CN104310504B - The treatment process of organic pollutant in a kind of dyeing waste water - Google Patents
The treatment process of organic pollutant in a kind of dyeing waste water Download PDFInfo
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- CN104310504B CN104310504B CN201410529169.6A CN201410529169A CN104310504B CN 104310504 B CN104310504 B CN 104310504B CN 201410529169 A CN201410529169 A CN 201410529169A CN 104310504 B CN104310504 B CN 104310504B
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Abstract
A treatment process for organic pollutant in dyeing waste water, adds copper sulfate, Dawson type polyacid and N, N '-bis-(Niacinamide base)-1,2-ethane in deionized water and mixes, water heat transfer title complex; Dyeing waste water is passed through heater heats, be fed through in sewage treatment pot, title complex is added in sewage treatment pot as degradation catalyst, pass into and be steam heated to 90 DEG C ~ 100 DEG C, insulation 60min ~ 90min, send in equipment for separating liquid from solid and carry out solid-liquid separation, the liquid obtained is discharged by the liquid exit of solid separating device, and solid can be used as degradation catalyst through recovery and reuses.Advantage is: technique is simple, and raw materials cost is low, and energy consumption is low, strong to water soluble contaminants affinity, does not need light source irradiation auxiliary catalysis to degrade, and only need heat and just have good catalytic degradation effect, and can not cause secondary environmental pollution.
Description
Technical field
The present invention relates to the treatment process of organic pollutant in a kind of dyeing waste water.
Background technology
The organic dye that methylenum coeruleum and rhodamine B are dye processing plant, printing and dyeing mill commonly uses, can bring serious pollution to environment by the direct discharging of waste water containing these dye molecules in environment.And this type of waste water from dyestuff has colourity is large, quantity discharged is large, toxicity is large, biodegradability is poor feature, what wherein have also contains the carcinogenic substances such as phenyl ring, amido, azo group, make it have the trend of anti-light solution and oxidation-resistance, be a difficult problem in wastewater treatment always.Thus. the common contaminant methylenum coeruleum in waste water from dyestuff and the catalyzed degradation of rhodamine B are effective ways of administering dyeing waste water and environment purification.
In recent years, Photocatalitic Technique of Semiconductor has become one of effective technology reducing contaminated wastewater.Under UV-irradiation, semi-conductor type materials can as the effective catalyst of organic dye molecule in degradation of dye waste water.Such as modal TiO
2and metalic contamination catalyzer can efficient degradation methylenum coeruleum and rhdamine B molecule, its advantage is that toxicity is low, corrosion-resistant, but its building-up process needs the multiple working procedures such as high-temperature roasting (400 DEG C ~ 600 DEG C) and grinding, and catalysis degradation modulus is to a great extent by the impact of wastewater pH, only can utilize small portion (3% ~ 5%) UV-light in sunlight in catalytic process, this makes the practical application of this type of catalyzer be restricted.Utilize existing catalyzer and photocatalytic degradation method treatment of dyeing and printing effect desirable not to the utmost, there is limitation and cost is higher, therefore, novel, the development of efficient catalytic agent material, application, and the exploitation of new catalyzed degradation method has great theory significance and using value.
Polyacid Base Metal-organic coordination compound is a kind of multifunctional material of inorganic-organic hybridization, and its complex structure is various, and has good catalytic performance, can have wide model application prospect as a kind of catalytic material.But current polyacid base inorganic-organic hybridization title complex, only just have catalyzed degradation performance under illumination condition, processing cost is higher, makes it apply in Industrial Wastewater Treatment and is limited to.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, raw materials cost is low, energy consumption is low, strong to water soluble contaminants affinity, do not need light source irradiation auxiliary catalysis to degrade and just there is good catalytic degradation effect, and the treatment process of organic pollutant in the dyeing waste water of secondary environmental pollution can not be caused.
Technical solution of the present invention is:
A treatment process for organic pollutant in dyeing waste water, its concrete steps are as follows:
1.1, the preparation of degradation catalyst
For raw material with copper sulfate, Dawson type polyacid and N, N '-bis-(Niacinamide base)-1,2-ethane, add in deionized water and mix, obtain mixing suspension, described Dawson type polyacid is K
6p
2w
18o
6215H
2o, adopt hydrothermal synthesis method, synthetic molecules formula is H
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the title complex of O, wherein, 3-dpye is N, N '-bis-(Niacinamide base)-1,2-ethane;
The process of 1.2 dyeing waste waters
Sewage treatment systems is adopted to process the carrying out of dyeing waste water, described dyeing waste water is for containing methylenum coeruleum, the water body of at least one organic pollutant in rhodamine B, by dyeing waste water by heater heats to 50 DEG C ~ 60 DEG C, be fed through in the sewage treatment pot of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot as degradation catalyst, containing methylenum coeruleum and the total mass of rhodamine B and the mass ratio of title complex in described dyeing waste water is 1:5 ~ 1:12, stir, pass into and be steam heated to 90 DEG C ~ 100 DEG C, insulation 60min ~ 90min, send in equipment for separating liquid from solid and carry out solid-liquid separation, the liquid obtained is discharged by the liquid exit of solid separating device, solid can be used as degradation catalyst through recovery and reuses.
Described N, N '-bis-(Niacinamide base)-1,2-ethane and K
6p
2w
18o
6215H
2the mol ratio of O is the mol ratio of 1:1 ~ 1:4, N, N '-bis-(Niacinamide base)-1,2-ethane and copper sulfate is 1:1 ~ 1:3.
N, N '-bis-(Niacinamide base)-1,2-ethane is 1:67mol/L ~ 1:120mol/L with the molecular volume ratio of deionized water.
During Hydrothermal Synthesis, adjust mixing suspension pH to 2.5 ~ 4.0 with hydrochloric acid, pour in autoclave and be warming up to 110 DEG C ~ 120 DEG C, under hydrothermal condition, be incubated 48h ~ 120h.
Described dyeing waste water is the concentration of middle methylenum coeruleum is 10.0mgL
– 1~ 25.0mgL
– 1, the concentration of rhodamine B is 10.0mgL
– 1~ 25.0mgL
– 1.
Described equipment for separating liquid from solid is pressure filter.
Described Sewage treatment systems, there is sewage treatment pot, the pipeline that the water-in of described sewage treatment pot connects is provided with well heater, and the water outlet of described sewage treatment pot is connected with pressure filter by pipeline, and the pipeline between described sewage treatment pot and pressure filter is provided with filter pressing pump.
Described copper sulfate is CuSO
42H
2o.
During intensification, temperature rise rate is 10 DEG C/h ~ 15 DEG C/h; During cooling, rate of temperature fall is 5 DEG C/h ~ 10 DEG C/h.
The add-on of described deionized water is 45% ~ 48% of autoclave volume.
Beneficial effect of the present invention:
(1) water heat transfer is adopted, synthetic method is simple, select Dawson type polyacid as anion ligand, N, N '-bis-(Niacinamide base)-1, amide group in 2-ethane organic ligand is polar group, there is good wetting ability, accelerate crystallisation process during synthesis copper complex, shorten synthesis cycle, improve synthetic yield, reduce synthesis cost; The organic solvent that the title complex synthesized is water insoluble and general, uses as degradation catalyst and is easy to reclaim, can avoid the secondary pollution that it causes environment as catalyzer;
(2) H synthesized
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o is Dawson type polyacid K
6p
2w
18o
6215H
2the negatively charged ion of O as the copper complex with 3-dimensional metal-organic framework structured of template, Dawson type polyacid volume is large, be rich in end oxygen and
μ 2-O bridging oxygen atom, its catalytic activity is higher compared with other types polyacid, and be in the functional complexes of template in Dawson type polyacid, its structures and characteristics is constant, and due to [the P of the non-coordination of its template action
2w
18o
62]
6 –in the duct that polyanionic is filled in as guest molecule, metal-organic framework is supported and forms large pore passage structure, the 3-dimensional metal organic backbone of title complex illustrate that a kind of single node 4-of novelty connects { 8
68
68
78
78
78
7topological framework, add the contact area between catalyzed organic molecule and functional complexes catalyzer, be conducive to the catalytic performance improving this type of functional complexes material;
(3) amide group and Rou – (CH can be introduced at N, N '-bis-(Niacinamide base)-1,2-in ethane part
2)
2– group, the length of adjustment organic ligand and snappiness, and change part configuration flexibly according to the coordination demand of transition metal ion, thus the final structure of regulation and control title complex; The introducing of amide group can increase the wetting ability of title complex, thus increases title complex to the catalytic activity of water soluble contaminants molecule; The affinity of title complex to water miscible organic pollutant molecule of synthesis is strong, catalytic degradation effect good, only in a heated condition, just to organic pollutant catalyzed degradation, can improve catalytic efficiency.
Accompanying drawing explanation
Fig. 1 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the PXRD diffractogram of O;
Fig. 2 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the thermogram of O;
In figure: 1-H
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o;
Fig. 3 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the coordination environment figure of cupric ion in O;
Fig. 4 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the structure iron of Dawson type polyacid in O;
Fig. 5 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the three dimensional skeletal structure figure of cvdmetallorganiccvd ligand in O;
Fig. 6 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the spiral-link composition of the cvdmetallorganiccvd ligand in O;
Fig. 7 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the structure iron in two kinds of ducts in O three dimensional skeletal structure;
Fig. 8 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o comprises the tomograph of polyoxoanion;
Fig. 9 is the H that the present invention synthesizes
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the three dimensional topology figure of O;
Figure 10 is the structural representation of the Sewage treatment systems that the present invention adopts;
In figure: 1-sewage treatment pot, 2-well heater, 3-pressure filter, 4-filter pressing pump;
Figure 11 is the H adding the present invention's synthesis
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the uv-absorbing figure of O photocatalytic degradation methylenum coeruleum (MB) when heating 100 DEG C and degradation rate variation diagram;
Figure 12 is the H adding the present invention's synthesis
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the uv-absorbing figure of O photocatalytic degradation rhodamine B (RhB) when heating 100 DEG C and degradation rate variation diagram;
Figure 13 is the H adding the present invention's synthesis
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o is photocatalytic degradation rhodamine B (RhB) when heating 100 DEG C, and the histogram of rhodamine B (RhB) the degradation rate change of experiment is taken turns in catalyzer recycling five.
Embodiment
Embodiment 1
1.1, the preparation of degradation catalyst
By 0.20molCuSO
42H
2o, 0.10molN, N '-bis-(Niacinamide base)-1,2-ethane, 0.10molK
6p
2w
18o
6215H
2o and 12.0LH
2o joins in 25L beaker successively, at room temperature stir 30min, obtain suspended mixture, after reconciling the pH to 2.5 of suspended mixture with the HCl solution of 0.5mol/L, transfer in the autoclave of 25L, be warming up to 110 DEG C with the heating rate of 10 DEG C/h, under hydrothermal condition, be incubated 120h, cool the temperature to room temperature with the rate of temperature fall of 10 DEG C/h, obtain blue bulk crystals, with deionized water rinsing 3 times, naturally dry under room temperature, obtain H
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o title complex, wherein, 3-dpye is N, N '-bis-(Niacinamide base)-1,2-ethane, and structural formula is:
, productive rate is 45%, its PXRD diffracting spectrum as shown in Figure 1, the coordination environment figure of metal copper ion as shown in Figure 3, [the P of non-coordination
2w
18o
62]
6 –as shown in Figure 4, as shown in Figure 5, as shown in Figure 6, the two kinds of duct figure (duct: A and B) in title complex three-dimensional framework as shown in Figure 7, comprise [P to the coiled strand structure that metal copper ion linking ligand is formed to the three-dimensional network figure of title complex to polyanionic structure iron
2w
18o
62]
6 –as shown in Figure 8, the topological diagram of three-dimensional net structure as shown in Figure 9 for the three-dimensional net structure of polyanionic guest molecule.
The process of 1.2 dyeing waste waters
As shown in Figure 10, this Sewage treatment systems, there is sewage treatment pot 1, the pipeline that the water-in of described sewage treatment pot 1 connects is provided with well heater 2, the water outlet of described sewage treatment pot 1 is connected with pressure filter 3 by pipeline, and the pipeline between described sewage treatment pot 1 and pressure filter 3 is provided with filter pressing pump 4.
(in waste water, the concentration of methylenum coeruleum is 25.0mgL to the dyeing waste water containing methylenum coeruleum organic pollutant to adopt Sewage treatment systems
– 1) carrying out process, dyeing waste water is heated to 60 DEG C by well heater 2, be fed through in the sewage treatment pot 1 of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot 1 as degradation catalyst, every 1000L dyeing waste water need add title complex 125g (in dyeing waste water be 1:5 containing the quality of methylenum coeruleum and the mass ratio of title complex), stir, pass into and be steam heated to 90 DEG C, insulation 60min, waste water after process is squeezed in pressure filter 3 and is carried out solid-liquid separation by unlatching filter pressing pump 4, the liquid obtained is discharged by the liquid exit of pressure filter 3, solid can be used as degradation catalyst through recovery and reuses.
(in waste water, the concentration of rhodamine B is 25.0mgL to the dyeing waste water containing rhodamine B organic pollutant to adopt Sewage treatment systems
– 1) carrying out process, dyeing waste water is heated to 60 DEG C by well heater 2, be fed through in the sewage treatment pot 1 of Sewage treatment systems, every 1000L dyeing waste water need add title complex 125g (in dyeing waste water be 1:5 containing the quality of rhodamine B and the mass ratio of title complex), stir, pass into and be steam heated to 90 DEG C, insulation 60min, waste water after process is squeezed in pressure filter 3 and is carried out solid-liquid separation by unlatching filter pressing pump 4, the liquid obtained is discharged by the liquid exit of solid pressure filter 3, and solid can be used as degradation catalyst through recovery and reuses.
In treatment of dyeing wastewater process, in order to monitor the catalytic degradation effect of dyeing waste water, taking out 50mL solution every 30min and carrying out centrifugation, obtain clarification upper solution and carry out UV test.As shown in figure 11, after 60min, the characteristic absorbance of methylene blue solution significantly reduces, and shows that this material part is decomposed.Wherein, the catalytic degradation efficiency of the title complex that step 1.1 is synthesized is 80.58%, shows that title complex 1 can play katalysis to the degraded of methylenum coeruleum at short notice as catalyzer.As shown in figure 12, after 60min, the characteristic absorbance significant proportion of rhodamine B solution reduces, and shows that the major part of this material is decomposed.Wherein, the catalytic degradation efficiency of the title complex that step 1.1 is synthesized is 90.52%, shows that the title complex that step 1.1 is synthesized can play certain katalysis to the degraded of rhodamine B as catalyzer in 60min.Result shows, the degraded of title complex to organic pollutant molecule methylenum coeruleum and rhodamine B that under heating condition, step 1.1 is synthesized has obvious catalytic activity.
Embodiment 2
1.1, the preparation of degradation catalyst
By 0.45molCuSO
42H
2o, 0.15molN, N '-bis-(Niacinamide base)-1,2-ethane, 0.30molK
6p
2w
18o
6215H
2o and 11.0LH
2o joins in 25L container successively, at room temperature stir 50min, obtain suspended mixture, after reconciling the pH to 3.5 of suspended mixture with the HCl solution of 0.1mol/L, transfer in the autoclave of 25L, be warming up to 115 DEG C with the heating rate of 15 DEG C/h, under hydrothermal condition, be incubated 48h, cool the temperature to room temperature with the rate of temperature fall of 5 DEG C/h, obtain blue bulk crystals, with deionized water rinsing 2 times, naturally dry under room temperature, obtain H
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o, wherein, 3-dpye is N, N '-bis-(Niacinamide base)-1,2-ethane, and productive rate is 47%, its PXRD diffracting spectrum as shown in Figure 1, the coordination environment figure of metal copper ion as shown in Figure 3, [the P of non-coordination
2w
18o
62]
6 –as shown in Figure 4, as shown in Figure 5, as shown in Figure 6, the two kinds of duct figure (duct: A and B) in title complex three-dimensional framework as shown in Figure 7, comprise [P to the coiled strand structure that metal copper ion linking ligand is formed to the three-dimensional network figure of title complex to polyanionic structure iron
2w
18o
62]
6 –as shown in Figure 8, the topological diagram of three-dimensional net structure as shown in Figure 9 for the three-dimensional net structure of polyanionic guest molecule.
The process of 1.2 dyeing waste waters
As shown in Figure 10, this Sewage treatment systems, there is sewage treatment pot 1, the pipeline that the water-in of described sewage treatment pot 1 connects is provided with well heater 2, the water outlet of described sewage treatment pot 1 is connected with pressure filter 3 by pipeline, and the pipeline between described sewage treatment pot 1 and pressure filter 3 is provided with filter pressing pump 4.
(in waste water, the concentration of methylenum coeruleum is 20.0mgL to the dyeing waste water containing methylenum coeruleum organic pollutant to adopt Sewage treatment systems
– 1) carrying out process, dyeing waste water is heated to 55 DEG C by well heater 2, be fed through in the sewage treatment pot 1 of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot 1 as degradation catalyst, every 1000L dyeing waste water need add title complex 200g (in dyeing waste water be 1:10 containing the quality of methylenum coeruleum and the mass ratio of title complex), stir, pass into and be steam heated to 95 DEG C, insulation 75min, waste water after process is squeezed in pressure filter 3 and is carried out solid-liquid separation by unlatching filter pressing pump 4, the liquid obtained is discharged by the liquid exit of pressure filter 3, solid can be used as degradation catalyst through recovery and reuses.
(in waste water, the concentration of rhodamine B is 20.0mgL to the dyeing waste water containing rhodamine B organic pollutant to adopt Sewage treatment systems
– 1) carrying out process, dyeing waste water is heated to 55 DEG C by well heater 2, be fed through in the sewage treatment pot 1 of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot 1 as degradation catalyst, every 1000L dyeing waste water need add title complex 200g (in dyeing waste water be 1:10 containing the quality of rhodamine B and the mass ratio of title complex), stir, pass into and be steam heated to 95 DEG C, insulation 75min, waste water after process is squeezed in pressure filter 3 and is carried out solid-liquid separation by unlatching filter pressing pump 4, the liquid obtained is discharged by the liquid exit of pressure filter 3, solid can be used as degradation catalyst through recovery and reuses.
In treatment of dyeing wastewater process, in order to monitor the catalytic degradation effect of dyeing waste water, taking out 50mL solution every 30min and carrying out centrifugation, obtain clarification upper solution and carry out UV test.As shown in figure 11, after 75min, the characteristic absorbance of methylene blue solution significantly reduces, and shows that this material overwhelming majority is decomposed.Wherein, the catalytic degradation efficiency of the title complex that step 1.1 is synthesized is 91.85%, shows that title complex 1 can play significant katalysis to the degraded of methylenum coeruleum as catalyzer in 75min.As shown in figure 12, after 75min, the characteristic absorbance of rhodamine B solution reduces obviously, shows that the major part of this material is decomposed.Wherein, the catalytic degradation efficiency of the title complex that step 1.1 is synthesized is 94.68%, shows that the title complex that step 1.1 is synthesized can play extraordinary katalysis to the degraded of rhodamine B as catalyzer in 75min.Result shows, the degraded of title complex to organic pollutant molecule methylenum coeruleum and rhodamine B that under heating condition, step 1.1 is synthesized has obvious catalytic activity.
Embodiment 3
1.1, the preparation of degradation catalyst
By 0.15molCuSO
42H
2o, 0.15molN, N '-bis-(Niacinamide base)-1,2-ethane, 0.6molK
6p
2w
18o
6215H
2o and 10.0LH
2o joins in 25L beaker successively, at room temperature stir 20min, obtain suspended mixture, after reconciling the pH to 4.0 of suspended mixture with the HCl solution of 1.0mol/L, transfer in the autoclave of 25L, be warming up to 120 DEG C with the heating rate of 15 DEG C/h, under hydrothermal condition, be incubated 96h, cool the temperature to room temperature with the rate of temperature fall of 10 DEG C/h, obtain blue bulk crystals, by washed with de-ionized water 3 times, naturally dry under room temperature, obtain H
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2o, wherein, 3-dpye is N, N '-bis-(Niacinamide base)-1,2-ethane, and productive rate is 54%, its PXRD diffracting spectrum as shown in Figure 1, the coordination environment figure of metal copper ion as shown in Figure 3, [the P of non-coordination
2w
18o
62]
6 –as shown in Figure 4, as shown in Figure 5, as shown in Figure 6, the two kinds of duct figure (duct: A and B) in title complex three-dimensional framework as shown in Figure 7, comprise [P to the coiled strand structure that metal copper ion linking ligand is formed to the three-dimensional network figure of title complex to polyanionic structure iron
2w
18o
62]
6 –as shown in Figure 8, the topological diagram of three-dimensional net structure as shown in Figure 9 for the three-dimensional net structure of polyanionic guest molecule.
The process of 1.2 dyeing waste waters
As shown in Figure 10, this Sewage treatment systems, there is sewage treatment pot 1, the pipeline that the water-in of described sewage treatment pot 1 connects is provided with well heater 2, the water outlet of described sewage treatment pot 1 is connected with pressure filter 3 by pipeline, and the pipeline between described sewage treatment pot 1 and pressure filter 3 is provided with filter pressing pump 4.
(in waste water, the concentration of methylenum coeruleum is 10.0mgL to the dyeing waste water containing methylenum coeruleum organic pollutant to adopt Sewage treatment systems
– 1) carrying out process, dyeing waste water is heated to 50 DEG C by well heater 2, be fed through in the sewage treatment pot 1 of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot 1 as degradation catalyst, every 1000L dyeing waste water need add title complex 120g (in dyeing waste water be 1:12 containing the quality of methylenum coeruleum and the mass ratio of title complex), stir, pass into and be steam heated to 100 DEG C, insulation 90min, waste water after process is squeezed in pressure filter 3 and is carried out solid-liquid separation by unlatching filter pressing pump 4, the liquid obtained is discharged by the liquid exit of pressure filter 3, solid can be used as degradation catalyst through recovery and reuses.
(in waste water, the concentration of rhodamine B is 10.0mgL to the dyeing waste water containing rhodamine B organic pollutant to adopt Sewage treatment systems
– 1) carrying out process, dyeing waste water is heated to 50 DEG C by well heater 2, be fed through in the sewage treatment pot 1 of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot 1 as degradation catalyst, every 1000L dyeing waste water need add title complex 120g (in dyeing waste water be 1:12 containing the quality of rhodamine B and the mass ratio of title complex), stir, pass into and be steam heated to 100 DEG C, insulation 90min, waste water after process is squeezed in pressure filter 3 and is carried out solid-liquid separation by unlatching filter pressing pump 4, the liquid obtained is discharged by the liquid exit of pressure filter 3, solid can be used as degradation catalyst through recovery and reuses.
In treatment of dyeing wastewater process, in order to monitor the catalytic degradation effect of dyeing waste water, taking out 50mL solution every 30min and carrying out centrifugation, obtain clarification upper solution and carry out UV test.As shown in figure 11, after 90min, the characteristic absorbance of methylene blue solution almost disappears, and shows that this material is almost decomposed completely.Wherein, the catalytic degradation efficiency of the title complex that step 1.1 is synthesized is 99.67%, shows that title complex 1 can play fabulous katalysis to the degraded of methylenum coeruleum as catalyzer in 90min.As shown in figure 12, after 90min, the characteristic absorbance almost completely dissolve of rhodamine B solution, shows that this material is decomposed completely.Wherein, the catalytic degradation efficiency of the title complex that step 1.1 is synthesized is 99.11%, shows that the title complex that step 1.1 is synthesized can play splendid catalytic effect to the degraded of rhodamine B as catalyzer.Result shows, the degraded of title complex to organic pollutant molecule methylenum coeruleum and rhodamine B that under heating condition, step 1.1 is synthesized has high catalytic efficiency.Because title complex 1 synthesizes under hydrothermal condition, be not extremely water insolublely also soluble in general organic solvent, the title complex therefore in catalyst system can precipitate rear Reusability.As shown in figure 13, have studied title complex 1 and repeat as catalyzer the experiment that five take turns rhodamine B degradation under heating condition, degradation rate does not have considerable change, and show that title complex 1 can recycle as catalyzer, therefore title complex 1 can as a kind of stable, environment amenable catalyzer.
Comparative example 1
The method of embodiment 1 does not add catalyzed degradation agent, and direct heating is to 100 DEG C;
The aqueous solution of methylene blue of control group is heated to 100 DEG C, and after 90min, degradation rate is 6%, shows that this material cannot only by being heated to 100 DEG C and degrading;
The rhodamine B aqueous solution of control group is heated to 100 DEG C, and after 90min, degradation rate is 3%, shows that this material cannot only by being heated to 100 DEG C and degrading.
Table 1
Based on the sign of embodiment 1 ~ embodiment 3 copper complex
(1) powdery diffractometry characterizes the stability of phase purity and catalyzer
RigakuUltimaIV powder x-ray diffraction collects powdered diffraction data, and actuating current is 40mA, and voltage is 40kV.Adopt copper target X-ray.Scanning constant, receiving slit wide is 0.1mm.Density data collects use 2
θ/
θscan pattern, sweep limit 5
oto 50
o, sweep velocity is 5
o/ s, span is 0.02
o/ time.Data fitting uses Cerius2 program, and single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury1.4.1.
As shown in Figure 1, based on the powder x-ray diffraction spectrogram of title complex and the PXRD spectrogram of matching substantially identical, show that title complex is pure phase.The powder x-ray diffraction spectrogram of title complex after being heated to 100 DEG C and after being heated to 100 DEG C of DeRs is contained respectively in Fig. 1, be all consistent with the PXRD spectrogram of theory, indicate title complex and the stability that all had of title complex after photochemical catalysis of Hydrothermal Synthesis.
(2) thermogravimetric exosyndrome material stability
Thermostability adopts PE-PyrisDiamondS-II thermal analyzer to complete, heating rate 10 DEG C/min, temperature range 20 DEG C ~ 800 DEG C.Fig. 2 shows that the decomposition temperature scope of the title complex that the present invention synthesizes is 70 DEG C ~ 800 DEG C.
(3) crystal structure determination
Choose the monocrystalline of suitable size with microscope, under room temperature, adopt BrukerSMARTAPEXII diffractometer (graphite monochromator, Mo-K
a,
l=0.71073) diffraction data is collected.Scan mode
w-φ, diffraction data uses SADABS program to carry out absorption correction.Reduction of data and structure elucidation use SAINT and SHELXTL program to complete respectively.Method of least squares determines whole non-hydrogen atom coordinate, and obtains hydrogen atom position with theoretical hydrogenation method.Method of least squares is adopted to carry out refine to crystalline structure.Fig. 3 ~ Fig. 8 to show in embodiment 1 ~ embodiment 4 basic coordination situation and the expansion structure of the copper complex based on flexible two Pyridine bisamide organic ligand and Dawson type polyacid of synthesis.The partial parameters of its crystallography point diffraction data gathering and structure refinement is as shown in table 2 below:
Table 2
Claims (10)
1. the treatment process of organic pollutant in dyeing waste water, is characterized in that: concrete steps are as follows:
1.1, the preparation of degradation catalyst
For raw material with copper sulfate, Dawson type polyacid and N, N '-bis-(Niacinamide base)-1,2-ethane, add in deionized water and mix, obtain mixing suspension, described Dawson type polyacid is K
6p
2w
18o
6215H
2o, adopt hydrothermal synthesis method, synthetic molecules formula is H
6[Cu
3(H
2o)
6(P
2w
18o
62)
2(3-dpye)
6] 28H
2the title complex of O, wherein, 3-dpye is N, N '-bis-(Niacinamide base)-1,2-ethane;
The process of 1.2 dyeing waste waters
Sewage treatment systems is adopted to process dyeing waste water, described dyeing waste water is for containing methylenum coeruleum, the water body of at least one organic pollutant in rhodamine B, by dyeing waste water by heater heats to 50 DEG C ~ 60 DEG C, be fed through in the sewage treatment pot of Sewage treatment systems, title complex step 1.1 synthesized adds in sewage treatment pot as degradation catalyst, containing methylenum coeruleum and the total mass of rhodamine B and the mass ratio of title complex in described dyeing waste water is 1:5 ~ 1:12, stir, pass into and be steam heated to 90 DEG C ~ 100 DEG C, insulation 60min ~ 90min, send in equipment for separating liquid from solid and carry out solid-liquid separation, the liquid obtained is discharged by the liquid exit of solid separating device, solid is reused as degradation catalyst through reclaiming.
2. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: described N, N '-bis-(Niacinamide base)-1,2-ethane and K
6p
2w
18o
6215H
2the mol ratio of O is the mol ratio of 1:1 ~ 1:4, N, N '-bis-(Niacinamide base)-1,2-ethane and copper sulfate is 1:1 ~ 1:3.
3. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: the molecular volume of N, N '-bis-(Niacinamide base)-1,2-ethane and deionized water is than being 1:67mol/L ~ 1:120mol/L.
4. the treatment process of organic pollutant in dyeing waste water according to claim 1, it is characterized in that: during Hydrothermal Synthesis, adjust mixing suspension pH to 2.5 ~ 4.0 with hydrochloric acid, pour in autoclave and be warming up to 110 DEG C ~ 120 DEG C, under hydrothermal condition, be incubated 48h ~ 120h.
5. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: described dyeing waste water is the concentration of middle methylenum coeruleum is 10.0mgL
– 1~ 25.0mgL
– 1, the concentration of rhodamine B is 10.0mgL
– 1~ 25.0mgL
– 1.
6. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: described equipment for separating liquid from solid is pressure filter.
7. the treatment process of organic pollutant in dyeing waste water according to claim 6, it is characterized in that: described Sewage treatment systems, there is sewage treatment pot, the pipeline that the water-in of described sewage treatment pot connects is provided with well heater, the water outlet of described sewage treatment pot is connected with pressure filter by pipeline, and the pipeline between described sewage treatment pot and pressure filter is provided with filter pressing pump.
8. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: described copper sulfate is CuSO
42H
2o.
9. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: in Hydrothermal Synthesis step, during intensification, temperature rise rate is 10 DEG C/and h ~ 15 DEG C/h; During cooling, rate of temperature fall is 5 DEG C/h ~ 10 DEG C/h.
10. the treatment process of organic pollutant in dyeing waste water according to claim 1, is characterized in that: the add-on of described deionized water is 45% ~ 48% of autoclave volume.
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