adjusted to be alkaline (about 9) after the reaction is finished, and then solid-liquid separation is carried out, so that the wastewater of the polyvinyl alcohol after degradation treatment is obtained.
The COD value of the polyvinyl alcohol in the wastewater subjected to degradation treatment by the polyvinyl alcohol of the embodiment is reduced from about 20 ten thousand mg/L to about 1100mg/L, and the removal rate of the COD is 99.45%. Although the degradation effect is good, a large amount of iron mud is generated, and the subsequent treatment cost is high.
Claims (12)
1. A combined degradation treatment method of high-concentration high-polymerization-degree polyvinyl alcohol wastewater is characterized by comprising the following steps:
(1) adding a strong oxidant into wastewater with the polymerization degree of at least 500 and the concentration of 10-45 wt% and completely dissolved polyvinyl alcohol for pre-oxidation degradation, and stirring for reaction until the polymerization degree of the polyvinyl alcohol is not higher than 200 to obtain a solution B after pre-oxidation treatment;
the strong oxidant is sodium hypochlorite; the strong oxidant is added in a molar ratio of (1-4) to the polyvinyl alcohol: 1, adding;
(2) adding a hydrogen peroxide solution and a transition metal catalyst into the solution B obtained in the step (1), performing catalytic oxidation degradation by an advanced oxidation method, stirring for reaction for 10-60 min, and performing solid-liquid separation to obtain wastewater of polyvinyl alcohol subjected to degradation treatment;
the transition metal catalyst is a supported metal catalyst; the supported metal catalyst is a carrier catalyst loaded with transition/composite metal and/or transition/composite metal oxide, the transition metal is one of copper, iron, manganese and cobalt, the composite metal is copper-cobalt or copper-manganese, and the carrier is a porous carrier; the mass content of the composite metal and/or the composite metal oxide in the carrier type catalyst is 2-15%, and the mass ratio of copper to cobalt is (1-9): 1, the mass ratio of copper to manganese metal is (1-9): 1.
2. the combined degradation treatment method according to claim 1, wherein: the wastewater in the step (1) is obtained by directly discharging/pretreating wastewater with completely dissolved polyvinyl alcohol, wherein the polymerization degree of the polyvinyl alcohol is at least 500 and the concentration of the polyvinyl alcohol is 10-30 wt% under normal pressure.
3. The combined degradation treatment method according to claim 1, wherein: the wastewater in the step (1) is obtained by directly discharging/pretreating wastewater with completely dissolved polyvinyl alcohol, wherein the polymerization degree of the polyvinyl alcohol is at least 500 and the concentration of the polyvinyl alcohol is 10-45 wt% under a pressurized condition.
4. The combined degradation treatment method according to claim 1, wherein: the strong oxidant in the step (1) is added in a molar ratio of (2.5-4) to the polyvinyl alcohol: addition was carried out in the manner of 1.
5. The combined degradation treatment method according to claim 1, wherein: stirring technological parameters corresponding to the stirring reaction in the step (1) are as follows: the mechanical stirring speed is 300-1200 r/min, the stirring reaction time is 1-2 h, and the reaction temperature is 25-90 ℃.
6. The combined degradation treatment method according to claim 1, wherein: the carrier is activated carbon, and the activated carbon with the particle size of 6-50 meshes is selected.
7. The combined degradation treatment method according to claim 1, wherein: the addition amount of the carrier type catalyst is 0.048 g/mL-0.144 g/mL calculated by the volume of the solution B.
8. The combined degradation treatment method according to claim 1, wherein: the mass concentration of the hydrogen peroxide solution in the step (2) is 10-50%, and the addition amount is that the molar ratio of hydrogen peroxide to polyvinyl alcohol is (5-15): 1.
9. the combined degradation treatment method according to claim 1, wherein: the corresponding process parameters of the catalytic oxidative degradation in the step (2) are as follows: the mechanical stirring speed is 300-1200 r/min, the reaction time is 10-60 min, and the reaction temperature is 25-90 ℃.
10. The combined degradation treatment method according to claim 1, wherein: and (3) the solid-liquid separation in the step (2) is one or combination of gravity settling, filtration separation and centrifugal separation.
11. The combined degradation treatment method according to claim 1, comprising the steps of:
(1) adding 37.5-60 parts of strong oxidant into 100 parts of polyvinyl alcohol wastewater with the polymerization degree of 1700-2600 and the concentration of 10-15 wt.% to perform pre-oxidation degradation through stirring reaction, so as to obtain a pre-oxidized solution B; the stirring process parameters are as follows: the mechanical stirring speed is 300-600 r/min, the stirring reaction time is 1-2 h, and the reaction temperature is 25-50 ℃;
(2) adjusting the pH value of the solution B obtained in the step (1) to 2-5, adding 150-225 parts of hydrogen peroxide solution with the mass concentration of 10% -50% and 4.8-14.4 parts of activated carbon carrier type catalyst loaded with composite metal and/or composite metal oxide, carrying out catalytic oxidation degradation through stirring reaction, and finally carrying out solid-liquid separation to obtain wastewater subjected to degradation treatment on polyvinyl alcohol; the stirring process parameters are as follows: the mechanical stirring speed is 300-600 r/min, the stirring reaction time is 30-50 min, and the reaction temperature is 25-50 ℃;
wherein the mass content of the composite metal and/or the composite metal oxide in the activated carbon carrier type catalyst is 10-15%; wherein the composite metal is a copper-cobalt composite metal/composite metal oxide or a copper-manganese composite metal/composite metal oxide, and the mass ratio of the copper to the cobalt is (1-4): 1, the mass ratio of copper to manganese metal is (1-4): 1.
12. the combined degradation treatment method according to any one of claims 1 to 11, which is applied to nuclear power industry, paper industry, textile and printing and dyeing desizing industry.
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