CN115231754B - 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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- CN115231754B CN115231754B CN202210891915.0A CN202210891915A CN115231754B CN 115231754 B CN115231754 B CN 115231754B CN 202210891915 A CN202210891915 A CN 202210891915A CN 115231754 B CN115231754 B CN 115231754B
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 121
- 239000010949 copper Substances 0.000 title claims abstract description 98
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 94
- 239000004471 Glycine Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- 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 216
- 235000006408 oxalic acid Nutrition 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 59
- 239000010802 sludge Substances 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 36
- 238000010009 beating Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 18
- 239000002351 wastewater Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 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
- 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
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 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
- 238000004090 dissolution Methods 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
- 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
- 210000003462 vein Anatomy 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013049 sediment Substances 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
- 238000000605 extraction Methods 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 31
- 230000000694 effects Effects 0.000 description 27
- 229910001385 heavy metal Inorganic materials 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate 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
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000010865 sewage Substances 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
- 239000003513 alkali Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002329 infrared spectrum 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
- 229910000510 noble metal Inorganic materials 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
- 238000004064 recycling Methods 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 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
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a treatment method for industrial wastewater containing high-concentration copper and glycine, which comprises the following steps: 1. breaking collaterals; 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, and can maximally extract copper and glycine in industrial wastewater, thereby realizing waste regeneration and resource utilization.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating industrial wastewater containing high-concentration copper and glycine.
Background
The heavy metal wastewater becomes one of the main environmental pollution problems to be solved urgently, and has certain complexity for treating industrial heavy metal wastewater because of complex components of the heavy metal wastewater and great treatment difficulty. With the development of the chemical industry, the use amount of heavy metals by human beings is continuously increased, so that heavy metal pollution is also increased. The emission of heavy metal wastewater does not reach the standard, so that not only can metal resources be wasted and economic benefits are affected, but also serious harm is caused to ecological environment.
The heavy metal wastewater has large water quantity, complex water quality and difficult control of components, and contains chromium, copper, nickel, zinc and other heavy metal ions with high toxicity, wherein part of heavy metal ions belong to cancerogenic, teratogenic and mutagenic virulent substances, and the heavy metal ions have great harm to human beings. Heavy metal wastewater is one of the wastewater with the most serious environmental pollution and the greatest harm to human beings, and after the heavy metal wastewater is discharged into natural water, the heavy metal can remain, accumulate and migrate in the natural water in various chemical states or chemical forms, thereby causing harm. The traditional treatment method is adopted to treat the wastewater, and the problems of poor water quality, high treatment process cost, difficult recovery of noble metals and the like exist in the treated wastewater. The alkali precipitation has the advantages of low price, easy control of dosage and the like, however, the method has poor effect of treating the industrial wastewater containing the complex copper, and the treated wastewater can not reach the wastewater discharge standard. Meanwhile, in the aspect of treating heavy metal wastewater, not only is the environment treatment goal of efficiently extracting heavy metal sought, but also the environmental economic benefit goal of higher level such as avoiding secondary pollution and fully recycling valuable resources is also sought.
Therefore, there is a need for a treatment process for industrial wastewater containing high concentrations of copper and glycine to increase the extraction of heavy metals.
Disclosure of Invention
In order to solve the technical problems, the invention provides a treatment method for industrial wastewater containing high-concentration copper and glycine.
The technical scheme of the invention is as follows: a method for treating industrial wastewater containing high-concentration copper and glycine, which comprises the following steps:
step one, vein breaking treatment:
heating the oxalic acid solution prepared in the container until oxalic acid crystals in the oxalic acid solution are completely dissolved to obtain oxalic acid solution, and mixing industrial wastewater with the oxalic acid solution in proportion to obtain a first mixed solution;
step two, 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;
step three, extracting compound copper and elemental copper:
continuously heating and continuously stirring the second mixed solution, and filtering the second mixed solution to obtain a blue precipitate and filtrate, wherein the blue precipitate is compound copper, and red elemental copper is attached to the bottom of the container;
step four, extracting glycine:
naturally cooling the filtrate to room temperature, and separating out to obtain 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 facilitate the determination of the optimal working concentration of the oxalic acid solution, thereby determining the highest extraction rate of the oxalic acid solution for copper and glycine in 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 volume ratio is selected to facilitate determination of the optimal addition of oxalic acid solution, thereby determining the highest extraction rate of oxalic acid solution for copper and glycine in industrial wastewater.
In the third step, when the second mixed solution is heated and stirred, the heating temperature is 55-65 ℃ and the heating time is 5-10 min. The heating parameter selection can separate out more compound copper and simple substance copper, and the obtained compound copper and simple substance copper are not easy to extract due to the excessively high or excessively low temperature.
Further, the heating in the first step, the heating in the second step and the third step and the continuous stirring are all completed by adopting a magnetic heater. The magnetic heater can enable the dissolution degree of oxalic acid crystals to be more complete under the action of a magnetic field, and enables oxalic acid dissolution liquid and industrial wastewater to be mixed more uniformly under the magnetic stirring, so that the oxalic acid dissolution liquid and the industrial wastewater can be reacted more completely, and more compounds copper and glycine are obtained.
Further, in the first step, the heating temperature of the oxalic acid solution is 45-55 ℃. The selection of the parameters enables the oxalic acid crystal to be dissolved more completely, so that the purity of the obtained oxalic acid dissolving solution is higher.
Further, in the second step, the heating temperature of the first mixed solution is 55-65 ℃. The selection of the parameters enables the industrial wastewater to be mixed with the oxalic acid dissolving solution more uniformly, enables the oxalic acid dissolving solution to react with copper and glycine more completely, and accordingly improves the extraction efficiency of the oxalic acid dissolving solution on the copper and glycine.
Further, the filtering mode in the third step is filter paper filtering. The filter paper has excellent drainage performance, loose paper quality and strong absorption to liquid, and can separate sediment from liquid well.
Further, the industrial wastewater is pretreated before being mixed with oxalic acid dissolution liquid, 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 Is a sludge of (2);
2) The method comprises the steps of beating 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 introducing 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 percent to obtain activated sludge; the constant-speed beating speed and the sludge volume meet the formula (1), the volume of the sludge and the volume of the industrial wastewater meet the formula (2), the diameter of the cylindrical rod and the volume of the sludge meet the formula (3),
wherein v is the constant-speed beating rate, and the unit is taken for times/min; t is the time of 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 to 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 and uniformly stirring the activated sludge and the industrial wastewater stock solution 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 is provided with innumerable air holes, the air holes with larger diameters in the sludge are dispersed into tiny air holes through uniform-speed beating, the contact area with mixed gas is increased, and therefore the combination effect with the mixed gas is improved, and the obtained activated sludge has good catalytic performance.
The beneficial effects of the invention are as follows:
(1) The method utilizes oxalic acid solution to perform vein breaking treatment on copper and glycine in industrial wastewater, can effectively extract copper in high-concentration complex copper wastewater, can effectively recover glycine component in wastewater, is simple to operate, does not need to additionally adjust pH, and is suitable for treating industrial wastewater containing high-concentration copper and glycine in large and medium-sized factories.
(2) According to the invention, the activated sludge is obtained by pretreatment of the industrial wastewater, so that the catalytic performance of the activated sludge is enhanced, the vein breaking effect of oxalic acid solution on copper and glycine in the industrial wastewater is enhanced, and the vein breaking treatment efficiency is improved.
Drawings
FIG. 1 is a graph showing the comparison of oxalic acid concentrations versus copper extraction rates in the present invention;
FIG. 2 is a graph showing the comparison of copper extraction rates with different volume ratios of industrial wastewater to oxalic acid in the present invention;
FIG. 3 is a diagram of the mixed solution obtained in the first step of example 1;
FIG. 4 is a graph of a white cloudy mixed solution obtained by the treatment in step two of example 1;
FIG. 5 is a graph showing the actual effect of copper oxalate obtained by the filtration in step three of example 1;
FIG. 6 is a graph showing glycine effects obtained by the treatment in step four of example 1;
FIG. 7 is an infrared spectrum obtained by infrared measurement of white crystals in the present invention;
FIG. 8 is the residual amount of copper in industrial wastewater in example 1;
FIG. 9 is the residual amount of glycine in industrial wastewater in example 1.
Detailed Description
The invention will be described in further detail with reference to the following embodiments to better embody the advantages of the invention.
Example 1
A method for treating industrial wastewater containing high-concentration copper and glycine, which comprises the following steps:
step one, 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 industrial wastewater with the oxalic acid solution according to the proportion of 1:2, mixing the industrial wastewater in a proportion of 1L to obtain a first mixed solution;
step two, 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 ℃;
step three, extracting compound copper and elemental copper:
continuously heating the second mixed solution at 60 ℃ for 8min and continuously stirring, filtering the second mixed solution by using filter paper, wherein the blue precipitate is compound copper, the compound copper is copper oxalate, and red elemental copper is attached to the bottom of the container;
step four, extracting glycine:
naturally cooling the filtrate to room temperature, and separating out to obtain white crystals, wherein the white crystals are glycine.
Example 2
This example differs from example 1 in that in the first step, the concentration of the oxalic acid solution is 0.5mol/L.
Example 3
This example differs from example 1 in that in the first step, the concentration of the oxalic acid solution is 3mol/L.
Example 4
The difference between this example and example 1 is that 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 1:2.
example 5
The difference between this example and example 1 is that in the first step, the volume of the industrial wastewater is unchanged, and the volume ratio of oxalic acid to industrial wastewater is 3:1.
example 6
The difference between this example and example 1 is that in the third step, the heating temperature is 55 ℃ and the heating time is 10min when the mixed solution is heated and stirred.
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
This example differs from example 1 in that in the first step, 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
This example differs from example 1 in that in the first step, 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
This example differs from example 1 in that the industrial wastewater is subjected to pretreatment before being mixed with the oxalic acid dissolution liquid, the pretreatment method being as follows:
1) Heating 1L of industrial wastewater to 80 ℃, sequentially adding 25g of polyacrylamide and 20g of sodium alginate into the industrial wastewater to obtain a mixed solution, magnetically stirring the mixed solution for 25min, and then carrying out solid-liquid separation to obtain an industrial wastewater stock solution and 365cm 3 Is a sludge of (2);
2) The method comprises the steps of beating sludge at a constant speed by using a cylindrical rod with the diameter of 3.65cm, and simultaneously introducing mixed gas into the sludge, wherein the introducing 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 by mass percent to obtain activated sludge; the constant-speed beating speed and the sludge volume meet the formula (1), the volume of the sludge and the volume of the industrial wastewater meet the formula (2), the diameter of the cylindrical rod and the volume of the sludge meet the formula (3),
wherein v is the constant-speed beating rate, and the unit is taken for times/min; t is the time of 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 to 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 and uniformly stirring the activated sludge and the industrial wastewater stock solution to obtain pretreated industrial wastewater, and then mixing the pretreated industrial wastewater with the oxalic acid dissolving solution;
y=365 cm 3 Substituting the formula (3) to obtain n=7.3 cm;
y=365 cm 3 X=1l is substituted into the above formula (2), to obtain v=365 cm 3 /L；
Let t=18 min, v=365 cm 3 and/L, substituting a=50% into the formula (1) to obtain v=81 times/min.
Example 11
The present example is different from example 10 in that the heating temperature of the industrial wastewater in the step 1) is 70 ℃; the magnetic stirring time of the mixed solution is 20min.
Example 12
The difference between this example and example 10 is that the heating temperature of the industrial wastewater in the step 1) is 90 ℃; the magnetic stirring time of the mixed solution is 30min.
Example 13
The difference between this example and example 10 is that in the above-mentioned step 1), 20g of polyacrylamide and 25g of sodium alginate are added into the industrial wastewater in sequence; after the solid-liquid separation step, 355cm of a solid-liquid mixture was obtained 3 Is a sludge of (a) a sewage treatment plant.
Example 14
The difference between this example and example 10 is that in the above-mentioned step 1), 30g of polyacrylamide and 15g of sodium alginate are added into the industrial wastewater in sequence; after the solid-liquid separation step, 360cm of solid-liquid separation was obtained 3 Is a sludge of (a) a sewage treatment plant.
Example 15
The difference between this embodiment and embodiment 10 is that in the step 2), the introducing time of the mixed gas is 15min;
let t=15min, v=365 cm 3 and/L, substituting a=50% into the formula (1), and obtaining v=97 times/min.
Example 16
The difference between this embodiment and embodiment 10 is that in the step 2), the introducing time of the mixed gas is 20min;
let t=20min, v=365 cm 3 and/L, substituting a=50% into the formula (1), and obtaining v=73 times/min.
Example 17
This example differs from example 10 in that, in step 2), the volume of the mixed gas is 40% of the volume of the sludge,
let t=18 min, v=365 cm 3 and/L, substituting a=60% into the formula (1), and obtaining v=65 times/min.
Example 18
This example differs from example 10 in that, in step 2), the volume of the mixed gas is 60% of the volume of the sludge,
let t=18 min, v=365 cm 3 and/L, substituting a=60% into the formula (1), and obtaining v=97 times/min.
Example 19
This example is different from example 10 in that in the step 2), the mixed gas includes 90% ozone, 5% helium and 5% sulfuryl fluoride by mass.
Example 20
This example is different from example 10 in that in the step 2), the mixed gas includes ozone, helium, and sulfuryl fluoride in an amount of 95% by mass, 3% by mass, and 2% by mass.
Experimental example
Aiming at the treatment methods of the industrial wastewater containing high-concentration copper and glycine in each embodiment, the extraction rates of the method of the invention on the copper and glycine in the industrial wastewater are respectively tested, and the specific exploration is as follows:
1. the effect of different concentrations of oxalic acid solution on copper and glycine in industrial wastewater was investigated.
The results of the experiments were shown in Table 1 below, with examples 1-3 and comparative examples 1-3 as experimental comparisons:
TABLE 1 extraction rates of copper and glycine for examples 1-3 and comparative examples 1-3
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Copper (Cu) | 90％ | 38％ | 76％ | 55％ | 76％ | 84％ |
| Glycine (Gly) | 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 of table 1, it can be seen that different oxalic acid solution concentrations have a certain effect on the extraction of copper and glycine from industrial wastewater, and as the concentration of oxalic acid solution increases, the extraction rate of copper and glycine from oxalic acid solution increases in a nonlinear manner, but begins to decrease after reaching a peak value, so that it can be seen that the concentration of oxalic acid solution in example 1 has the highest extraction rate of copper and glycine in comparison with fig. 1.
2. The influence of different volume ratios of oxalic acid solution to industrial wastewater on copper and glycine in the industrial wastewater is explored.
With examples 1 and 4-5 and comparative examples 4-7 as experimental comparisons, the results are shown in Table 2 below:
TABLE 2 extraction rates of copper and Glycine from Industrial wastewater for examples 1 and 4-5, 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, a step of; 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, a step of; 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, a step of;
as is clear from the results of table 2, the different volume ratios of the oxalic acid solution to the industrial wastewater have a certain effect on the extraction of copper and glycine, and in a certain volume of industrial wastewater, the extraction rate of the oxalic acid solution to copper and glycine reaches the peak value at the volume ratio of the oxalic acid solution to industrial wastewater of 2:1, and when more oxalic acid solution is continuously added, the extraction rate of the oxalic acid solution to copper and glycine is reduced, so that the comparison of fig. 2 shows that the extraction rate of the oxalic acid solution to copper and glycine is the highest.
3. In the third step, the influence of the difference of heating parameters on copper and glycine in industrial wastewater is explored.
The results of the experiments conducted in example 1 and examples 6 to 7 are shown in Table 3 below:
TABLE 3 extraction of copper and Glycine from Industrial wastewater from example 1, examples 6-7
| Example 1 | Example 6 | Example 7 | |
| Copper (Cu) | 90％ | 85％ | 89％ |
| Glycine (Gly) | 98％ | 92％ | 97％ |
As is clear from the results of Table 3, the difference of the heating parameters in the third step has a certain influence on the extraction rate of copper and glycine in the industrial wastewater, and when the heating temperature is increased and the heating time is prolonged, the extraction rate of oxalic acid solution on copper and glycine is reduced after reaching the highest, and the comparison shows that the heating parameters of example 1 have the highest extraction rate of copper and glycine.
4. The influence of the difference of the heating parameters in the first step and the second step on copper and glycine in industrial wastewater is explored.
The results of the experiments conducted in example 1 and examples 8 to 9 are shown in Table 4 below:
TABLE 4 extraction of copper and Glycine from Industrial wastewater from example 1, examples 8-9
| Example 1 | Example 8 | Example 9 | |
| Copper (Cu) | 90.1％ | 84.9％ | 90.2％ |
| Glycine (Gly) | 98.6％ | 93.5％ | 98.8％ |
As is clear from the results of table 4, the difference in heating parameters in the first and second steps has a certain effect on the extraction rate of copper and glycine from the industrial wastewater, and the effect of example 1 is relatively better from the standpoint of production cost and the like because the extraction rate of copper and glycine is relatively higher in example 9 and the heating temperature required in example 9 is also relatively higher than in example 1.
5. In the pretreatment of industrial wastewater, the influence of heating and stirring parameters on copper and glycine in the industrial wastewater is explored.
The results of the experiments conducted in example 1 and examples 10 to 12 are shown in Table 5 below:
TABLE 5 extraction of copper and Glycine from Industrial wastewater from example 1, examples 10-12
| Example 1 | Example 10 | Example 11 | Example 12 | |
| Copper (Cu) | 90.1％ | 93.5％ | 92.0％ | 93.6％ |
| Glycine (Gly) | 98.6％ | 99.7％ | 99.1％ | 99.8％ |
As is clear from the results of Table 5, in the pretreatment of industrial wastewater, the heating and stirring parameters have a certain influence on the extraction rate of copper and glycine in industrial wastewater, and the extraction rate of copper and glycine in example 12 is relatively higher than that in example 1, but the heating temperature required in example 12 is also relatively higher, and the difference between the whole and example 1 is small, so that the effect of example 1 is relatively better from the viewpoint of production cost and the like.
6. In pretreatment of industrial wastewater, the influence of the addition amount of sodium alginate and polyacrylamide on the volume of sludge is explored.
The results of the experiment were shown in Table 6 below, using example 1, examples 10, 13 to 14 and comparative examples 8 to 9 as experimental comparisons:
TABLE 6 influence of example 1, examples 10, 13-14 and comparative examples 8-9 on sludge volume
Comparative example 8: the difference from example 10 is that sodium alginate is not added in the step 1) under the condition that other conditions are not changed, and the addition amount of polyacrylamide is 45g; after the solid-liquid separation step, 330cm of the solid-liquid mixture was obtained 3 Is a sludge of (2);
comparative example 9: the difference from example 10 is that in the case of other conditions, no polyacrylamide is added in the step 1), and the addition amount of sodium alginate is 45g; after the solid-liquid separation step, 340cm of a solid-liquid mixture was obtained 3 Is a sludge of (2);
from the results of table 6, it is found that the amount of sludge obtained is too small compared with example 10, regardless of the lack of sodium alginate or polyacrylamide, and thus the effect of example 10 is relatively superior to that of example 10.
7. In pretreatment of industrial wastewater, the influence of the introducing time of the mixed gas on copper and glycine in the industrial wastewater is explored.
The results are shown in Table 7 below, with examples 1, 10, 15-16, and comparative examples 10-11 as experimental comparisons:
TABLE 7 extraction of copper and Glycine from Industrial wastewater from example 1, examples 10, 15-16, comparative examples 10-11
The difference between comparative example 10 and example 15 is that the charging time of the mixed gas is 15min and the hammering rate is still kept at 81 times/min under the condition that other conditions are not changed; the beating rate is faster than the beating rate calculated by the formula (1), but the effect is not greatly enhanced, so that the beating rate is increased to consume more power, the economy is poor, and the effect of the embodiment 15 is better compared with the effect;
comparative example 11 is different from example 16 in that the charging time of the mixed gas was 20min and the hammering rate was maintained at 81 times/min under the condition that other conditions were not changed; the beating rate is slower than the beating rate calculated by the formula (1), and the effect of the beating rate of the embodiment 16 is not achieved, so that the effect of the embodiment 16 is better compared with the effect;
from the comprehensive analysis of the results in table 7, it is clear that in the pretreatment of industrial wastewater, the feeding time of the mixed gas has a certain influence on the extraction rate of copper and glycine in industrial wastewater, the feeding time of the mixed gas can influence the speed of beating sludge at a constant speed, and the excessive or too slow constant speed beating speed can reduce the extraction of copper and glycine in industrial wastewater by oxalic acid solution, so the effect is optimal compared with that in example 10.
8. In pretreatment of industrial wastewater, the influence of the introduced volume of the mixed gas on copper and glycine in the industrial wastewater is explored.
The results of the experiments were shown in Table 8 below, with examples 1, 10, 17 to 18 and comparative examples 12 to 13 as experimental comparisons:
TABLE 8 extraction of copper and Glycine from Industrial wastewater from example 1, examples 10, 17-18, comparative examples 12-13
Comparative example 12 is different from example 17 in that the volume of the mixed gas is 40% of the volume of the sludge under the condition that other conditions are not changed, and the hammering rate is still kept at 81 times/min; the beating rate is faster than the beating rate calculated by the formula (1), but the effect is not further enhanced, so that the beating rate is increased to consume more power, the economy is poor, and the effect of the embodiment 17 is better compared with the effect;
comparative example 13 is different from example 18 in that the volume of the mixed gas is 60% of the volume of the sludge under the condition that other conditions are not changed, and the hammering rate is still kept at 81 times/min; the beating rate is slower than the beating rate calculated by the formula (1), and the effect brought by the beating rate of the embodiment 18 is not achieved, so that the effect of the embodiment 18 is better compared with the effect;
from the comprehensive analysis of the results in table 8, it can be seen that the inflow volume of the mixed gas has a certain influence on the extraction rate of copper and glycine in the industrial wastewater in the pretreatment of the industrial wastewater, and it can be seen that the uniform speed beating rate of sludge is influenced when the inflow volume of the mixed gas is reduced or increased, and the extraction rate of copper and glycine in the industrial wastewater by the oxalic acid solution is reduced by the too fast or too slow uniform speed beating rate, so that the effect of comparative example 10 is optimal.
9. In pretreatment of industrial wastewater, the influence of the proportioning relation of the mixed gas components on copper and glycine in the industrial wastewater is explored.
The results are shown in Table 9 below, with example 1, examples 10, 19-20 and comparative example 14 as experimental comparisons:
table 9 extraction of copper and glycine from industrial wastewater from example 1, examples 10, 19-20 and comparative example 14
Comparative example 14 is different from example 10 in that the mixed gas includes 93% ozone and 7% helium by mass under the condition that other conditions are not changed;
as is clear from the results of Table 9, in the pretreatment of industrial wastewater, the ratio of the mixed gas components had a certain effect on the extraction rate of copper and glycine, and it can be seen from the comparison of comparative example 14 that the extraction rate of copper and glycine from the oxalic acid solution was reduced in the absence of sulfuryl fluoride as compared with examples 10 and 19 to 20, and thus it can be seen that the ratio of the mixed gas components of example 10 was relatively higher in the extraction rate of copper and glycine.
Claims (8)
1. A method for treating industrial wastewater containing high-concentration copper and glycine, which is characterized by comprising the following steps:
step one, vein breaking treatment:
heating the oxalic acid solution prepared in the container until oxalic acid crystals in the oxalic acid solution are completely dissolved to obtain oxalic acid solution, and mixing industrial wastewater with the oxalic acid solution in proportion to obtain a first mixed solution;
before the industrial wastewater is mixed with oxalic acid dissolution liquid, the industrial wastewater is pretreated by 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 Is a sludge of (2);
2) The method comprises the steps of beating 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 introducing 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 percent to obtain activated sludge; the constant-speed beating speed and the sludge volume meet the formula (1), the volume of the sludge and the volume of the industrial wastewater meet the formula (2), the diameter of the cylindrical rod and the volume of the sludge meet the formula (3),
wherein v is the constant-speed beating rate, and the unit is taken for times/min; t is the time of 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 to 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 and uniformly stirring the activated sludge and the industrial wastewater stock solution to obtain pretreated industrial wastewater, and then mixing the pretreated industrial wastewater with the oxalic acid dissolving solution;
step two, 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;
step three, extracting 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 sediment and filtrate, wherein the blue sediment is compound copper, and red elemental copper is attached to the bottom of the container;
step four, extracting glycine:
naturally cooling the filtrate to room temperature, and separating out to obtain white crystals, wherein the white crystals are glycine.
2. The method for treating industrial wastewater containing high-concentration copper and glycine according to 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 industrial wastewater containing high-concentration copper and glycine according to claim 1, wherein in the first step, the industrial wastewater volume is unchanged, and the volume ratio of oxalic acid solution to industrial wastewater is (0.5-3): 1.
4. the method for treating industrial wastewater containing high-concentration copper and glycine according to 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 industrial wastewater containing high concentration of copper and glycine according to claim 1, wherein the heating in the first step, the heating in the second step and the heating in the third step and the continuous stirring are all completed by using a magnetic heater.
6. The method for treating industrial wastewater containing high concentration of copper and glycine according to claim 1, wherein in the first step, the heating temperature of the oxalic acid solution is 45-55 ℃.
7. The method for treating industrial wastewater containing high concentration of copper and glycine according to claim 1, wherein in the second step, the heating temperature of the first mixed solution is 55-65 ℃.
8. The method for treating industrial wastewater containing high concentration of copper and glycine according to claim 1, wherein the filtering mode in the third step is filter paper filtering.
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| 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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| CN111394587A (en) * | 2020-04-26 | 2020-07-10 | 郑州大学 | Method for leaching copper from acid-washed copper slag of zinc hydrometallurgy |
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