CN115231754A - Treatment method for industrial wastewater containing high-concentration copper and glycine - Google Patents
Treatment method for industrial wastewater containing high-concentration copper and glycine Download PDFInfo
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- CN115231754A CN115231754A CN202210891915.0A CN202210891915A CN115231754A CN 115231754 A CN115231754 A CN 115231754A CN 202210891915 A CN202210891915 A CN 202210891915A CN 115231754 A CN115231754 A CN 115231754A
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 122
- 239000010949 copper Substances 0.000 title claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 93
- 239000004471 Glycine Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 207
- 235000006408 oxalic acid Nutrition 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 61
- 239000010802 sludge Substances 0.000 claims description 58
- 238000000605 extraction Methods 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010009 beating Methods 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005935 Sulfuryl fluoride Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 6
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 210000003462 vein Anatomy 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- 230000000694 effects Effects 0.000 description 16
- 229910001385 heavy metal Inorganic materials 0.000 description 15
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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Abstract
The invention discloses a treatment method for industrial wastewater containing high-concentration copper and glycine, which comprises the following steps: 1. performing collateral breaking treatment; 2. heating treatment; 3. extracting compound copper and elemental copper; 4. extracting glycine; the treatment method has the advantages of good stability, low cost, simple treatment mode and short time consumption, can maximally extract copper and glycine in the industrial wastewater, and realizes waste regeneration and resource utilization.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a treatment method for industrial wastewater containing high-concentration copper and glycine.
Background
Heavy metal wastewater is one of the main environmental pollution problems to be solved urgently, and the treatment of industrial heavy metal wastewater has certain complexity, because the components of the heavy metal wastewater are complex, the treatment difficulty is very high. With the development of chemical industry, the use amount of heavy metals by human beings is increasing, and therefore, heavy metal pollution is becoming more serious. The discharge of the heavy metal wastewater does not reach the standard, so that the metal resources are wasted, the economic benefit is affected, and the ecological environment is seriously harmed.
Heavy metal wastewater has large water quantity, complex water quality and difficult control of components, heavy metal ions such as chromium, copper, nickel, zinc and the like have high toxicity, and part of the heavy metal ions belong to carcinogenic, teratogenic and mutagenic highly toxic substances and have great harm to human beings. Heavy metal wastewater is one of wastewater with the most serious environmental pollution and the most serious harm to human beings, and after the heavy metal wastewater is discharged into a natural water body, heavy metals can be retained, accumulated and migrated in the natural water body in various chemical states or chemical forms, so that harm is caused. The traditional treatment method is adopted to treat the wastewater, and the problems of poor quality of the treated wastewater, high cost of the treatment process, difficult recovery of precious metals and the like exist. The alkaline precipitation has the advantages of low price, easy control of the dosage and the like, but the method has poor effect on treating the industrial wastewater containing the complex copper and cannot reach the wastewater discharge standard after treatment. Meanwhile, in the aspect of treating heavy metal wastewater, the environmental management target of efficiently extracting heavy metals is pursued, secondary pollution is avoided, valuable resources are fully recovered, and other higher-level environmental and economic benefit targets are pursued.
Therefore, there is a need for a treatment method for industrial wastewater containing high concentration of copper and glycine to improve the extraction rate of heavy metals.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for treating industrial wastewater containing high-concentration copper and glycine.
The technical scheme of the invention is as follows: a treatment method for industrial wastewater containing high-concentration copper and glycine comprises the following steps:
1. and (3) vein breaking treatment:
heating an oxalic acid solution prepared in a container until oxalic acid crystals in the oxalic acid solution are completely dissolved to obtain an oxalic acid dissolved solution, and mixing industrial wastewater and the oxalic acid dissolved solution in proportion to obtain a first mixed solution;
2. heating treatment:
heating the first mixed solution and continuously stirring until the first mixed solution is white and turbid to obtain a second mixed solution;
3. extraction of compound copper and elemental copper:
continuously heating and continuously stirring the second mixed solution, and filtering the second mixed solution to obtain blue precipitate and filtrate, wherein the blue precipitate is compound copper, and red elemental copper is attached to the bottom of the container;
4. extraction of glycine:
and naturally cooling the filtrate to room temperature, and separating out white crystals, wherein the white crystals are glycine.
Further, in the first step, the concentration of the oxalic acid solution is 0.5-3 mol/L. The parameters are convenient for determining the optimal action concentration of the oxalic acid solution, thereby determining the highest extraction rate of the oxalic acid solution to copper and glycine in the industrial wastewater.
Further, in the first step, the volume of the industrial wastewater is unchanged, and the volume ratio of the oxalic acid solution to the industrial wastewater is (0.5-3): 1. the selection of the volume ratio is convenient for determining the optimal addition amount of the oxalic acid solution, thereby determining the highest extraction rate of the oxalic acid solution to the copper and the glycine in the industrial wastewater.
Further, in the third step, the second mixed solution is heated and stirred at the heating temperature of 55-65 ℃ for 5-10 min. The heating parameters are selected to precipitate more compound copper and elemental copper, and the obtained compound copper and elemental copper are difficult to extract due to over-high or over-low temperature.
Further, the heating of the step one, the heating of the step two and the step three and the continuous stirring are all completed by adopting a magnetic heater. The magnetic heater can enable the dissolution degree of the oxalic acid crystal to be more complete under the action of a magnetic field, and enable the oxalic acid dissolving solution and the industrial wastewater to be more uniformly mixed under the magnetic stirring, so that the oxalic acid dissolving solution and the industrial wastewater can be more completely reacted, and more compounds of copper and glycine can be obtained.
Further, in the first step, the heating temperature of the oxalic acid solution is 45-55 ℃. The parameters are selected to enable the oxalic acid crystal to be dissolved more completely, so that the obtained oxalic acid dissolving solution is higher in purity.
In the second step, the heating temperature of the first mixed solution is 55 to 65 ℃. The selection of the parameters enables the industrial wastewater and the oxalic acid dissolving solution to be mixed more uniformly, so that the oxalic acid dissolving solution and the copper and the glycine react more completely, and the extraction efficiency of the oxalic acid dissolving solution on the copper and the glycine is improved.
Further, the filtration mode in the third step is filter paper filtration. The filter paper has excellent water filtering performance, loose paper quality and strong liquid absorption, and can better separate precipitates from liquid.
Further, before the industrial wastewater is mixed with the oxalic acid dissolving solution, the industrial wastewater is pretreated, and the pretreatment method comprises the following steps:
1) Heating x L industrial wastewater to 70-90 ℃, sequentially adding 20-30 g/L polyacrylamide and 15-25 g/L sodium alginate into the industrial wastewater to obtain a mixed solution, magnetically stirring the mixed solution for 20-30 min, and performing solid-liquid separation to obtain an industrial wastewater stock solution and y cm 3 The sludge of (2);
2) Beating the sludge at a constant speed by using a cylindrical rod with the diameter of n cm, and simultaneously introducing mixed gas into the sludge, wherein the introduction time of the mixed gas is 15-20 min, the volume of the mixed gas accounts for 40-60% of the volume of the sludge, and the mixed gas comprises 90-95% of ozone, 3-5% of helium and 2-5% of sulfuryl fluoride by mass percentage to obtain activated sludge; the speed of uniformly beating the sludge and the volume of the sludge meet a formula (1), the volume of the sludge and the volume of the industrial wastewater meet a formula (2), the diameter of the cylindrical rod and the volume of the sludge meet a formula (3),
wherein v is the speed of uniform beating, and the unit is taken once/min; t is the time for introducing the mixed gas, and the unit is min; v is the volume ratio of the volume of the sludge to the volume of the wastewater, and the unit is cm 3 L; a is the volume percentage of the volume of the mixed gas in the volume of the sludge, y is the volume of the sludge, x is the volume of the industrial wastewater, and n is the diameter of the cylindrical rod;
3) And mixing the mixed sludge and the industrial wastewater stock solution, uniformly stirring to obtain pretreated industrial wastewater, and then mixing the pretreated industrial wastewater with the oxalic acid dissolving solution.
After the industrial wastewater is treated to form sludge, the sludge has countless air holes, then the air holes with larger diameters in the sludge are dispersed into fine air holes through uniform-speed hammering, the contact area with mixed gas is increased, so that the combination effect with the mixed gas is improved, and the obtained activated sludge has good catalytic performance.
The invention has the beneficial effects that:
(1) According to the invention, the oxalic acid solution is used for carrying out the decomplexation treatment on the copper and the glycine in the industrial wastewater, so that the copper in the high-concentration complex copper wastewater can be effectively extracted, the glycine component in the wastewater can be effectively recovered, the operation is simple, the pH is not required to be additionally adjusted, and the method is suitable for treating the industrial wastewater containing the high-concentration copper and the glycine in large and medium-sized factories.
(2) According to the invention, the industrial wastewater is pretreated to obtain the activated sludge, so that the catalytic performance of the activated sludge is enhanced, the complex breaking effect of the oxalic acid solution on copper and glycine in the industrial wastewater is enhanced, and the complex breaking treatment efficiency is improved.
Drawings
FIG. 1 is a graph showing the comparison of the extraction rate of copper with different oxalic acid concentrations;
FIG. 2 is a graph showing the comparison of the volume ratio of industrial wastewater to oxalic acid to the extraction rate of copper in the present invention;
FIG. 3 is a diagram of a mixed solution obtained by the treatment of the first step in example 1;
FIG. 4 is a photograph of a white turbid mixed solution obtained by the second treatment in step two of example 1;
FIG. 5 is a graph showing the actual effect of copper oxalate obtained after filtration in step three of example 1;
FIG. 6 is a graph showing the effect of glycine obtained by the fourth treatment in step four of example 1;
FIG. 7 is an infrared spectrum obtained by infrared measurement of a white crystal in the present invention;
FIG. 8 shows the remaining amount of copper in the industrial wastewater of example 1;
FIG. 9 shows the remaining amount of glycine in the industrial wastewater of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof for better understanding the advantages of the invention.
Example 1
A treatment method for industrial wastewater containing high-concentration copper and glycine comprises the following steps:
1. and (3) vein breaking treatment:
heating 2L of oxalic acid solution with the concentration of 2mol/L prepared in a container to 50 ℃, completely dissolving oxalic acid crystals in the oxalic acid solution at the moment to obtain oxalic acid solution, and mixing the industrial wastewater and the oxalic acid solution according to the ratio of 1:2, the volume of the industrial wastewater is 1L, and a first mixed solution is obtained;
2. heating treatment:
heating the first mixed solution and continuously stirring until the first mixed solution is white and turbid to obtain a second mixed solution, wherein the heating temperature is 60 ℃;
3. extraction of compound copper and elemental copper:
continuously heating the second mixed solution at 60 ℃ for 8min and continuously stirring, and filtering the second mixed solution by using filter paper, wherein the blue precipitate is a compound copper, the compound copper is cupric oxalate, and the bottom of the container is attached with red elemental copper;
4. extraction of glycine:
and naturally cooling the filtrate to room temperature, and precipitating to obtain white crystals, wherein the white crystals are glycine.
Example 2
The difference between the embodiment and the embodiment 1 is that in the first step, the concentration of the oxalic acid solution is 0.5mol/L.
Example 3
The difference between the embodiment and the embodiment 1 is that in the first step, the concentration of the oxalic acid solution is 3mol/L.
Example 4
The difference between the present embodiment and embodiment 1 is that, in the step one, the volume of the industrial wastewater is not changed, and the volume ratio of the oxalic acid solution to the industrial wastewater is 1:2.
example 5
The difference between the embodiment and embodiment 1 is that in the step one, the volume of the industrial wastewater is not changed, and the volume ratio of the oxalic acid to the industrial wastewater is 3:1.
example 6
The difference between this example and example 1 is that, in the third step, when the mixed solution is heated and stirred, the heating temperature is 55 ℃, and the heating time is 10min.
Example 7
The difference between this example and example 1 is that, in the third step, the heating temperature is 65 ℃ and the heating time is 5min when the mixed solution is heated and stirred.
Example 8
The difference between the embodiment and the embodiment 1 is that in the step one, the heating temperature of the oxalic acid solution is 45 ℃; in the second step, the heating temperature of the mixed solution is 55 ℃.
Example 9
The difference between the embodiment and the embodiment 1 is that in the step one, the heating temperature of the oxalic acid solution is 55 ℃; in the second step, the heating temperature of the mixed solution is 65 ℃.
Example 10
The difference between the embodiment and the embodiment 1 is that the industrial wastewater is pretreated before being mixed with the oxalic acid dissolving solution, and the pretreatment method comprises the following steps:
1) Heating 1L of industrial wastewater to 80 ℃, and sequentially adding 25g of polyacrylamide and 20g of sodium alginate into the industrial wastewater to obtainMagnetically stirring the mixed solution for 25min, and performing solid-liquid separation to obtain industrial wastewater stock solution of 365cm 3 The sludge of (2);
2) Beating the sludge at a constant speed by using a cylindrical rod with the diameter of 3.65cm, and introducing mixed gas into the sludge, wherein the introduction time of the mixed gas is 18min, the volume of the mixed gas accounts for 50% of the volume of the sludge, and the mixed gas comprises 93% of ozone, 4% of helium and 3% of sulfuryl fluoride in percentage by mass, so as to obtain activated sludge; the speed of uniformly beating the sludge and the volume of the sludge meet a formula (1), the volume of the sludge and the volume of the industrial wastewater meet a formula (2), the diameter of the cylindrical rod and the volume of the sludge meet a formula (3),
wherein v is the speed of uniform beating, and the unit is taken once/min; t is the time for introducing the mixed gas, and the unit is min; v is the volume ratio of the volume of the sludge to the volume of the wastewater, and the unit is cm 3 L; a is the volume percentage of the volume of the mixed gas in the volume of the sludge, y is the volume of the sludge, x is the volume of the industrial wastewater, and n is the diameter of the cylindrical rod;
3) Mixing the mixed sludge and the industrial wastewater stock solution, uniformly stirring to obtain pretreated industrial wastewater, and then mixing the pretreated industrial wastewater and the oxalic acid dissolving solution;
let y =365cm 3 Substituting into the formula (3) to obtain n =7.3cm;
let y =365cm 3 And x =1L is substituted into the formula (2) to obtain V =365cm 3 /L；
Mixing t =18min, V =365cm 3 and/L, substituting a =50% into the formula (1) to obtain v =81 times/min.
Example 11
The difference between the embodiment and the embodiment 10 is that the heating temperature of the industrial wastewater in the step 1) is 70 ℃; the time for magnetically stirring the mixed solution was 20min.
Example 12
The difference between the embodiment and the embodiment 10 is that the heating temperature of the industrial wastewater in the step 1) is 90 ℃; the time for magnetically stirring the mixed solution was 30min.
Example 13
The difference between the embodiment and the embodiment 10 is that in the step 1), 20g of polyacrylamide and 25g of sodium alginate are sequentially added into industrial wastewater; 355cm was obtained after the solid-liquid separation step 3 The sludge of (2).
Example 14
The difference between the embodiment and the embodiment 10 is that in the step 1), 30g of polyacrylamide and 15g of sodium alginate are sequentially added into the industrial wastewater; after the solid-liquid separation step, 360cm was obtained 3 The sludge of (2).
Example 15
The difference between the embodiment and embodiment 10 is that in the step 2), the time for introducing the mixed gas is 15min;
mixing t =15min, V =365cm 3 and/L, substituting a =50% into the formula (1) to obtain v =97 times/min.
Example 16
The difference between the embodiment and the embodiment 10 is that in the step 2), the time for introducing the mixed gas is 20min;
mixing t =20min, V =365cm 3 and/L, substituting a =50% into the formula (1) to obtain v =73 times/min.
Example 17
The difference between the embodiment and the embodiment 10 is that in the step 2), the volume of the mixed gas accounts for 40 percent of the volume of the sludge,
the sum of t =18min is compared with the sum of t =18min,V＝365cm 3 and/L, substituting a =60% into the formula (1) to obtain v =65 times/min.
Example 18
The difference between the embodiment and the embodiment 10 is that in the step 2), the volume of the mixed gas accounts for 60 percent of the volume of the sludge,
mixing t =18min, V =365cm 3 and/L, substituting a =60% into the formula (1) to obtain v =97 times/min.
Example 19
The difference between the embodiment and the embodiment 10 is that, in the step 2), the mixed gas includes 90% by mass of ozone, 5% by mass of helium, and 5% by mass of sulfuryl fluoride.
Example 20
The difference between this embodiment and embodiment 10 is that, in step 2), the mixed gas includes, by mass, 95% of ozone, 3% of helium, and 2% of sulfuryl fluoride.
Examples of the experiments
Aiming at the treatment method of the industrial wastewater containing high-concentration copper and glycine in each embodiment, the extraction rates of the method for the copper and the glycine in the industrial wastewater are respectively tested, and the following specific researches are carried out:
1. the influence of different concentrations of oxalic acid solution on copper and glycine in industrial wastewater is explored.
The results of experimental comparisons of examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1 below:
TABLE 1 tables of extraction rates of examples 1 to 3 and comparative examples 1 to 3 for copper and glycine
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Copper (Cu) | 90％ | 38％ | 76％ | 55％ | 76％ | 84％ |
| Glycine | 98％ | 40％ | 81％ | 62％ | 80％ | 87％ |
Comparative example 1: the concentration of the oxalic acid solution is 1mol/L; comparative example 2: the concentration of the oxalic acid solution is 1.5mol/L; comparative example 3: the concentration of the oxalic acid solution is 2.5mol/L;
from the results in table 1, it can be seen that different concentrations of oxalic acid solution have certain influence on the extraction of copper and glycine from industrial wastewater, and as the concentration of oxalic acid solution increases, the extraction rate of the oxalic acid solution to copper and glycine increases nonlinearly, but starts to decrease after reaching the peak value, so the comparison with fig. 1 shows that the extraction rate of the oxalic acid solution concentration to copper and glycine in example 1 is the highest.
2. The influence of different volume ratios of the oxalic acid solution and the industrial wastewater on copper and glycine in the industrial wastewater is researched.
The results of experimental comparisons of examples 1 and 4-5, and comparative examples 4-7 are shown in Table 2 below:
TABLE 2 extraction rates of copper and glycine from industrial wastewater of examples 1 and 4-5, and comparative examples 4-7
Comparative example 4: the volume of the industrial wastewater is unchanged, and the volume ratio of the oxalic acid solution to the industrial wastewater is 1:1.5; comparative example 5: the volume of the industrial wastewater is unchanged, and the volume ratio of the oxalic acid solution to the industrial wastewater is 1:1; comparative example 6: the volume of the industrial wastewater is unchanged, and the volume ratio of the oxalic acid solution to the industrial wastewater is 1.5:1; comparative example 7: the volume of the industrial wastewater is unchanged, and the volume ratio of the oxalic acid solution to the industrial wastewater is 2.5:1;
as can be seen from the results in table 2, different volume ratios of the oxalic acid solution to the industrial wastewater have certain influence on the extraction of copper and glycine, and in a certain volume of industrial wastewater, the extraction rates of the oxalic acid solution to copper and glycine reach peak values when the volume ratio of the oxalic acid solution to the industrial wastewater is 2.
3. In the third step, the influence of different heating parameters on copper and glycine in the industrial wastewater is researched.
The results of experimental comparisons of example 1 and examples 6-7 are shown in Table 3 below:
table 3 extraction rates of copper and glycine in industrial wastewater of example 1 and examples 6 to 7
| Example 1 | Example 6 | Example 7 | |
| Copper (Cu) | 90％ | 85％ | 89％ |
| Glycine | 98％ | 92％ | 97％ |
As can be seen from the results in table 3, the difference in the heating parameters in the third step has a certain influence on the extraction rates of copper and glycine in the industrial wastewater, when the heating temperature is increased and the heating time is prolonged, the extraction rates of the oxalic acid solution on copper and glycine are decreased after reaching the maximum, and the comparison shows that the extraction rates of the heating parameters in example 1 on copper and glycine are the highest.
4. And (3) researching the influence of the difference of the heating parameters in the first step and the second step on the copper and the glycine in the industrial wastewater.
The results of experimental comparisons of example 1 and examples 8-9 are shown in Table 4 below:
table 4 extraction of copper and glycine from industrial wastewater in examples 1 and 8 to 9
| Example 1 | Example 8 | Example 9 | |
| Copper (Cu) | 90.1％ | 84.9％ | 90.2％ |
| Glycine | 98.6％ | 93.5％ | 98.8％ |
From the results in table 4, it can be seen that the difference in the heating parameters in the first and second steps has a certain effect on the extraction rate of copper and glycine in the industrial wastewater, and compared to example 1, the extraction rate of copper and glycine in example 9 is relatively higher, and the heating temperature required for example 9 is also relatively higher, but the difference from example 1 is small, so the effect of example 1 is relatively better from the viewpoint of production cost and the like.
5. The influence of heating and stirring parameters on copper and glycine in the industrial wastewater during pretreatment of the industrial wastewater is explored.
The results of experimental comparisons of example 1 and examples 10-12 are shown in Table 5 below:
TABLE 5 extraction of copper and glycine from industrial waste water in examples 1 and 10-12
| Example 1 | Example 10 | Example 11 | Example 12 | |
| Copper (Cu) | 90.1％ | 93.5％ | 92.0％ | 93.6％ |
| Glycine | 98.6％ | 99.7％ | 99.1％ | 99.8％ |
From the results of table 5, it is understood that the heating and stirring parameters in the pretreatment of the industrial wastewater have a certain influence on the extraction rate of copper and glycine in the industrial wastewater, and compared with example 1, the extraction rate of copper and glycine in example 12 is relatively higher, but the heating temperature required for example 12 is relatively higher, and the difference from example 1 is small overall, so the effect of example 1 is relatively better from the viewpoint of production cost and the like.
6. The influence of the addition of sodium alginate and polyacrylamide on the volume of sludge in the pretreatment of industrial wastewater is explored.
The results of experimental comparisons of example 1, examples 10, 13-14 and controls 8-9 are shown in Table 6 below:
TABLE 6 influence of examples 1, 10, 13-14 and comparative examples 8-9 on the volume of sludge
Comparative example 8: the difference from the embodiment 10 is that under the condition that other conditions are not changed, sodium alginate is not added in the step 1), and the addition amount of polyacrylamide is 45g; after the solid-liquid separation step, 330cm was obtained 3 The sludge of (2);
comparative example 9: the difference from the embodiment 10 is that under the condition that other conditions are not changed, polyacrylamide is not added in the step 1), and the addition amount of sodium alginate is 45g; obtaining 340cm after the solid-liquid separation step 3 The sludge of (2);
from the results of Table 6, it is understood that the effect of example 10 is relatively superior in comparison with example 10 because the amount of sludge obtained is less than that of example 10 in the absence of sodium alginate or polyacrylamide.
7. The influence of the introduction time of the mixed gas on the copper and the glycine in the industrial wastewater in the pretreatment of the industrial wastewater is researched.
The results of experimental comparisons of example 1, examples 10, 15-16, and comparative examples 10-11 are shown in Table 7 below:
TABLE 7 extraction rates of copper and glycine in industrial wastewater of example 1, examples 10, 15 to 16, and comparative examples 10 to 11
Comparative example 10 differs from example 15 in that the mixed gas was passed through for 15min and the beating rate was maintained at 81 times/min under otherwise unchanged conditions; the hammering speed is faster than that calculated by the formula (1), but the effect is not greatly enhanced, so that the improvement of the hammering speed is more power consumption, the economy is not good, and the effect of the embodiment 15 is better in comparison;
comparative example 11 differs from example 16 in that the aeration time of the mixed gas was 20min and the beating rate was maintained at 81 times/min under otherwise unchanged conditions; the hammering rate was slower than that calculated by equation (1), and did not achieve the effect of the hammering rate of example 16, so example 16 was more effective than it was;
from the above results of table 7, it can be seen that, in the pretreatment of industrial wastewater, the introduction time of the mixed gas has a certain influence on the extraction rate of copper and glycine in the industrial wastewater, the introduction time of the mixed gas affects the speed of uniformly beating the sludge, and the excessively fast or excessively slow speed of uniformly beating can reduce the extraction rate of the oxalic acid solution on copper and glycine in the industrial wastewater, so that the comparison shows that the effect of example 10 is optimal.
8. The influence of the introduced volume of the mixed gas on the copper and the glycine in the industrial wastewater in the pretreatment of the industrial wastewater is explored.
The results of experimental comparisons of example 1, examples 10, 17-18, and comparative examples 12-13 are shown in Table 8 below:
TABLE 8 extraction rates of copper and glycine in industrial wastewater of example 1, examples 10, 17 to 18, and comparative examples 12 to 13
Comparative example 12 differs from example 17 in that the volume of the mixed gas accounted for 40% of the volume of the sludge, with the beating rate still remaining at 81 times/min, under otherwise unchanged conditions; the hammering rate was faster than that calculated by the formula (1), but the effect was not further enhanced, so increasing the hammering rate was more power consumed and the economy was not good, so example 17 was more effective than comparative;
comparative example 13 differs from example 18 in that the volume of the mixed gas was 60% of the volume of the sludge under otherwise unchanged conditions, and the beating rate was maintained at 81 times/min; the tapping rate was slower than that calculated by equation (1), and did not achieve the effect of the tapping rate of example 18, so example 18 was more effective than it was;
from the above results of table 8, it can be seen that, in the pretreatment of industrial wastewater, the introduced volume of the mixed gas has a certain influence on the extraction rate of copper and glycine in industrial wastewater, and it can be seen that when the introduced volume of the mixed gas is decreased or increased, the speed of uniformly beating sludge is affected, and that the too fast or too slow speed of uniformly beating reduces the extraction rate of copper and glycine in industrial wastewater by the oxalic acid solution, so that the effect of example 10 is optimal by comparison.
9. The influence of the proportion relation of the mixed gas components on the copper and the glycine in the industrial wastewater in the pretreatment of the industrial wastewater is explored.
The results of experimental comparisons of example 1, examples 10, 19-20 and control 14 are shown in Table 9 below:
table 9 examples 1, 10, 19 to 20 and comparative example 14 extraction ratio of copper and glycine from industrial wastewater
Comparative example 14 is different from example 10 in that the mixed gas includes 93% by mass of ozone and 7% by mass of helium, under the same conditions;
from the results in Table 9, it can be seen that the gas mixture ratio in the pretreatment of industrial wastewater has a certain influence on the extraction rates of copper and glycine, and the comparison in comparative example 14 shows that the extraction rates of copper and glycine from the oxalic acid solution are reduced in the absence of sulfuryl fluoride compared with those of examples 10, 19 to 20, and thus it can be seen that the gas mixture ratio in example 10 has a relatively higher extraction rate of copper and glycine.
Claims (9)
1. A treatment method for industrial wastewater containing high-concentration copper and glycine is characterized by comprising the following steps:
1. and (3) vein breaking treatment:
heating an oxalic acid solution prepared in a container until oxalic acid crystals in the oxalic acid solution are completely dissolved to obtain an oxalic acid dissolved solution, and mixing industrial wastewater and the oxalic acid dissolved solution in proportion to obtain a first mixed solution;
2. heating treatment:
heating the first mixed solution and continuously stirring until the first mixed solution is white and turbid to obtain a second mixed solution;
3. extraction of compound copper and elemental copper:
continuously heating and continuously stirring the second mixed solution, and filtering the second mixed solution by using filter paper to obtain blue precipitate and filtrate, wherein the blue precipitate is compound copper, and red elemental copper is attached to the bottom of the container;
4. and (3) extraction of glycine:
and naturally cooling the filtrate to room temperature, and separating out white crystals, wherein the white crystals are glycine.
2. The method for treating the industrial wastewater containing high-concentration copper and glycine as claimed in claim 1, wherein in the first step, the concentration of the oxalic acid solution is 0.5-3 mol/L.
3. The method for treating the industrial wastewater containing high-concentration copper and glycine according to claim 1, wherein in the step one, the volume of the industrial wastewater is unchanged, and the volume ratio of the oxalic acid solution to the industrial wastewater is (0.5-3): 1.
4. the method for treating the industrial wastewater containing high-concentration copper and glycine as claimed in claim 1, wherein in the third step, the second mixed solution is heated and stirred at a temperature of 55-65 ℃ for 5-10 min.
5. The method for treating the industrial wastewater containing high concentration of copper and glycine as claimed in claim 1, wherein the heating of the first step, the heating of the second step and the heating of the third step and the continuous stirring are all performed by a magnetic heater.
6. The method for treating the industrial wastewater containing the high-concentration copper and the glycine as claimed in claim 1, wherein the heating temperature of the oxalic acid solution in the first step is 45-55 ℃.
7. The method for treating the industrial wastewater containing high-concentration copper and glycine as claimed in claim 1, wherein the heating temperature of the first mixed solution in the second step is 55-65 ℃.
8. The method for treating the industrial wastewater containing high concentration of copper and glycine as claimed in claim 1, wherein the filtration in the third step is filter paper filtration.
9. The treatment method for the industrial wastewater containing high-concentration copper and glycine as claimed in claim 1, wherein the industrial wastewater is pretreated before being mixed with the oxalic acid dissolving solution, and the pretreatment method comprises the following steps:
1) Heating x L industrial wastewater to 70-90 ℃, sequentially adding 20-30 g/L polyacrylamide and 15-25 g/L sodium alginate into the industrial wastewater to obtain a mixed solution, magnetically stirring the mixed solution for 20-30 min, and then carrying out solid-liquid separation to obtain an industrial wastewater stock solution and y cm 3 The sludge of (2);
2) Beating the sludge at a constant speed by using a cylindrical rod with the diameter of n cm, and introducing mixed gas into the sludge, wherein the introduction time of the mixed gas is 15-20 min, the volume of the mixed gas accounts for 40-60% of the volume of the sludge, and the mixed gas comprises 90-95% of ozone, 3-5% of helium and 2-5% of sulfuryl fluoride by mass percentage to obtain activated sludge; the speed of uniformly beating the sludge and the volume of the sludge meet a formula (1), the volume of the sludge and the volume of the industrial wastewater meet a formula (2), the diameter of the cylindrical rod and the volume of the sludge meet a formula (3),
wherein v is the speed of uniform beating, and the unit is taken once/min; t is the time for introducing the mixed gas, and the unit is min; v is the volume ratio of the volume of the sludge to the volume of the wastewater, and the unit is cm 3 L; a is the volume percentage of the volume of the mixed gas in the volume of the sludge, y is the volume of the sludge, x is the volume of the industrial wastewater, and n is the diameter of the cylindrical rod;
3) And mixing the mixed sludge and the industrial wastewater stock solution, uniformly stirring to obtain pretreated industrial wastewater, and then mixing the pretreated industrial wastewater with the oxalic acid dissolving solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060278583A1 (en) * | 2003-07-29 | 2006-12-14 | Hung-Yuan Hsiao | Method for recycling sludge during waste-water treatment |
| CN106442607A (en) * | 2016-08-31 | 2017-02-22 | 河北科技大学 | Method for controlling temperature of glycine cooling crystallization crystal point |
| CN111394587A (en) * | 2020-04-26 | 2020-07-10 | 郑州大学 | Method for leaching copper from acid-washed copper slag of zinc hydrometallurgy |
| CN111455188A (en) * | 2020-04-26 | 2020-07-28 | 郑州大学 | Process method for leaching copper from matte slag by alkaline wet method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060278583A1 (en) * | 2003-07-29 | 2006-12-14 | Hung-Yuan Hsiao | Method for recycling sludge during waste-water treatment |
| CN106442607A (en) * | 2016-08-31 | 2017-02-22 | 河北科技大学 | Method for controlling temperature of glycine cooling crystallization crystal point |
| CN111394587A (en) * | 2020-04-26 | 2020-07-10 | 郑州大学 | Method for leaching copper from acid-washed copper slag of zinc hydrometallurgy |
| CN111455188A (en) * | 2020-04-26 | 2020-07-28 | 郑州大学 | Process method for leaching copper from matte slag by alkaline wet method |
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