Zn-杂多酸盐纳米管催化氧化难降解制药废水的研究
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摘要
本文以我国北方某大型合成制药企业的高浓度难降解废水为研究对象,开展了制药废水处理联合工艺的研究,取得了较好的效果,可以保证高浓度难降解制药废水经本文所提工艺处理后,达到国家达标排放的标准(GB8978-1996)的要求。
自主设计、首次合成了新型的纳米级金属杂多酸盐催化剂——Zn_(1.5)PW_(12)O_(40)纳米管。实验证明Zn_(1.5)PW_(12)O_(40)纳米管催化活性好、耐水性能好、易于与水分离。
通过GC/MS检测中间产物与文献报道自由基降解产物对比结合文献提供的羟基自由基机理,对Zn_(1.5)PW_(12)O_(40)紫外光降解苯酚和Zn_(1.5)PW_(12)O_(40)臭氧催化氧化降解苯胺的机理进行了探讨。Zn_(1.5)PW_(12)O_(40)紫外光降解苯酚和Zn_(1.5)PW_(12)O_(40)臭氧催化氧化降解苯胺时,·OH自由基起主导作用,并由自由基引发一系列的化学反应对复杂有机物进行了有效的降解。
研究了Zn_(1.5)PW_(12)O_(40)纳米管在紫外、空气及臭氧体系中对难降解制药废水的催化氧化,获取了最佳操作条件。
通过对Zn_(1.5)PW_(12)O_(40)纳米管在三个体系中的经济性和可操作性比较分析,确定了Zn_(1.5)PW_(12)O_(40)/ O3体系为难降解制药废水预处理工艺。该体系能将废水的B/C值由0.05提高到0.6,有利于后续的生物处理。采用GC/MS对制药废水中的难降解的硝基苯类、吡啶类等有机物经该工艺处理后的组成进行了测定,定量说明了硝基苯等难降解类有机物的去除效率。
采用UNITANK-BAF组合工艺处理Zn_(1.5)PW_(12)O_(40)催化臭氧氧化后废水,出水清澈透明,COD浓度小于500mg/L,符合国家达标排放的标准的要求。为难降解制药废水的有效处理提供了一种新方法和新催化剂。
With the swift progress and develop of the medicine industry in recent years, medicine industry rise year by year in specific gravity in national economy. However, pharmacy waste water also becomes main pollution sources to many water bodies, which was a hotspot problem of the environment protection field. Cause of the shifty water quality, large flow, and great amount and species of the non-biodegradable organic in it, the Pharmacy waste water could not be treated by ordinary sewage treatment technology solely. The high thickness and non-biodegradable pharmacy waste water is the investigate subject in this study, started with to promote water biodegradability, the pharmacy waste water combined treatment handicraft has been investigated, and has got fairly good effect. The treated outflow quality from this processes can accord with the national discharge standard(GB 8978-1996).
According to the peculiar characteristic of pharmacy waste water and metal polyoxometalates, with the stencil of natural material (filter paper), a new stype nanoscale metal polyoxometalates catalyst, Zn_(1.5)PW_(12)O_(40) nanotubes, had been designed and composed autonomously during this study, which adopted the sol and gel method. Zn_(1.5)PW_(12)O_(40) nanotubes has good water resistance and easy to be separated from water. A routine represent method for polyoxometalates has been adopted to the Zn_(1.5)PW_(12)O_(40) nanotubes. Observed by transmission electron microscope, the crystal grain conformation is hollow nanotubes, tubes length between 200-900nm, the tubes diameter is 70 nm, the hollow tubes inside diameter is 20 nm about. Adopted the element analysis approach, the Zn_(1.5)PW_(12)O_(40) nanotubes catalyst compositions has been confirmed. The study result was that: Zn_(1.5)PW_(12)O_(40) nanotubes polyanion still maintain the initial Keggin type structure, in which Infrared Spectrum and X-ray powder diffraction (XRD) and 31P magnetic resonance (31P MAS NMR) methods had been used.
Through the common use method in the world, the Zn_(1.5)PW_(12)O_(40) nanotubes has been evaluated, which was used to evaluate the catalysis activity of polyoxometalates at present.In the study Safranine T was taken as the characteristic material, which has the similar constructure to Rhodamine B, but more difficult to be biodegraded. The catalysis activity of Zn_(1.5)PW_(12)O_(40) nanotubes has been investigated by degraded the Safranine T, included photocatalysis activity and chemistry catalyzing the result indicated that: Zn_(1.5)PW_(12)O_(40) nanotubes catalysis activity is fair good.
In three catalytic oxidation systems, which include ultraviolet radiation system, air oxidation system and ozone catalyzes oxidation system, Zn_(1.5)PW_(12)O_(40) nanotubes catalysis effect to non-biodegradable pharmacy waste water had been studied systematically. Only in the USA and Japan etc., polyoxometalates (POM) was applied in photocatalysis chemistry field now, and the studying were mainly carried on the purely-organics, the practical apply study is still few.
The optimum operate condition of Zn_(1.5)PW_(12)O_(40) nanotubes catalyzes oxidation for the pharmacy waste water in ultraviolet radiation system, air oxidation system and ozone catalyzes oxidation system has been got in this research. The particular results as follow:
(1)Takes the promotion of bio-degradability and remove rate of COD as the index, the optimum operation condition of Zn_(1.5)PW_(12)O_(40) nanotubes catalyzing oxidation treats the non-biodegradable pharmacy waste water under room temperature and pressure air system has been obtained. The results is that: air flow rate is 4.5L/h, and temperature is 50℃, and initial pH is above 9, and catalyst amounts is 30g/L, and reaction time 24 hours. There are three influent factors within above, which are air flow rate and catalyst amount and reaction time, which took the remarkable effect to the experiment results. Under the optimum operation condition, the B/C of pharmacy waste water can be promoted from 0.05 to 0.3, which can be propitious to follow bio-process.
(2)The experiment of Zn_(1.5)PW_(12)O_(40) nanotubes/ O3 Catalyzes Oxidation treated non-biodegradable pharmacy waste water has been carried out, the results indicated that: Zn_(1.5)PW_(12)O_(40) nanotubes catalyst have the very good adsorption and high surface activity. It was able to accelerate ozone decomposition generating the Hydroxyl Radical·OH, that makes the difficult to degrade organic by ozone (for instance nitrobenzene and pyrrolidinone etc.) can be degraded under O3/Zn_(1.5)PW_(12)O_(40) handicraft process, at the same time, can shorten the reaction residence time, and accelerate oxide reaction speed, cut down the sources of energy consumption and treatment cost. With this process, the B/C of pharmacy waste water can be promoted from 0.05 to 0.6, which can be propitious to follow bio-process. The obtained optimum operation condition of O3/Zn_(1.5)PW_(12)O_(40) nanotubes is that: catalyst amounts is 2g/L, and Ozone liquid phase thickness is above 0.3mg/L, initial pH between 7.5~9, reaction time is more than 10 minutes. Within those influent factors, the reaction time and ozone thickness made the great effect to the experiment results. On the COD remove rate, it was 46% when ozone thickness was 0.1mg/L, but it can reach 85% when ozone thickness was 0.3mg/L.
By way of comparison and analyses the economy and maneuverability of O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation system and air oxidation system and ultraviolet radiation system, the practical pretreatment process was confirmed to be O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation system. This system can promote the bio-degradability of waste water, and can make the COD remove rate above 74% at the same time.
The mechanism of Zn_(1.5)PW_(12)O_(40) ultraviolet radiation degrade phenol and O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation degrade aniline has been studied on. Through detect the intermediate product by way of GC/MS to conclude the mechanism of Zn_(1.5)PW_(12)O_(40) ultraviolet radiation degrade phenol and O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation degrade aniline:·OH free radical plays the leading role, and a series of chemical reaction has carried out effective degradation on complicated organic from free radical initiation.
Using GC/MS, the inflow and outflow waste water component from the O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation system have been mensurated and analyzed. Result indicates: under a certain process condition, the 44 kinds organic in the raw waste water, include some non-biodegradable organic such as nitrobenzene and aniline and pyridine and pyrimidine, transformed to alcohol and carboxylic acids and aldehyde and ester and alkane after treated by O3/Zn_(1.5)PW_(12)O_(40) system. Bio-toxicity of Waste water reduces obviously, but the bio-degradability improves obviously.
Adopt UNITANK-BAF combined process treat the waste water, which treated by Zn_(1.5)PW_(12)O_(40)/ Ozone Catalyzes Oxidation, and had obtained the optimum operation condition. This process can reduced the raw waste water COD thickness from 4000~5000mg/L to 500mg/L below. The obtained optimum operation condition of UNITANK-BAF combined process treat the out flow waste water from Zn_(1.5)PW_(12)O_(40)/Ozone Catalyzes Oxidation as follow:○1 UNITANK: sludge thickness is 5000~6000mg/L, and DO 2~4 mg/L, and ratio of gas and liquid is above 100:1, and inflow COD thickness 4000~5000mg/L, BOD 2400~3000mg/L, pH is 6, and BOD:N: P=100: 5:1,and HRT is more than 60 hours, room temperature 20~30℃.○2 BAF: pH 6-7, ratio of gas and liquid is above 15:1, and HRT is more than 6 hours, and room temperature 20~30℃. Under this operation condition, the average COD remove rate of UNITANK-BAF combined process can reach 91.4%.
The out flow is limpidity and lucent, COD thickness lower than 500 mg/L, accord with the national waste water discharge standard. Prove that: That Zn_(1.5)PW_(12)O_(40)/ Ozone Catalyzes Oxidation is an effective pretreatment process to the high concentration non-biodegradable pharmacy waste water. Zn_(1.5)PW_(12)O_(40)/O3 Catalyzes Oxidation -UNITANK-BAF allying unite process is the suitable handicraft for the high concentration non-biodegradable pharmacy waste water.
Non-biodegradable pharmacy waste water treated by Zn_(1.5)PW_(12)O_(40)/O3 Catalyzes Oxidation -UNITANK-BAF allying unite process had been detected with GC/MS, results indicated: after treated by Zn_(1.5)PW_(12)O_(40)/O3 Catalyzes Oxidation-UNITANK-BAF allying unite process, the organic detected in Non-biodegradable pharmacy waste water out flow were small molecule carboxylic acid and alcohol, bio-toxity was less, and the out flow is limpidity and lucent, COD thickness was below 500mg/L, which can accord with the national discharge standard(GB 8978-1996).
This study a new style catalyst, Zn_(1.5)PW_(12)O_(40) ultraviolet, has been achieved to exploited. Used with ozone Oxidation, this catalyst can promoted the sewage biodegradability observably, and then the non-biodegradable pharmacy waste water treated continually by UNITANK-BAF combined process can accord with the national discharge standard(GB 8978-1996). The results have important theory meaning and guide function, as well as significance applying value, to the waste water contain non-biodegradable organics.
自主设计、首次合成了新型的纳米级金属杂多酸盐催化剂——Zn_(1.5)PW_(12)O_(40)纳米管。实验证明Zn_(1.5)PW_(12)O_(40)纳米管催化活性好、耐水性能好、易于与水分离。
通过GC/MS检测中间产物与文献报道自由基降解产物对比结合文献提供的羟基自由基机理,对Zn_(1.5)PW_(12)O_(40)紫外光降解苯酚和Zn_(1.5)PW_(12)O_(40)臭氧催化氧化降解苯胺的机理进行了探讨。Zn_(1.5)PW_(12)O_(40)紫外光降解苯酚和Zn_(1.5)PW_(12)O_(40)臭氧催化氧化降解苯胺时,·OH自由基起主导作用,并由自由基引发一系列的化学反应对复杂有机物进行了有效的降解。
研究了Zn_(1.5)PW_(12)O_(40)纳米管在紫外、空气及臭氧体系中对难降解制药废水的催化氧化,获取了最佳操作条件。
通过对Zn_(1.5)PW_(12)O_(40)纳米管在三个体系中的经济性和可操作性比较分析,确定了Zn_(1.5)PW_(12)O_(40)/ O3体系为难降解制药废水预处理工艺。该体系能将废水的B/C值由0.05提高到0.6,有利于后续的生物处理。采用GC/MS对制药废水中的难降解的硝基苯类、吡啶类等有机物经该工艺处理后的组成进行了测定,定量说明了硝基苯等难降解类有机物的去除效率。
采用UNITANK-BAF组合工艺处理Zn_(1.5)PW_(12)O_(40)催化臭氧氧化后废水,出水清澈透明,COD浓度小于500mg/L,符合国家达标排放的标准的要求。为难降解制药废水的有效处理提供了一种新方法和新催化剂。
With the swift progress and develop of the medicine industry in recent years, medicine industry rise year by year in specific gravity in national economy. However, pharmacy waste water also becomes main pollution sources to many water bodies, which was a hotspot problem of the environment protection field. Cause of the shifty water quality, large flow, and great amount and species of the non-biodegradable organic in it, the Pharmacy waste water could not be treated by ordinary sewage treatment technology solely. The high thickness and non-biodegradable pharmacy waste water is the investigate subject in this study, started with to promote water biodegradability, the pharmacy waste water combined treatment handicraft has been investigated, and has got fairly good effect. The treated outflow quality from this processes can accord with the national discharge standard(GB 8978-1996).
According to the peculiar characteristic of pharmacy waste water and metal polyoxometalates, with the stencil of natural material (filter paper), a new stype nanoscale metal polyoxometalates catalyst, Zn_(1.5)PW_(12)O_(40) nanotubes, had been designed and composed autonomously during this study, which adopted the sol and gel method. Zn_(1.5)PW_(12)O_(40) nanotubes has good water resistance and easy to be separated from water. A routine represent method for polyoxometalates has been adopted to the Zn_(1.5)PW_(12)O_(40) nanotubes. Observed by transmission electron microscope, the crystal grain conformation is hollow nanotubes, tubes length between 200-900nm, the tubes diameter is 70 nm, the hollow tubes inside diameter is 20 nm about. Adopted the element analysis approach, the Zn_(1.5)PW_(12)O_(40) nanotubes catalyst compositions has been confirmed. The study result was that: Zn_(1.5)PW_(12)O_(40) nanotubes polyanion still maintain the initial Keggin type structure, in which Infrared Spectrum and X-ray powder diffraction (XRD) and 31P magnetic resonance (31P MAS NMR) methods had been used.
Through the common use method in the world, the Zn_(1.5)PW_(12)O_(40) nanotubes has been evaluated, which was used to evaluate the catalysis activity of polyoxometalates at present.In the study Safranine T was taken as the characteristic material, which has the similar constructure to Rhodamine B, but more difficult to be biodegraded. The catalysis activity of Zn_(1.5)PW_(12)O_(40) nanotubes has been investigated by degraded the Safranine T, included photocatalysis activity and chemistry catalyzing the result indicated that: Zn_(1.5)PW_(12)O_(40) nanotubes catalysis activity is fair good.
In three catalytic oxidation systems, which include ultraviolet radiation system, air oxidation system and ozone catalyzes oxidation system, Zn_(1.5)PW_(12)O_(40) nanotubes catalysis effect to non-biodegradable pharmacy waste water had been studied systematically. Only in the USA and Japan etc., polyoxometalates (POM) was applied in photocatalysis chemistry field now, and the studying were mainly carried on the purely-organics, the practical apply study is still few.
The optimum operate condition of Zn_(1.5)PW_(12)O_(40) nanotubes catalyzes oxidation for the pharmacy waste water in ultraviolet radiation system, air oxidation system and ozone catalyzes oxidation system has been got in this research. The particular results as follow:
(1)Takes the promotion of bio-degradability and remove rate of COD as the index, the optimum operation condition of Zn_(1.5)PW_(12)O_(40) nanotubes catalyzing oxidation treats the non-biodegradable pharmacy waste water under room temperature and pressure air system has been obtained. The results is that: air flow rate is 4.5L/h, and temperature is 50℃, and initial pH is above 9, and catalyst amounts is 30g/L, and reaction time 24 hours. There are three influent factors within above, which are air flow rate and catalyst amount and reaction time, which took the remarkable effect to the experiment results. Under the optimum operation condition, the B/C of pharmacy waste water can be promoted from 0.05 to 0.3, which can be propitious to follow bio-process.
(2)The experiment of Zn_(1.5)PW_(12)O_(40) nanotubes/ O3 Catalyzes Oxidation treated non-biodegradable pharmacy waste water has been carried out, the results indicated that: Zn_(1.5)PW_(12)O_(40) nanotubes catalyst have the very good adsorption and high surface activity. It was able to accelerate ozone decomposition generating the Hydroxyl Radical·OH, that makes the difficult to degrade organic by ozone (for instance nitrobenzene and pyrrolidinone etc.) can be degraded under O3/Zn_(1.5)PW_(12)O_(40) handicraft process, at the same time, can shorten the reaction residence time, and accelerate oxide reaction speed, cut down the sources of energy consumption and treatment cost. With this process, the B/C of pharmacy waste water can be promoted from 0.05 to 0.6, which can be propitious to follow bio-process. The obtained optimum operation condition of O3/Zn_(1.5)PW_(12)O_(40) nanotubes is that: catalyst amounts is 2g/L, and Ozone liquid phase thickness is above 0.3mg/L, initial pH between 7.5~9, reaction time is more than 10 minutes. Within those influent factors, the reaction time and ozone thickness made the great effect to the experiment results. On the COD remove rate, it was 46% when ozone thickness was 0.1mg/L, but it can reach 85% when ozone thickness was 0.3mg/L.
By way of comparison and analyses the economy and maneuverability of O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation system and air oxidation system and ultraviolet radiation system, the practical pretreatment process was confirmed to be O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation system. This system can promote the bio-degradability of waste water, and can make the COD remove rate above 74% at the same time.
The mechanism of Zn_(1.5)PW_(12)O_(40) ultraviolet radiation degrade phenol and O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation degrade aniline has been studied on. Through detect the intermediate product by way of GC/MS to conclude the mechanism of Zn_(1.5)PW_(12)O_(40) ultraviolet radiation degrade phenol and O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation degrade aniline:·OH free radical plays the leading role, and a series of chemical reaction has carried out effective degradation on complicated organic from free radical initiation.
Using GC/MS, the inflow and outflow waste water component from the O3/Zn_(1.5)PW_(12)O_(40) nanotubes catalytic oxidation system have been mensurated and analyzed. Result indicates: under a certain process condition, the 44 kinds organic in the raw waste water, include some non-biodegradable organic such as nitrobenzene and aniline and pyridine and pyrimidine, transformed to alcohol and carboxylic acids and aldehyde and ester and alkane after treated by O3/Zn_(1.5)PW_(12)O_(40) system. Bio-toxicity of Waste water reduces obviously, but the bio-degradability improves obviously.
Adopt UNITANK-BAF combined process treat the waste water, which treated by Zn_(1.5)PW_(12)O_(40)/ Ozone Catalyzes Oxidation, and had obtained the optimum operation condition. This process can reduced the raw waste water COD thickness from 4000~5000mg/L to 500mg/L below. The obtained optimum operation condition of UNITANK-BAF combined process treat the out flow waste water from Zn_(1.5)PW_(12)O_(40)/Ozone Catalyzes Oxidation as follow:○1 UNITANK: sludge thickness is 5000~6000mg/L, and DO 2~4 mg/L, and ratio of gas and liquid is above 100:1, and inflow COD thickness 4000~5000mg/L, BOD 2400~3000mg/L, pH is 6, and BOD:N: P=100: 5:1,and HRT is more than 60 hours, room temperature 20~30℃.○2 BAF: pH 6-7, ratio of gas and liquid is above 15:1, and HRT is more than 6 hours, and room temperature 20~30℃. Under this operation condition, the average COD remove rate of UNITANK-BAF combined process can reach 91.4%.
The out flow is limpidity and lucent, COD thickness lower than 500 mg/L, accord with the national waste water discharge standard. Prove that: That Zn_(1.5)PW_(12)O_(40)/ Ozone Catalyzes Oxidation is an effective pretreatment process to the high concentration non-biodegradable pharmacy waste water. Zn_(1.5)PW_(12)O_(40)/O3 Catalyzes Oxidation -UNITANK-BAF allying unite process is the suitable handicraft for the high concentration non-biodegradable pharmacy waste water.
Non-biodegradable pharmacy waste water treated by Zn_(1.5)PW_(12)O_(40)/O3 Catalyzes Oxidation -UNITANK-BAF allying unite process had been detected with GC/MS, results indicated: after treated by Zn_(1.5)PW_(12)O_(40)/O3 Catalyzes Oxidation-UNITANK-BAF allying unite process, the organic detected in Non-biodegradable pharmacy waste water out flow were small molecule carboxylic acid and alcohol, bio-toxity was less, and the out flow is limpidity and lucent, COD thickness was below 500mg/L, which can accord with the national discharge standard(GB 8978-1996).
This study a new style catalyst, Zn_(1.5)PW_(12)O_(40) ultraviolet, has been achieved to exploited. Used with ozone Oxidation, this catalyst can promoted the sewage biodegradability observably, and then the non-biodegradable pharmacy waste water treated continually by UNITANK-BAF combined process can accord with the national discharge standard(GB 8978-1996). The results have important theory meaning and guide function, as well as significance applying value, to the waste water contain non-biodegradable organics.
引文
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