CN117247124A - Intelligent treatment method and treatment system for copper-containing etching waste liquid - Google Patents
Intelligent treatment method and treatment system for copper-containing etching waste liquid Download PDFInfo
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- CN117247124A CN117247124A CN202311496408.8A CN202311496408A CN117247124A CN 117247124 A CN117247124 A CN 117247124A CN 202311496408 A CN202311496408 A CN 202311496408A CN 117247124 A CN117247124 A CN 117247124A
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- waste liquid
- etching waste
- containing etching
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- 239000007788 liquid Substances 0.000 title claims abstract description 483
- 239000002699 waste material Substances 0.000 title claims abstract description 451
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 408
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 408
- 239000010949 copper Substances 0.000 title claims abstract description 404
- 238000005530 etching Methods 0.000 title claims abstract description 384
- 238000000034 method Methods 0.000 title claims abstract description 88
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 115
- 238000003756 stirring Methods 0.000 claims abstract description 98
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 53
- 239000006228 supernatant Substances 0.000 claims abstract description 53
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 52
- 230000008569 process Effects 0.000 claims abstract description 38
- 238000001556 precipitation Methods 0.000 claims abstract description 30
- 238000007781 pre-processing Methods 0.000 claims abstract description 12
- 238000005273 aeration Methods 0.000 claims description 93
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 82
- 238000012545 processing Methods 0.000 claims description 70
- 230000003472 neutralizing effect Effects 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 43
- 238000012937 correction Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001514 detection method Methods 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000004422 calculation algorithm Methods 0.000 claims description 6
- 238000012797 qualification Methods 0.000 claims description 3
- 239000002801 charged material Substances 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 86
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000004364 calculation method Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 23
- 239000002253 acid Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000003513 alkali Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000523 sample Substances 0.000 description 10
- 238000004590 computer program Methods 0.000 description 9
- -1 hydroxyl ions Chemical class 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229960004643 cupric oxide Drugs 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000008713 feedback mechanism Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000752 ionisation method Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F7/00—Aeration of stretches of water
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The embodiment of the invention relates to the technical field of chemical industry, and discloses an intelligent treatment method and a treatment system for copper-containing etching waste liquid, wherein the method comprises the following steps: if the volume ratio relation between the waste liquid and the alkaline neutralization solution exists, preprocessing the waste liquid to enable the potential value to reach a specified threshold value, adding the alkaline neutralization solution into the waste liquid according to the volume ratio relation, stirring and aerating the waste liquid in sequence, adding the waste liquid into the waste liquid according to the calculated secondary adding amount of the alkaline neutralization solution if the PH value of the supernatant liquid of the waste liquid is not in a qualified threshold value range, and confirming that the waste liquid treatment process is finished if the PH value of the supernatant liquid is in the qualified threshold value range after the secondary stirring treatment of the waste liquid; if the volume ratio relation does not exist, calculating a target PH value required by metal hydroxide precipitation of the waste liquid, calculating the volume ratio relation according to an acid-base volume ratio formula, and executing the operation of pretreatment of the waste liquid. By implementing the embodiment of the invention, more accurate pH adjustment can be realized.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to an intelligent treatment method and system for copper-containing etching waste liquid.
Background
Copper-containing etching waste liquid is one of the common waste liquids in the industries of electronics, semiconductors, photovoltaics and the like. These waste solutions often contain high concentrations of copper ions, are strongly acidic and highly toxic, pose serious environmental pollution and health risks.
To solve this problem, various neutralization treatment methods have been developed for treating copper-containing etching waste liquid, which aim to convert copper ions in the waste liquid into harmless or recyclable form, while adjusting the pH of the waste liquid to achieve the neutralization effect.
However, in practice, it has been found that the conventional method for neutralizing the copper-containing etching waste liquid is that an operator gradually adds an acid or a base to reach a desired pH range according to experience or test results, and this method requires manual monitoring and control, which is inefficient and may have some error.
Disclosure of Invention
The embodiment of the invention discloses an intelligent treatment method and a treatment system for copper-containing etching waste liquid, which can realize more accurate pH adjustment.
The first aspect of the embodiment of the invention discloses an intelligent treatment method of copper-containing etching waste liquid, which comprises the following steps:
detecting whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution exists or not; if yes, preprocessing the current copper-containing etching waste liquid to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value;
The alkaline neutralization solution is put into the current copper-containing etching waste liquid according to the volume ratio relation;
after the stirring frequency and the aeration power value required by the copper-containing etching waste liquid after neutralization are calculated according to the total volume of the materials put in, stirring and aerating the copper-containing etching waste liquid after neutralization according to the stirring frequency and the aeration power value;
after the neutralized copper-containing etching waste liquid is kept stand for a period of time, detecting whether the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid is within a qualified threshold value range; if not, calculating the secondary adding amount of the alkaline neutralization solution according to the pH deviation value of the supernatant of the neutralized copper-containing etching waste liquid, and adding the alkaline neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
after the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization is calculated according to the total volume of the materials fed in the secondary, stirring the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency;
after the secondary neutralized copper-containing etching waste liquid is kept stand for a period of time, if the PH value of the supernatant liquid of the secondary neutralized copper-containing etching waste liquid is within the qualified threshold value range, confirming that the current copper-containing etching waste liquid treatment process is completed;
If the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution is detected to be absent, calculating a target PH value required by metal hydroxide precipitation of the current copper-containing etching waste liquid;
calculating the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula and the target PH value;
and executing the operation of preprocessing the current copper-containing etching waste liquid so as to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value.
As another alternative, in the first aspect of the embodiment of the present invention, the calculating the target PH required for the precipitation of the metal hydroxide in the current copper-containing etching waste solution includes:
calculating the minimum PH value of metal hydroxide precipitation required by the current copper-containing etching waste liquid;
after the current voltage value and the current temperature value of the current copper-containing etching waste liquid are obtained, calculating a PH temperature compensation value required by the current copper-containing etching waste liquid by using a surface fitting algorithm;
and combining the lowest PH value of the metal hydroxide precipitate and the PH temperature compensation value to determine the target PH value.
As another alternative, in the first aspect of the embodiment of the present invention, the calculating the minimum PH of the metal hydroxide precipitate required for the current copper-containing etching waste liquid includes:
Calculating the square root of the quotient of the metal hydroxide solubility of the current copper-containing etching waste liquid and the metal ion concentration in the copper-containing etching waste liquid to obtain the hydroxide ion concentration in the current copper-containing etching waste liquid; wherein, N is the metal ion order in the current copper-containing etching waste liquid;
the ion product constant of water is divided by the hydroxide ion concentration to calculate the minimum PH of the metal hydroxide precipitate.
As another optional implementation manner, in the first aspect of the embodiment of the present invention, the pre-treating the current copper-containing etching waste liquid to make the potential value of the current copper-containing etching waste liquid reach a specified threshold value includes:
after the pretreatment aeration power value required by the current copper-containing etching waste liquid is calculated according to the volume of the current copper-containing etching waste liquid, carrying out aeration treatment on the current copper-containing etching waste liquid according to the pretreatment aeration power value;
detecting whether the potential value of the current copper-containing etching waste liquid reaches a specified threshold value or not; if not, calculating the addition amount of the hydrogen peroxide to be added according to the oxidation volume ratio between the hydrogen peroxide solution and the monovalent copper content, and adding the hydrogen peroxide solution to the current copper-containing etching waste liquid according to the addition amount of the hydrogen peroxide;
After the current copper-containing etching waste liquid is kept stand for a period of time, detecting whether the potential value of the current copper-containing etching waste liquid reaches the specified threshold value or not again; and if so, executing the operation of throwing the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio relation.
As another optional implementation manner, in the first aspect of the embodiment of the present invention, the calculating the stirring frequency and the aeration power value required for the neutralized copper-containing etching waste liquid according to the total volume of the fed material includes:
respectively obtaining a stirring power coefficient value and a stirring power correction coefficient which increase along with the increase of the volume;
adding the product of the multiplied total volume of the materials to be added and the stirring power correction coefficient to calculate the stirring frequency;
respectively obtaining an aeration power coefficient value and an aeration power correction coefficient which increase along with the increase of the volume;
adding the product of the multiplied total volume of the materials to be added and the aeration power correction coefficient to calculate the aeration power value;
and calculating the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization according to the volume of the secondary total put material, wherein the method comprises the following steps:
Adding the product of the multiplied total volume of the secondary added material and the stirring power coefficient value to the stirring power correction coefficient to calculate the secondary stirring frequency;
and calculating a pretreatment aeration power value required by the current copper-containing etching waste liquid according to the current copper-containing etching waste liquid volume, wherein the pretreatment aeration power value comprises:
and adding the product obtained by multiplying the current copper-containing etching waste liquid volume by the aeration power coefficient value and the aeration power correction coefficient to calculate the pretreatment aeration power value.
As another alternative implementation manner, in the first aspect of the embodiment of the present invention, after the copper-containing etching waste liquid after neutralization is left for a period of time and before the step of detecting whether the PH value of the supernatant liquid of the copper-containing etching waste liquid after neutralization is within the acceptable threshold value range, the method further includes:
calculating the height of the neutralized copper-containing etching waste liquid by utilizing a volume formula according to the neutralized copper-containing etching waste liquid and the bottom area of a holding device for holding the neutralized copper-containing etching waste liquid;
determining the liquid level position of the neutralized copper-containing etching waste liquid according to the height of the neutralized copper-containing etching waste liquid;
Acquiring the PH value at a specified distance below the liquid level; the PH value of the position with the specified distance is the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid.
In another optional implementation manner, in the first aspect of the embodiment of the present invention, the calculating the secondary adding amount of the alkaline neutralization solution according to the PH deviation value of the supernatant of the neutralized copper-containing etching waste liquid, and adding the alkaline neutralization solution to the current copper-containing etching waste liquid according to the secondary adding amount includes:
by means ofCalculating the hydrogen ion concentration in the neutralized copper-containing etching waste liquid>；
If the PH value of the supernatant of the neutralized copper-containing etching waste liquid is smaller than the minimum value of the qualified threshold range, utilizingCalculating the secondary throwing amount;
the alkaline neutralization solution is added into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
if the PH value of the supernatant of the neutralized copper-containing etching waste liquid is larger than the maximum value of the qualified threshold range, utilizingCalculating the secondary throwing amount;
the acidic neutralization solution is added into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
Wherein the saidFor the solution hydrogen ion concentration at a pH value within said qualification threshold range, said +.>The hydrogen ion concentration in the alkaline neutralization solution.
A second aspect of an embodiment of the present invention discloses a processing system, including:
the first detection unit is used for detecting whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution exists or not;
the pretreatment unit is used for pretreating the current copper-containing etching waste liquid when the first detection unit detects that the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution exists, so that the potential value of the current copper-containing etching waste liquid reaches a specified threshold value;
the first throwing unit is used for throwing the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio relation;
the first treatment unit is used for sequentially stirring and aerating the neutralized copper-containing etching waste liquid according to the stirring frequency and the aeration power value after calculating the stirring frequency and the aeration power value required by the neutralized copper-containing etching waste liquid according to the total volume of the materials put in;
the second detection unit is used for detecting whether the PH value of the supernatant of the neutralized copper-containing etching waste liquid is within a qualified threshold value range after the neutralized copper-containing etching waste liquid is kept stand for a period of time;
The calculating and adding unit is used for calculating the secondary adding amount of the alkaline neutralization solution according to the pH deviation value of the supernatant of the neutralized copper-containing etching waste liquid when the second detection unit detects that the pH value of the supernatant of the neutralized copper-containing etching waste liquid is not in the qualified threshold range, and adding the alkaline neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
the second treatment unit is used for stirring the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency after calculating the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization according to the total volume of the materials fed in the secondary;
a first determining unit, configured to determine that the current copper-containing etching waste liquid treatment process is completed if the PH value of the supernatant of the copper-containing etching waste liquid after the secondary neutralization is within the acceptable threshold value range after the copper-containing etching waste liquid after the secondary neutralization is left for a period of time;
the first calculating unit is used for calculating a target PH value required by metal hydroxide precipitation of the current copper-containing etching waste liquid when the first detecting unit detects that the volume ratio relation of the current copper-containing etching waste liquid and the alkaline neutralizing solution does not exist;
The second calculating unit is used for calculating the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula and the target PH value;
and the execution unit is used for executing the operation of preprocessing the current copper-containing etching waste liquid so as to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value.
As another optional implementation manner, in the second aspect of the embodiment of the present invention, the first computing unit includes:
a first calculating subunit, configured to calculate a minimum PH value of metal hydroxide precipitation required by the current copper-containing etching waste liquid;
the second calculating subunit is used for calculating a PH temperature compensation value required by the current copper-containing etching waste liquid by using a surface fitting algorithm after the current voltage value and the current temperature value of the current copper-containing etching waste liquid are obtained;
and the determining subunit is used for combining the lowest PH value of the metal hydroxide precipitation and the PH temperature compensation value to determine the target PH value.
A third aspect of an embodiment of the present invention discloses a processing system, including:
a memory storing executable program code;
A processor coupled to the memory;
the processor calls the executable program codes stored in the memory to execute the intelligent processing method of the copper-containing etching waste liquid disclosed in the first aspect of the embodiment of the invention.
A fourth aspect of the embodiment of the present invention discloses a computer-readable storage medium storing a computer program, where the computer program causes a computer to execute an intelligent treatment method for copper-containing etching waste liquid disclosed in the first aspect of the embodiment of the present invention.
A fifth aspect of the embodiments of the present invention discloses a computer program product, which when run on a computer causes the computer to perform part or all of the steps of any one of the intelligent methods for treating copper-containing etching waste solutions of the first aspect.
A sixth aspect of the embodiments of the present invention discloses an application publishing platform for publishing a computer program product, wherein the computer program product, when run on a computer, causes the computer to perform part or all of the steps of any one of the intelligent methods for treating copper-containing etching waste liquid of the first aspect.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
In the embodiment of the invention, whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution exists is detected; if yes, preprocessing the current copper-containing etching waste liquid to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value; the alkaline neutralization solution is put into the current copper-containing etching waste liquid according to the volume ratio relation; after the stirring frequency and the aeration power value required by the copper-containing etching waste liquid after neutralization are calculated according to the total volume of the materials put in, stirring and aerating the copper-containing etching waste liquid after neutralization according to the stirring frequency and the aeration power value; after the neutralized copper-containing etching waste liquid is kept stand for a period of time, detecting whether the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid is within a qualified threshold value range; if not, calculating the secondary adding amount of the alkaline neutralization solution according to the pH deviation value of the supernatant of the neutralized copper-containing etching waste liquid, and adding the alkaline neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary adding amount; after the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization is calculated according to the total volume of the materials fed in the secondary, stirring the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency; after the secondary neutralized copper-containing etching waste liquid is kept stand for a period of time, if the PH value of the supernatant liquid of the secondary neutralized copper-containing etching waste liquid is within the qualified threshold value range, confirming that the current copper-containing etching waste liquid treatment process is completed; if the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution is detected to be absent, calculating a target PH value required by metal hydroxide precipitation of the current copper-containing etching waste liquid; calculating the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula and the target PH value; and executing the operation of preprocessing the current copper-containing etching waste liquid so as to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value. It can be seen that the embodiments of the present invention enable more accurate pH adjustment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an intelligent treatment method for copper-containing etching waste liquid, disclosed in the embodiment of the invention;
FIG. 2 is a schematic flow chart of another method for intelligent treatment of copper-containing etching waste liquid according to an embodiment of the present invention;
FIG. 3 is a schematic flow chart of another method for intelligent treatment of copper-containing etching waste liquid according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a processing system according to an embodiment of the present disclosure;
FIG. 5 is a schematic diagram of another processing system according to an embodiment of the present disclosure;
FIG. 6 is a schematic diagram of another processing system according to an embodiment of the present disclosure.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the terms "first," "second," "third," "fourth," and the like in the description and in the claims of the present invention are used for distinguishing between different objects and not necessarily for describing a particular sequential or chronological order. The terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed or inherent to such process, method, article, or apparatus.
The embodiment of the invention discloses an intelligent treatment method and a treatment system for copper-containing etching waste liquid, which can realize more accurate pH adjustment.
The following detailed description refers to the accompanying drawings.
Example 1
Referring to fig. 1, fig. 1 is a schematic flow chart of an intelligent treatment method for copper-containing etching waste liquid according to an embodiment of the invention. As shown in fig. 1, the intelligent treatment method of the copper-containing etching waste liquid may include the following steps.
101. The processing system detects whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution exists, if not, the processing system executes the steps 102-107, and if yes, the processing system executes the steps 104-107.
In an embodiment of the present invention, the volume ratio relationship may be manually set and uploaded to the system, or may be calculated by the system before the copper-containing etching waste liquid treatment process, which is not limited in this application.
102. The treatment system calculates the target pH value required for the precipitation of the metal hydroxide of the current copper-containing etching waste liquid.
In the embodiment of the invention, the method can be based on the principle that the heavy metal ions and the hydroxyl ions form indissolvable hydroxide precipitates, and the precipitation effect depends on the concentration of the heavy metal ions and the concentration of the hydroxyl ions in the solution. That is, the PH of the solution is a determining condition for a certain concentration of heavy metal ions. Thus, the present application can be based on the precipitation dissolution equilibrium of metal hydroxide, and the ionic product of waterThe minimum pH required for precipitation of the metal hydroxide is calculated, i.e. +.>The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>The concentration product of the metal hydroxide is used for calculating the target PH value required by the metal hydroxide precipitation of the current copper-containing etching waste liquid.
As an alternative embodiment, in an embodiment of the present invention, the system may determine the dissolution reaction equation of the metal hydroxide first, followed by According to the dissolution reaction equation, the concentration expression of metal ions and hydroxide ions can be established, the concentration expression of hydroxide ions is substituted into the dissolution reaction equation, the concentration expression of metal ions can be obtained, and the self-ionization process of water can be ignored under the condition that the metal hydroxide precipitation occurs at higher concentration of metal ions, namely. The system can then calculate the concentration of metal ions using the known equilibrium constant for dissolution of metal hydroxide (Ksp), which represents the equilibrium of metal hydroxide precipitation and dissolution, whereas for a given metal hydroxide the corresponding Ksp value can be found, followed by->The minimum pH required for precipitation of the metal hydroxide can be calculated.
103. And the processing system calculates the volume ratio relation of the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula and a target PH value.
As an alternative implementation manner, in the embodiment of the present invention, a known acid-base volume ratio formula is obtained first, where the acid-base volume ratio formula may be a formula for calculating the volume ratio of acid or base required for the acid-base neutralization reaction.
As an alternative embodiment, in the embodiment of the present invention, the chemical reaction equation between the acid in the etching waste liquid and the alkali in the alkali neutralization solution may be determined first, for example, assuming that the acid in the etching waste liquid containing copper is HCl and the alkali in the alkali neutralization solution is NaOH, the reaction equation may be written as:
HCl (aq) +NaOH (aq). Fwdarw.NaCl (aq) +H2O (l), in which reaction the acid and base react to form a salt and water. The system may then determine the molar ratio of acid to base based on the molar coefficients in the reaction equation, e.g., if the molar coefficients in the reaction equation are 1:1, the molar ratio of acid in the waste stream to base in the alkaline neutralization solution is 1:1, and then, taking into account the relationship between molar concentration and volume, the system may compare the molar ratioThe molar ratio is converted to a volume ratio, for example, if the molar ratio of the acid in the waste liquid to the alkali in the alkali neutralizing solution is 1:1, and the volumes of the acid in the waste liquid and the alkali in the alkali neutralizing solution are respectivelyAndthe volume ratio is: />:/>=1:1, which means that the volume ratio of waste liquid and alkaline neutralizing solution is equal.
104. The processing system preprocesses the current copper-containing etching waste liquid so that the potential value of the current copper-containing etching waste liquid reaches a specified threshold value.
As an alternative implementation, in the embodiment of the present invention, if the current potential value of the copper-containing etching waste liquid is lower than the target threshold value, the system may add an oxidizing agent (such as hydrogen peroxide or potassium permanganate) to increase the oxidation-reduction reaction, increase the potential value, and if the current potential value is higher than the target threshold value, the system may add a reducing agent (such as sulfite or sodium thiosulfate) to promote the reduction reaction, and decrease the potential value. The pH value of the waste liquid can also influence the potential value, and if necessary, the system can also add acid or alkali to adjust the pH value of the waste liquid so as to influence the potential value.
As an alternative implementation manner, in the embodiment of the present invention, when the treating agent is added, the system may control the addition amount according to the volume of the waste liquid and the requirement of the target threshold, and the addition amount may be specifically performed by referring to the related treating agent use instruction or manually set standard or a system-set calculation program.
105. And the treatment system puts the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio.
106. After the stirring frequency and the aeration power value required by the neutralized copper-containing etching waste liquid are calculated according to the total volume of the materials put in, the processing system sequentially carries out stirring and aeration treatment on the neutralized copper-containing etching waste liquid according to the stirring frequency and the aeration power value.
As an alternative embodiment, in an embodiment of the present invention, the aeration power value is the energy used to introduce gas into the waste liquid by means of bubbles or mechanical means. The system can select an appropriate aeration power value according to the characteristics of the waste liquid and the oxidation-reduction reaction required, and the aeration power value is usually expressed as power per unit volume (such as per liter) and is expressed as W/m. The specific aeration power value depends on the viscosity of the waste liquid, the gas transmission efficiency and the required redox reaction performance.
As an alternative implementation mode, in the embodiment of the invention, the system can sequentially stir and aerate the neutralized copper-containing etching waste liquid according to the calculated stirring frequency and aeration power value and the specification and operation requirements of equipment so as to ensure that the stirring equipment and an aeration system can provide required stirring frequency and aeration power.
107. After the neutralized copper-containing etching waste liquid is kept stand for a period of time, the processing system detects whether the PH value of the supernatant of the neutralized copper-containing etching waste liquid is within a qualified threshold range, if not, the steps 108-110 are executed, and if yes, the process is ended.
108. And the treatment system calculates the secondary adding amount of the alkaline neutralization solution according to the pH deviation value of the supernatant of the neutralized copper-containing etching waste liquid, and adds the alkaline neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary adding amount.
As an alternative embodiment, in the embodiment of the present invention, the system may calculate the secondary dosage of the alkaline neutralizing solution according to the pH deviation value, and the size of the secondary dosage depends on the volume of the waste liquid, the desired pH change and the concentration of the alkaline neutralizing solution, and the volume or the molar concentration of the alkaline solution may be used to calculate the dosage.
As an alternative implementation, in the embodiment of the present invention, the system may use an accurate instrument or device to put the alkaline neutralization solution into the waste liquid according to the secondary dosage under appropriate conditions according to the calculation result.
109. And after the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization is calculated according to the total volume of the materials fed in the secondary, the processing system carries out stirring processing on the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency.
110. After the copper-containing etching waste liquid is kept stand for a period of time after the secondary neutralization, if the PH value of the supernatant liquid of the copper-containing etching waste liquid after the secondary neutralization is within the range of the qualified threshold value, the processing system confirms that the current processing process of the copper-containing etching waste liquid is finished, and the flow is ended.
As an optional implementation manner, in the embodiment of the invention, the treatment process can be monitored and adjusted in real time according to the set parameters and the set threshold value, so that the accuracy and the efficiency of waste liquid treatment are improved, and the human error and the treatment time are reduced.
As an alternative implementation, in the present example, the present application may stably maintain the desired processing conditions and results through an automated control and feedback mechanism to ensure that the process remains consistent from lot to lot.
As an alternative implementation manner, in the embodiment of the present invention, the present application may reduce the need for manual operations. This helps to reduce labor costs and reduces the impact of human factors on the process.
As an optional implementation manner, in the embodiment of the invention, various parameters and indexes in the waste liquid treatment process can be monitored in real time, and corresponding adjustment is made, so that potential problems or abnormal conditions can be found and corrected in time, and the safety of the treatment process is improved.
As an alternative implementation, in the embodiment of the present invention, the present application may record and store various data and parameters during the treatment process, and these data may be used for subsequent analysis and optimization, to help improve the effect and flow of the waste liquid treatment.
In the method for intelligently treating copper-containing etching waste liquid in fig. 1, a treatment system is described as an execution subject. It should be noted that, the execution body of the intelligent processing method of the copper-containing etching waste liquid in fig. 1 may also be a stand-alone device associated with the processing system, which is not limited by the embodiment of the present invention.
It can be seen that implementing an intelligent treatment method for copper-containing etching waste liquid as described in fig. 1 enables more accurate pH adjustment.
In addition, by implementing the intelligent treatment method of the copper-containing etching waste liquid described in fig. 1, the accuracy and efficiency of waste liquid treatment can be improved.
Example two
Referring to fig. 2, fig. 2 is a flow chart illustrating another intelligent treatment method for copper-containing etching waste liquid according to an embodiment of the invention. As shown in fig. 2, the intelligent treatment method of the copper-containing etching waste liquid may include the following steps:
201. the processing system detects whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution exists, if not, the processing system executes the steps 202-209, and if yes, the processing system executes the steps 206-209.
202. The treatment system calculates the minimum PH value of the metal hydroxide precipitate required by the current copper-containing etching waste liquid.
In this embodiment, the present application may calculate the quotient of the metal hydroxide solubility product of the current copper-containing etching waste liquid divided by the metal ion concentration in the copper-containing etching waste liquid by N times to obtain the hydroxide ion concentration in the current copper-containing etching waste liquid; wherein N is the metal ion order in the current copper-containing etching waste liquid, and then dividing the ion product constant of water by the hydroxide ion concentration to calculate the lowest PH value of the metal hydroxide precipitate.
203. After the processing system obtains the current voltage value and the current temperature value of the current copper-containing etching waste liquid, calculating the PH temperature compensation value required by the current copper-containing etching waste liquid by using a surface fitting algorithm.
As an alternative embodiment, in an embodiment of the present invention, the system may collect a series of sample data relating to the copper-containing etching waste, including voltage values, temperature values, and corresponding pH values, to ensure that the data covers a range of waste at different temperatures. The system may then pre-process the collected sample data, for example, to check the data for outliers or missing values, and perform the necessary data cleaning and processing. The system may then select an appropriate surface fitting model (e.g., quadratic polynomial, polynomial regression, gaussian process regression, etc.) to fit the data based on the actual situation and the characteristics of the data distribution. The system may then fit a pH model that is dependent on voltage and temperature using the voltage and temperature values as independent variables and pH values as dependent variables. Finally, the system can calculate the corresponding pH value by utilizing the pH model obtained by fitting according to the current voltage value and the current temperature value of the current copper-containing etching waste liquid, and takes the difference between the calculated pH value and the actually measured pH value as a temperature compensation value, namely, the pH compensation value = the calculated pH value-the actually measured pH value, and obviously, if the pH compensation value is a positive number, the corresponding pH value is required to be increased for compensating the waste liquid; if the pH compensation value is negative, it means that the waste liquid needs to be reduced by the corresponding pH value to compensate.
204. The processing system combines the minimum pH of the metal hydroxide precipitate with the pH temperature compensation to determine a target pH.
205. And the processing system calculates the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula.
206. The processing system obtains an aeration power coefficient value and an aeration power correction coefficient which increase with the increase of the volume respectively.
207. And adding the product obtained by multiplying the current copper-containing etching waste liquid volume by the aeration power coefficient value and the aeration power correction coefficient by the processing system to calculate a pretreatment aeration power value.
208. And the treatment system carries out aeration treatment on the current copper-containing etching waste liquid according to the pretreatment aeration power value.
As an optional implementation manner, in the embodiment of the invention, after the system determines the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution, a flowmeter of a copper-containing etching waste liquid storage tank is opened, then a self-priming pump of the copper-containing etching waste liquid storage tank is opened, when the flowmeter detects that the volume reaches a set value, the self-priming pump is closed (the flowmeter controls the opening and closing of the pump), meanwhile, a liquid level meter of the neutralization reaction kettle receives information of the volume required by the copper-containing etching waste liquid reaction sent by the system, and if the liquid level is higher than the copper-containing etching waste liquid volume required by a formula, the self-priming pump also stops conveying raw materials, so that double guarantees of quantitative pumping of the self-priming pump and verification of the volume by the liquid level meter in the neutralization kettle are realized. And when the self-priming pump stops pumping acid water, the system can automatically open the Roots blower valve to perform aeration treatment on the copper-containing etching waste liquid.
In the embodiment of the invention, the aeration power of the pretreatment of the acidic copper-containing waste liquid increases along with the increase of the addition value of the copper-containing etching waste liquid, so that the aeration power value is increased by X cubic meters of air per minute every 1 liter of copper-containing etching waste liquid, and the final aeration power needs to be added with the correction coefficient of Y cubic meters of air per minute. I.e. the present application。
209. The processing system detects whether the current potential value of the copper-containing etching waste liquid reaches a specified threshold value, if not, step 210 to step 211 are executed, and if yes, step 212 to step 220 are executed.
As an optional implementation manner, in the embodiment of the invention, after aeration treatment is started, the system can start an ORP potentiometer, and after normal reading of the ORP potentiometer is obtained, if the current potential value of the copper-containing etching waste liquid is more than or equal to a specified threshold value, the system enters the next link; if the potential value of the current copper-containing etching waste liquid is smaller than the designated threshold value, starting a hydrogen peroxide mechanical diaphragm metering pump to start adding hydrogen peroxide into the current copper-containing etching waste liquid until the potential value of the current copper-containing etching waste liquid is larger than or equal to the designated threshold value, closing the hydrogen peroxide metering pump, then starting a timer by the system, closing the timer after a certain time, then starting an ORP meter to read the potential value again, if the potential value of the current copper-containing etching waste liquid is larger than or equal to the designated threshold value, entering the next link by the system, otherwise, returning to the upper stage to perform hydrogen peroxide adding again. And after the system obtains the data that the potential value of the current copper-containing etching waste liquid is more than or equal to the specified threshold value, the system reads the data of the hydrogen peroxide flowmeter to obtain the hydrogen peroxide usage amount. And after the pretreatment of the current copper-containing etching waste liquid is finished, the system can close the Roots blower air supply valve to stop aeration.
210. The treatment system calculates the addition amount of the hydrogen peroxide required to be added according to the oxidation volume ratio between the hydrogen peroxide solution and the monovalent copper content, and adds the hydrogen peroxide solution to the current copper-containing etching waste liquid according to the addition amount of the hydrogen peroxide.
As an alternative embodiment, in the present example, since the subsequent process requires the existence of copper in a divalent form, the copper-containing etching waste liquid pretreatment of the present application is an oxidation reaction for converting all monovalent copper into divalent copper, and when the potential value is above a specified threshold value, the monovalent copper content is hardly found, and thus the specified threshold value can be regarded as the end point of the conversion reaction.
As an alternative embodiment, in the embodiment of the present invention, since the oxidation volume ratio between the hydrogen peroxide solution and the monovalent copper content is known, that is, 27.5% of hydrogen peroxide of 120L may oxidize 0.6% of the monovalent copper content, and the change amount of the electric potential is about 5mv, the present application may perform the supplementation of the electric potential value according to the oxidation volume ratio.
As an alternative implementation manner, in the embodiment of the present invention, an oxidation reaction equation between monovalent copper and hydrogen peroxide may be determined first, then, a molar ratio between monovalent copper and hydrogen peroxide may be determined according to a molar coefficient in the reaction equation, and according to the coefficient in the reaction equation, it is known that one mole of hydrogen peroxide is required for every two moles of monovalent copper, and since the concentration of hydrogen peroxide is generally expressed in terms of volume percent, it is required to convert the molar ratio into the volume ratio, the system may convert the molar ratio into the volume ratio according to the density and the molar ratio of hydrogen peroxide, and then calculate the required added hydrogen peroxide amount according to the concentration of monovalent copper in the copper-containing etching waste liquid and the required volume ratio.
211. After the current copper-containing etching waste liquid is kept stand for a period of time, the processing system detects whether the potential value of the current copper-containing etching waste liquid reaches a specified threshold value again, if yes, step 212-step 220 are executed, and if not, the process is ended.
212. And the treatment system puts the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio.
213. The processing system obtains a stirring power coefficient value and a stirring power correction coefficient, respectively, which increase with an increase in volume.
214. The processing system calculates the stirring frequency by adding the product of the multiplied total volume of the material to be added and the stirring power correction coefficient.
215. The processing system calculates the aeration power value by adding the product of the multiplied total volume of the material and the aeration power coefficient value and the aeration power correction coefficient.
216. And the treatment system sequentially carries out stirring and aeration treatment on the neutralized copper-containing etching waste liquid according to the stirring frequency and the aeration power value.
In the embodiment of the invention, the stirring power of the neutralization reaction kettle stirrer increases along with the increase of the total volume of the fed raw materials, and further the stirring power increases every 1 liter of total volume of the raw materials Hz, final->The power needs to be added with a correction factor of (-1/Y) Hz. I.e. & gt of the present application>。
As an optional implementation manner, in the embodiment of the invention, after the pretreatment of the copper-containing etching waste liquid is completed, the system can send a first-stage signal to the frequency converter of the neutralization reaction kettle stirrer, the neutralization reaction kettle stirrer is started to adjust to a designated frequency, the system can add the alkaline neutralization solution according to the volume ratio relation of the copper-containing etching waste liquid and the alkaline neutralization solution, and meanwhile, the system can adjust the stirring frequency according to the volume of the total amount of added raw materials.
As an alternative implementation mode, in the embodiment of the invention, after all materials are put (after an alkaline neutralizing solution self-priming pump is closed and a reaction kettle liquid level meter verifies that the input amount is accurate), a neutralizing reaction kettle stirrer is closed, a Roots blower is started to aerate the neutralizing materials, a timer is started to count after the blower is started, the materials can fully react, and after a certain time, a system can shut down the Roots blower to stop aeration and count time, so that the materials are kept still.
217. After the neutralized copper-containing etching waste liquid is kept stand for a period of time, the processing system calculates the height of the neutralized copper-containing etching waste liquid by utilizing a volume formula according to the neutralized copper-containing etching waste liquid and the bottom area of a holding device for holding the neutralized copper-containing etching waste liquid.
218. And the processing system determines the liquid level position of the neutralized copper-containing etching waste liquid according to the height of the neutralized copper-containing etching waste liquid.
219. The processing system acquires the PH value at a specified distance position below the liquid level position; wherein the PH value at the designated distance position is the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid.
In an embodiment of the invention, after the copper-containing etching waste liquid is kept stand for a period of time after neutralization, a mechanical arm (a pH meter is arranged on the mechanical arm) can be started, according to the liquid level information fed back by the liquid level meter of the neutralization reaction kettle, the mechanical arm vertically immerses the probe of the pH meter into the supernatant (the probe is completely inserted into the supernatant and is about 5cm away from the liquid level, the pH value is obtained after the reading is stabilized, if the pH value of the supernatant is between 5.6 and 5.8, the neutralization reaction is completed, the mechanical arm withdraws the pH meter from the liquid level, and the pH meter is inserted into the pH meter cleaning device to be automatically flushed with purified water and returned to the buffer solution for soaking for standby, and if the pH value of the supernatant is not between 5.6 and 5.8, the mechanical arm withdraws the pH meter from the liquid level and automatically flushes the pH meter into the buffer solution for standby after the pH meter is inserted into the pH meter cleaning device to be automatically flushed with purified water.
As an alternative implementation mode, in the embodiment of the invention, when the reaction kettle is a cylindrical device with a flat bottom surface, the system can be utilizedTo calculate the position to be reached by the glass electrode at the bottom of the pH meter probe, wherein X is the distance X cm below the liquid level of the neutralized copper-containing etching waste liquid.
Referring to fig. 4, fig. 4 is a flow chart illustrating another intelligent treatment method for copper-containing etching waste liquid according to an embodiment of the invention. As shown in fig. 4, the intelligent treatment method of the copper-containing etching waste liquid may include the following steps:
220. the processing system detects whether the pH value of the supernatant of the neutralized copper-containing etching waste liquid is within a qualified threshold range, if not, step 221 is executed, and if yes, the process is ended.
221. Processing system utilizationCalculating the hydrogen ion concentration in the neutralized copper-containing etching waste liquid>Step 222 to step 223 or step 224 to step 225 are performed.
222. If the pH value of the supernatant of the neutralized copper-containing etching waste liquid is smaller than the minimum value of the qualified threshold range, the processing system utilizesAnd calculating the secondary throwing amount.
223. And the treatment system puts the alkaline neutralizing solution into the neutralized copper-containing etching waste liquid according to the secondary feeding amount, and steps 226-228 are executed.
In the present embodiment of the present invention, in the present embodiment,hydrogen ion concentration of the solution at a pH within a threshold limit, < >>The concentration of hydrogen ions in the solution is neutralized for alkalinity.
224. If the pH value of the supernatant of the neutralized copper-containing etching waste liquid is greater than the maximum value of the qualified threshold value range, the processing system utilizesAnd calculating the secondary throwing amount.
225. And the treatment system puts the acidic neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary putting amount, and steps 226-228 are executed.
In the present embodiment of the present invention, in the present embodiment,hydrogen ion concentration of the solution at a pH within a threshold limit, < >>The concentration of hydrogen ions in the solution is neutralized for alkalinity.
As an optional implementation manner, in the embodiment of the invention, after the system enters the fine adjustment link, the neutralizing reaction kettle stirrer can be started to adjust to the designated frequency, after the stirring is started, the timer can be started to stir the materials, then the fine adjustment adding amount can be set according to the designated formula to carry out the adding of the materials, after the adding of the fine adjustment adding amount is completed, the system can close the neutralizing reaction kettle stirrer, the timer is started to allow the materials to stand, and the pH detection process is repeated again to ensure that the pH is within the range of the qualified threshold value, and the neutralizing reaction can be completed.
226. And the processing system adds the product obtained by multiplying the volume of the secondary total put material by the stirring power coefficient value and the stirring power correction coefficient to calculate the secondary stirring frequency.
227. And the treatment system carries out stirring treatment on the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency.
228. And after the copper-containing etching waste liquid is kept stand for a period of time after the secondary neutralization, if the PH value of the supernatant liquid of the copper-containing etching waste liquid after the secondary neutralization is within a qualified threshold value range, confirming that the current copper-containing etching waste liquid treatment process is finished.
As an optional implementation manner, in the embodiment of the present invention, the amount of the treatment agent to be applied may be accurately determined according to the target parameter and the characteristics of the waste liquid through calculation, which helps to avoid excessive or insufficient application and ensure the best treatment effect.
As an alternative implementation manner, in the embodiment of the present invention, by adding the treatment agent according to the calculation result, a consistent treatment effect can be maintained between different batches, which helps to improve the repeatability and stability of the waste liquid treatment.
As an alternative implementation manner, in the embodiment of the invention, by accurately calculating the dosage of the treating agent, the excessive use of the treating agent can be avoided, so that the treating cost is reduced. Meanwhile, the waste product generated in the waste liquid treatment process is reduced.
As an alternative implementation manner, in the embodiment of the invention, the application determines the dosage of the treating agent through calculation, so that the degree of judgment of an operator is reduced, and the risk of operation errors is reduced.
As an optional implementation manner, in the embodiment of the invention, the dosage of the treating agent can be adjusted according to the actual condition of the waste liquid through calculation, so that a better treatment effect is achieved, and the purification efficiency and quality of the waste liquid are improved.
Therefore, by implementing another intelligent treatment method of copper-containing etching waste liquid described in fig. 2-3, more accurate pH adjustment can be realized.
In addition, by implementing another intelligent treatment method of copper-containing etching waste liquid described in fig. 2-3, the risk of operation errors can be reduced.
Example III
Referring to fig. 4, fig. 4 is a schematic diagram illustrating a processing system according to an embodiment of the invention. As shown in fig. 4, the processing system 300 may include a first detection unit 301, a preprocessing unit 302, a first delivery unit 303, a first processing unit 304, a second detection unit 305, a calculation and delivery unit 306, a second processing unit 307, a first determination unit 308, a first calculation unit 309, a second calculation unit 310, and an execution unit 311, wherein:
A first detecting unit 301 for detecting whether there is a volume ratio relationship between the current copper-containing etching waste liquid and the alkaline neutralizing solution.
And a pretreatment unit 302, configured to, when the first detection unit 301 detects that there is a volume ratio relationship between the current copper-containing etching waste liquid and the alkaline neutralization solution, pretreat the current copper-containing etching waste liquid so that a potential value of the current copper-containing etching waste liquid reaches a specified threshold value.
And the first throwing unit 303 is used for throwing the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio relation.
The first processing unit 304 is configured to sequentially perform stirring and aeration treatment on the neutralized copper-containing etching waste liquid according to the stirring frequency and the aeration power value after calculating the stirring frequency and the aeration power value required for the neutralized copper-containing etching waste liquid according to the total volume of the material to be added.
And a second detecting unit 305 for detecting whether the PH of the supernatant of the neutralized copper-containing etching waste liquid is within a qualified threshold value after the neutralized copper-containing etching waste liquid is left for a while.
And a calculating and adding unit 306, configured to calculate a secondary adding amount of the alkaline neutralization solution according to the PH deviation value of the supernatant of the neutralized copper-containing etching waste liquid when the second detecting unit 305 detects that the PH value of the supernatant of the neutralized copper-containing etching waste liquid is not within the acceptable threshold range, and add the alkaline neutralization solution to the neutralized copper-containing etching waste liquid according to the secondary adding amount.
And a second processing unit 307 for stirring the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency after calculating the secondary stirring frequency required for the copper-containing etching waste liquid after secondary neutralization according to the total volume of the materials put in the secondary.
The first determining unit 308 is configured to determine that the current treatment process of the copper-containing etching waste liquid is completed if the PH of the supernatant of the copper-containing etching waste liquid after the second neutralization is within the acceptable threshold value range after the copper-containing etching waste liquid after the second neutralization is left for a period of time.
A first calculating unit 309, configured to calculate a target PH value required for precipitation of metal hydroxide in the current copper-containing etching waste liquid when the first detecting unit 301 detects that there is no volume ratio relationship between the current copper-containing etching waste liquid and the alkaline neutralizing solution.
The second calculating unit 310 is configured to calculate a volume ratio relationship between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to the acid-base volume ratio formula and the target PH value.
The execution unit 311 is configured to perform an operation of preprocessing the current copper-containing etching waste liquid to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value.
In an embodiment of the present invention, the volume ratio relationship may be manually set and uploaded to the system, or may be calculated by the system before the copper-containing etching waste liquid treatment process, which is not limited in this application.
In the embodiment of the present invention, the first calculating unit 309 may be based on the principle that the heavy metal ions and the hydroxide ions generate poorly soluble hydroxide precipitates, and the precipitation effect depends on the concentration of the heavy metal ions and the concentration of the hydroxide ions in the solution. That is, the PH of the solution is a determining condition for a certain concentration of heavy metal ions. Thus, the present application can be based on the precipitation dissolution equilibrium of metal hydroxide, and the ionic product of waterThe minimum pH required for precipitation of the metal hydroxide is calculated, i.e. +.>The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>The concentration product of the metal hydroxide is used for calculating the target PH value required by the metal hydroxide precipitation of the current copper-containing etching waste liquid.
As an alternative embodiment, in the embodiment of the present invention, the first calculation unit 309 may determine the dissolution reaction equation of the metal hydroxide first, then may establish the concentration expression of the metal ion and the hydroxide ion according to the dissolution reaction equation, and substituting the concentration expression of the hydroxide ion into the dissolution reaction equation may obtain the concentration expression of the metal ion, and since precipitation of the metal hydroxide occurs inThe self-ionisation process of water can be neglected in the case of higher metal ion concentrations, i.e . Subsequently, the first calculation unit 309 may calculate the concentration of metal ions using a known equilibrium constant for dissolution of metal hydroxide (Ksp), which represents the equilibrium of precipitation and dissolution of metal hydroxide, whereas for a given metal hydroxide, the corresponding Ksp value may be found, followed byThe minimum pH required for precipitation of the metal hydroxide can be calculated.
As an alternative implementation, in the embodiment of the present invention, the second calculation unit 310 obtains a known acid-base volume ratio formula, where the acid-base volume ratio formula may be a formula for calculating the volume ratio of the acid or the base required for the acid-base neutralization reaction.
As an alternative implementation, in an embodiment of the present invention, the second calculation unit 310 may determine a chemical reaction equation between the acid in the etching waste liquid and the alkali in the alkali neutralization solution, for example, assuming that the acid in the copper-containing etching waste liquid is HCl and the alkali in the alkali neutralization solution is NaOH, the reaction equation may be written as:
HCl (aq) +NaOH (aq). Fwdarw.NaCl (aq) +H2O (l), in which reaction the acid and base react to form a salt and water. The second calculation unit 310 may then determine the molar ratio of the acid and the base according to the molar ratio in the reaction equation, for example, if the molar ratio in the reaction equation is 1:1, the molar ratio of the acid and the base in the basic neutralization solution in the waste liquid is 1:1, and then, in consideration of the relationship between the molar concentration and the volume, the second calculation unit 310 may convert the molar ratio into the volume ratio, for example, if the molar ratio of the acid and the base in the basic neutralization solution in the waste liquid is 1:1, and the volumes of the acid and the base in the basic neutralization solution in the waste liquid are respectively And->The volume ratio is: />:/>=1:1, which means that the volume ratio of waste liquid and alkaline neutralizing solution is equal.
As an alternative implementation, in an embodiment of the present invention, if the current potential value of the copper-containing etching waste liquid is lower than the target threshold value, the pretreatment unit 302 may add an oxidizing agent (such as hydrogen peroxide or potassium permanganate) to increase the oxidation-reduction reaction and increase the potential value, and if the current potential value is higher than the target threshold value, the pretreatment unit 302 may add a reducing agent (such as sulfite or sodium thiosulfate) to promote the reduction reaction and decrease the potential value. The ph of the waste liquid also affects the potential value, and if necessary, the pretreatment unit 302 may further add an acid or an alkali to adjust the ph of the waste liquid, thereby affecting the potential value.
As an alternative implementation manner, in the embodiment of the present invention, when the treating agent is added, the first adding unit 303 may control the adding amount according to the volume of the waste liquid and the requirement of the target threshold, and specifically may refer to the relevant treating agent use instruction or a manually set standard or a system set calculation program.
As an alternative embodiment, in an embodiment of the present invention, the aeration power value is the energy used to introduce gas into the waste liquid by means of bubbles or mechanical means. The first treatment unit 304 may select an appropriate aeration power value, typically expressed in units of volume (e.g., power per liter) in W/m, based on the characteristics of the waste stream and the desired redox reaction. The specific aeration power value depends on the viscosity of the waste liquid, the gas transmission efficiency and the required redox reaction performance.
As an alternative implementation manner, in an embodiment of the present invention, the first processing unit 304 may sequentially perform stirring and aeration treatment on the neutralized copper-containing etching waste liquid according to the specifications and operation requirements of the apparatus according to the calculated stirring frequency and aeration power value, so as to ensure that the stirring apparatus and the aeration system can provide the required stirring frequency and aeration power.
As an alternative embodiment, in the embodiment of the present invention, the calculating and adding unit 306 may calculate the secondary adding amount of the alkaline neutralizing solution according to the pH deviation value, and the size of the secondary adding amount depends on the volume of the waste liquid, the pH change desired to be achieved, and the concentration of the alkaline neutralizing solution, and the calculating and adding unit 306 may calculate the adding amount using the volume or the molar concentration of the alkaline solution.
As an alternative implementation manner, in the embodiment of the present invention, the calculating and adding unit 306 may use an accurate instrument or device to add the alkaline neutralization solution to the waste liquid according to the secondary adding amount under an appropriate condition according to the calculation result.
As an optional implementation manner, in the embodiment of the invention, the treatment process can be monitored and adjusted in real time according to the set parameters and the set threshold value, so that the accuracy and the efficiency of waste liquid treatment are improved, and the human error and the treatment time are reduced.
As an alternative implementation, in the present example, the present application may stably maintain the desired processing conditions and results through an automated control and feedback mechanism to ensure that the process remains consistent from lot to lot.
As an alternative implementation manner, in the embodiment of the present invention, the present application may reduce the need for manual operations. This helps to reduce labor costs and reduces the impact of human factors on the process.
As an optional implementation manner, in the embodiment of the invention, various parameters and indexes in the waste liquid treatment process can be monitored in real time, and corresponding adjustment is made, so that potential problems or abnormal conditions can be found and corrected in time, and the safety of the treatment process is improved.
As an alternative implementation, in the embodiment of the present invention, the present application may record and store various data and parameters during the treatment process, and these data may be used for subsequent analysis and optimization, to help improve the effect and flow of the waste liquid treatment.
It can be seen that implementing the treatment system depicted in fig. 4 enables more accurate pH adjustment.
In addition, implementing the treatment system described in FIG. 4 can improve the accuracy and efficiency of waste liquid treatment.
Example IV
Referring to fig. 5, fig. 5 is a schematic diagram illustrating a structure of another processing system according to an embodiment of the invention. Wherein the processing system of fig. 5 is optimized by the processing system of fig. 4. In comparison to the processing system of fig. 4, the first computing unit 309 of fig. 5 comprises:
the first calculating subunit 3091 is configured to calculate a minimum PH of metal hydroxide precipitate required for the current copper-containing etching waste liquid.
The second calculating subunit 3092 is configured to calculate, by using a surface fitting algorithm, a PH temperature compensation value required for the current copper-containing etching waste liquid after obtaining the current voltage value and the current temperature value of the current copper-containing etching waste liquid.
A determining subunit 3093, configured to combine the minimum PH value of the metal hydroxide precipitate and the PH temperature compensation value to determine the target PH value.
As an alternative embodiment, in an embodiment of the present invention, the second computing subunit 3092 may collect a series of sample data related to the copper-containing etching waste liquid, including voltage values, temperature values, and corresponding pH values, to ensure that the data covers a range of waste liquid at different temperatures. The second computing sub-unit 3092 may then pre-process the collected sample data, for example, to check whether the data has outliers or missing values, and perform the necessary data cleaning and processing. The second computing sub-unit 3092 may then select an appropriate surface fitting model (e.g., quadratic polynomial, polynomial regression, gaussian process regression, etc.) to fit the data based on the actual situation and the characteristics of the data distribution. The second computing subunit 3092 may then fit a pH model that is dependent on voltage and temperature using the voltage value and the temperature value as independent variables and the pH value as dependent variable. Finally, the second calculating subunit 3092 may calculate, according to the current voltage value and the current temperature value of the current copper-containing etching waste liquid, a corresponding pH value by using a pH model obtained by fitting, and use a difference between the calculated pH value and an actually measured pH value as a temperature compensation value, that is, a pH compensation value=the calculated pH value-the actually measured pH value, and obviously, if the pH compensation value is a positive number, it means that the waste liquid needs to be compensated by adding the corresponding pH value; if the pH compensation value is negative, it means that the waste liquid needs to be reduced by the corresponding pH value to compensate.
In comparison to the processing system of fig. 4, the first computing sub-unit 3091 of fig. 5 includes:
the first calculation module 30911 is used for calculating the quotient of the metal hydroxide solubility product of the current copper-containing etching waste liquid divided by the metal ion concentration in the copper-containing etching waste liquid to obtain the hydroxide ion concentration in the current copper-containing etching waste liquid; wherein N is the metal ion order in the current copper-containing etching waste liquid.
A second calculation module 30912 divides the ion product constant of water by the hydroxide ion concentration to calculate the minimum PH of the metal hydroxide precipitate.
In comparison to the processing system of fig. 4, the preprocessing unit 302 of fig. 5 includes:
and a processing subunit 3021, configured to perform aeration treatment on the current copper-containing etching waste liquid according to the pretreatment aeration power value after calculating the pretreatment aeration power value required by the current copper-containing etching waste liquid according to the current copper-containing etching waste liquid volume.
As an optional implementation manner, in the embodiment of the invention, after the system determines the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution, a flowmeter of a copper-containing etching waste liquid storage tank is opened, then a self-priming pump of the copper-containing etching waste liquid storage tank is opened, when the flowmeter detects that the volume reaches a set value, the self-priming pump is closed (the flowmeter controls the opening and closing of the pump), meanwhile, a liquid level meter of the neutralization reaction kettle receives information of the volume required by the copper-containing etching waste liquid reaction sent by the system, and if the liquid level is higher than the copper-containing etching waste liquid volume required by a formula, the self-priming pump also stops conveying raw materials, so that double guarantees of quantitative pumping of the self-priming pump and verification of the volume by the liquid level meter in the neutralization kettle are realized. And when the self-priming pump stops pumping acid water, the system can automatically open the Roots blower valve to perform aeration treatment on the copper-containing etching waste liquid.
In the embodiment of the invention, the aeration power of the pretreatment of the acidic copper-containing waste liquid increases along with the increase of the addition value of the copper-containing etching waste liquid, so that the aeration power value is increased by X cubic meters of air per minute every 1 liter of copper-containing etching waste liquid, and the final aeration power needs to be added with the correction coefficient of Y cubic meters of air per minute. I.e. the present application。
A detection subunit 3022 for detecting whether the current potential value of the copper-containing etching waste liquid reaches a specified threshold value.
As an optional implementation manner, in the embodiment of the invention, after aeration treatment is started, the system can start an ORP potentiometer, and after normal reading of the ORP potentiometer is obtained, if the current potential value of the copper-containing etching waste liquid is more than or equal to a specified threshold value, the system enters the next link; if the potential value of the current copper-containing etching waste liquid is smaller than the designated threshold value, starting a hydrogen peroxide mechanical diaphragm metering pump to start adding hydrogen peroxide into the current copper-containing etching waste liquid until the potential value of the current copper-containing etching waste liquid is larger than or equal to the designated threshold value, closing the hydrogen peroxide metering pump, then starting a timer by the system, closing the timer after a certain time, then starting an ORP meter to read the potential value again, if the potential value of the current copper-containing etching waste liquid is larger than or equal to the designated threshold value, entering the next link by the system, otherwise, returning to the upper stage to perform hydrogen peroxide adding again. And after the system obtains the data that the potential value of the current copper-containing etching waste liquid is more than or equal to the specified threshold value, the system reads the data of the hydrogen peroxide flowmeter to obtain the hydrogen peroxide usage amount. And after the pretreatment of the current copper-containing etching waste liquid is finished, the system can close the Roots blower air supply valve to stop aeration.
And a third calculation subunit 3023, configured to calculate an addition amount of hydrogen peroxide to be added according to an oxidation volume ratio between the hydrogen peroxide solution and the monovalent copper content when the detection subunit 3022 detects that the potential value of the current copper-containing etching waste liquid does not reach the specified threshold value, and perform addition of the hydrogen peroxide solution to the current copper-containing etching waste liquid according to the addition amount of hydrogen peroxide.
As an alternative embodiment, in the present example, since the subsequent process requires the existence of copper in a divalent form, the copper-containing etching waste liquid pretreatment of the present application is an oxidation reaction for converting all monovalent copper into divalent copper, and when the potential value is above a specified threshold value, the monovalent copper content is hardly found, and thus the specified threshold value can be regarded as the end point of the conversion reaction.
As an alternative embodiment, in the embodiment of the present invention, since the oxidation volume ratio between the hydrogen peroxide solution and the monovalent copper content is known, that is, 27.5% of hydrogen peroxide of 120L may oxidize 0.6% of the monovalent copper content, and the change amount of the electric potential is about 5mv, the present application may perform the supplementation of the electric potential value according to the oxidation volume ratio.
As an alternative implementation manner, in the embodiment of the present invention, an oxidation reaction equation between monovalent copper and hydrogen peroxide may be determined first, then, a molar ratio between monovalent copper and hydrogen peroxide may be determined according to a molar coefficient in the reaction equation, and according to the coefficient in the reaction equation, it is known that one mole of hydrogen peroxide is required for every two moles of monovalent copper, and since the concentration of hydrogen peroxide is generally expressed in terms of volume percent, it is required to convert the molar ratio into the volume ratio, the system may convert the molar ratio into the volume ratio according to the density and the molar ratio of hydrogen peroxide, and then calculate the required added hydrogen peroxide amount according to the concentration of monovalent copper in the copper-containing etching waste liquid and the required volume ratio.
As an alternative implementation, in an embodiment of the present invention, the detecting subunit 3022 is further configured to detect, again, whether the potential value of the current copper-containing etching waste liquid reaches the specified threshold value after the current copper-containing etching waste liquid is left to stand for a period of time.
And an execution subunit 3024 for executing the operation of adding the alkaline neutralizing solution to the current copper-containing etching waste liquid according to the volume ratio relationship when the detection subunit 3022 detects again that the potential value of the current copper-containing etching waste liquid reaches the specified threshold value.
In comparison to the processing system of fig. 4, the first processing unit 304 of fig. 5 comprises:
an acquisition subunit 3041 for acquiring a stirring power coefficient value and a stirring power correction coefficient, respectively, which increase with an increase in volume.
And a fourth calculating subunit 3042, configured to add the product of the multiplied total volume of the material to be added and the stirring power correction coefficient to calculate the stirring frequency.
As an alternative implementation, in an embodiment of the present invention, the acquiring subunit 3041 is further configured to acquire the aeration power coefficient value and the aeration power correction coefficient that increase with an increase in volume, respectively.
As an alternative implementation, in an embodiment of the present invention, the fourth calculating subunit 3042 is further configured to add the product of the multiplied total input material volume and the aeration power coefficient value to the aeration power correction coefficient to calculate the aeration power value.
As an alternative implementation, in this embodiment of the present invention, the fourth calculating subunit 3042 is further configured to add the product obtained by multiplying the total secondary input material volume by the stirring power coefficient value to the stirring power correction coefficient, so as to calculate the secondary stirring frequency.
As an alternative implementation, in an embodiment of the present invention, the fourth calculating subunit 3042 is further configured to add the product of the current copper-containing etching waste liquid volume multiplied by the aeration power coefficient value to the aeration power correction coefficient to calculate the pretreatment aeration power value.
In the embodiment of the invention, the stirring power of the neutralization reaction kettle stirrer increases along with the increase of the total volume of the fed raw materials, and further the stirring power increases every 1 liter of total volume of the raw materialsHz, final->The power needs to be added with a correction factor of (-1/Y) Hz. I.e. & gt of the present application>。
As an optional implementation manner, in the embodiment of the invention, after the pretreatment of the copper-containing etching waste liquid is completed, the system can send a first-stage signal to the frequency converter of the neutralization reaction kettle stirrer, the neutralization reaction kettle stirrer is started to adjust to a designated frequency, the system can add the alkaline neutralization solution according to the volume ratio relation of the copper-containing etching waste liquid and the alkaline neutralization solution, and meanwhile, the system can adjust the stirring frequency according to the volume of the total amount of added raw materials.
As an alternative implementation mode, in the embodiment of the invention, after all materials are put (after an alkaline neutralizing solution self-priming pump is closed and a reaction kettle liquid level meter verifies that the input amount is accurate), a neutralizing reaction kettle stirrer is closed, a Roots blower is started to aerate the neutralizing materials, a timer is started to count after the blower is started, the materials can fully react, and after a certain time, a system can shut down the Roots blower to stop aeration and count time, so that the materials are kept still.
In comparison to the processing system of fig. 4, the processing system of fig. 5 includes:
the third calculating unit 312 is configured to calculate the height of the neutralized copper-containing etching waste liquid according to the volume formula based on the neutralized copper-containing etching waste liquid and the bottom area of the device for containing the neutralized copper-containing etching waste liquid after the neutralized copper-containing etching waste liquid is left standing for a period of time and before the second detecting unit 305 detects whether the PH of the supernatant of the neutralized copper-containing etching waste liquid is within the acceptable threshold range.
And a second determining unit 313 for determining the liquid level position of the neutralized copper-containing etching waste liquid based on the height of the neutralized copper-containing etching waste liquid.
An acquisition unit 314 for acquiring a PH value at a specified distance position below the liquid level position; wherein the PH value at the designated distance position is the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid.
In an embodiment of the invention, after the copper-containing etching waste liquid is kept stand for a period of time after neutralization, a mechanical arm (a pH meter is arranged on the mechanical arm) can be started, according to the liquid level information fed back by the liquid level meter of the neutralization reaction kettle, the mechanical arm vertically immerses the probe of the pH meter into the supernatant (the probe is completely inserted into the supernatant and is about 5cm away from the liquid level, the pH value is obtained after the reading is stabilized, if the pH value of the supernatant is between 5.6 and 5.8, the neutralization reaction is completed, the mechanical arm withdraws the pH meter from the liquid level, and the pH meter is inserted into the pH meter cleaning device to be automatically flushed with purified water and returned to the buffer solution for soaking for standby, and if the pH value of the supernatant is not between 5.6 and 5.8, the mechanical arm withdraws the pH meter from the liquid level and automatically flushes the pH meter into the buffer solution for standby after the pH meter is inserted into the pH meter cleaning device to be automatically flushed with purified water.
As an alternative implementation mode, in the embodiment of the invention, when the reaction kettle is a cylindrical device with a flat bottom surface, the system can be utilizedTo calculate the position to be reached by the glass electrode at the bottom of the pH meter probe, wherein X is the distance X cm below the liquid level of the neutralized copper-containing etching waste liquid.
In comparison to the processing system of fig. 4, the calculation and delivery unit 306 of fig. 5 comprises:
a fifth calculation subunit 3061 for utilizingCalculating the hydrogen ion concentration in the neutralized copper-containing etching waste liquid>。
A sixth calculation subunit 3062 for using if the pH of the supernatant of the neutralized copper-containing etching waste liquid is less than the minimum value of the acceptable threshold rangeAnd calculating the secondary throwing amount.
And a delivering subunit 3063, configured to deliver the alkaline neutralizing solution to the neutralized copper-containing etching waste liquid according to the secondary delivering amount.
As an alternative embodiment, in the embodiment of the present invention, the sixth calculating subunit 3062 is further configured to utilize if the pH of the supernatant of the neutralized copper-containing etching waste liquid is greater than the maximum value within the acceptable threshold rangeAnd calculating the secondary throwing amount.
As an alternative embodiment, in the embodiment of the present invention, the delivering subunit 3063 is further configured to deliver the acidic neutralization solution to the neutralized copper-containing etching waste liquid according to the second delivery amount.
Wherein,is the concentration of hydrogen ions in the solution when the PH value is within the acceptable threshold value range,the concentration of hydrogen ions in the solution is neutralized for alkalinity.
As an optional implementation manner, in the embodiment of the invention, after the system enters the fine adjustment link, the neutralizing reaction kettle stirrer can be started to adjust to the designated frequency, after the stirring is started, the timer can be started to stir the materials, then the fine adjustment adding amount can be set according to the designated formula to carry out the adding of the materials, after the adding of the fine adjustment adding amount is completed, the system can close the neutralizing reaction kettle stirrer, the timer is started to allow the materials to stand, and the pH detection process is repeated again to ensure that the pH is within the range of the qualified threshold value, and the neutralizing reaction can be completed.
As an optional implementation manner, in the embodiment of the present invention, the amount of the treatment agent to be applied may be accurately determined according to the target parameter and the characteristics of the waste liquid through calculation, which helps to avoid excessive or insufficient application and ensure the best treatment effect.
As an alternative implementation manner, in the embodiment of the present invention, by adding the treatment agent according to the calculation result, a consistent treatment effect can be maintained between different batches, which helps to improve the repeatability and stability of the waste liquid treatment.
As an alternative implementation manner, in the embodiment of the invention, by accurately calculating the dosage of the treating agent, the excessive use of the treating agent can be avoided, so that the treating cost is reduced. Meanwhile, the waste product generated in the waste liquid treatment process is reduced.
As an alternative implementation manner, in the embodiment of the invention, the application determines the dosage of the treating agent through calculation, so that the degree of judgment of an operator is reduced, and the risk of operation errors is reduced.
As an optional implementation manner, in the embodiment of the invention, the dosage of the treating agent can be adjusted according to the actual condition of the waste liquid through calculation, so that a better treatment effect is achieved, and the purification efficiency and quality of the waste liquid are improved.
It can be seen that implementing another processing system as described in fig. 5 can improve recognition accuracy.
Furthermore, implementing the processing system depicted in FIG. 5 can reduce the probability of an incident.
Example five
Referring to fig. 6, fig. 6 is a schematic diagram illustrating a structure of another processing system according to an embodiment of the invention. As shown in fig. 6, the processing system may include:
a memory 501 in which executable program codes are stored;
a processor 502 coupled to the memory 501;
the processor 502 invokes executable program codes stored in the memory 501 to execute any one of the intelligent processing methods of the copper-containing etching waste liquid shown in fig. 1-2.
The embodiment of the invention discloses a computer readable storage medium which stores a computer program, wherein the computer program enables a computer to execute any one of the intelligent treatment methods of copper-containing etching waste liquid shown in fig. 1-2.
The embodiments of the present invention also disclose a computer program product, wherein the computer program product, when run on a computer, causes the computer to perform some or all of the steps of the method as in the method embodiments above.
Those of ordinary skill in the art will appreciate that all or part of the steps of the various methods of the above embodiments may be implemented by hardware associated with a program that may be stored in a computer-readable storage medium, including Read-Only Memory (ROM), random-access Memory (Random Access Memory, RAM), programmable Read-Only Memory (Programmable Read-Only Memory, PROM), erasable programmable Read-Only Memory (Erasable Programmable Read Only Memory, EPROM), one-time programmable Read-Only Memory (OTPROM), electrically erasable programmable Read-Only Memory (EEPROM), compact disc Read-Only Memory (Compact Disc Read-Only Memory, CD-ROM), or other optical disk Memory, magnetic disk Memory, tape Memory, or any other medium that can be used to carry or store data that is readable by a computer.
The above describes in detail a method and a system for treating copper-containing etching waste liquid disclosed in the embodiments of the present invention, and specific examples are applied to illustrate the principles and embodiments of the present invention, and the above description of the embodiments is only for helping to understand the method and core ideas of the present invention; meanwhile, as those skilled in the art will vary in the specific embodiments and application scope according to the idea of the present invention, the present disclosure should not be construed as limiting the present invention in summary.
Claims (10)
1. An intelligent treatment method for copper-containing etching waste liquid is characterized by comprising the following steps:
detecting whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution exists or not; if yes, preprocessing the current copper-containing etching waste liquid to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value;
the alkaline neutralization solution is put into the current copper-containing etching waste liquid according to the volume ratio relation;
after the stirring frequency and the aeration power value required by the copper-containing etching waste liquid after neutralization are calculated according to the total volume of the materials put in, stirring and aerating the copper-containing etching waste liquid after neutralization according to the stirring frequency and the aeration power value;
After the neutralized copper-containing etching waste liquid is kept stand for a period of time, detecting whether the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid is within a qualified threshold value range; if not, calculating the secondary adding amount of the alkaline neutralization solution according to the pH deviation value of the supernatant of the neutralized copper-containing etching waste liquid, and adding the alkaline neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
after the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization is calculated according to the total volume of the materials fed in the secondary, stirring the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency;
after the secondary neutralized copper-containing etching waste liquid is kept stand for a period of time, if the PH value of the supernatant liquid of the secondary neutralized copper-containing etching waste liquid is within the qualified threshold value range, confirming that the current copper-containing etching waste liquid treatment process is completed;
if the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution is detected to be absent, calculating a target PH value required by metal hydroxide precipitation of the current copper-containing etching waste liquid;
calculating the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula and the target PH value;
And executing the operation of preprocessing the current copper-containing etching waste liquid so as to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value.
2. The method of claim 1, wherein calculating the target PH required for precipitation of the metal hydroxide of the current copper-containing etching waste stream comprises:
calculating the minimum PH value of metal hydroxide precipitation required by the current copper-containing etching waste liquid;
after the current voltage value and the current temperature value of the current copper-containing etching waste liquid are obtained, calculating a PH temperature compensation value required by the current copper-containing etching waste liquid by using a surface fitting algorithm;
and combining the lowest PH value of the metal hydroxide precipitate and the PH temperature compensation value to determine the target PH value.
3. The method of claim 2, wherein calculating the minimum PH of the metal hydroxide precipitate required for the current copper-containing etching waste stream comprises:
calculating the square root of the quotient of the metal hydroxide solubility of the current copper-containing etching waste liquid and the metal ion concentration in the copper-containing etching waste liquid to obtain the hydroxide ion concentration in the current copper-containing etching waste liquid; wherein, N is the metal ion order in the current copper-containing etching waste liquid;
The ion product constant of water is divided by the hydroxide ion concentration to calculate the minimum PH of the metal hydroxide precipitate.
4. The method of claim 1, wherein the pre-treating the current copper-containing etching waste liquid to bring the potential value of the current copper-containing etching waste liquid to a specified threshold value comprises:
after the pretreatment aeration power value required by the current copper-containing etching waste liquid is calculated according to the volume of the current copper-containing etching waste liquid, carrying out aeration treatment on the current copper-containing etching waste liquid according to the pretreatment aeration power value;
detecting whether the potential value of the current copper-containing etching waste liquid reaches a specified threshold value or not; if not, calculating the addition amount of the hydrogen peroxide to be added according to the oxidation volume ratio between the hydrogen peroxide solution and the monovalent copper content, and adding the hydrogen peroxide solution to the current copper-containing etching waste liquid according to the addition amount of the hydrogen peroxide;
after the current copper-containing etching waste liquid is kept stand for a period of time, detecting whether the potential value of the current copper-containing etching waste liquid reaches the specified threshold value or not again; and if so, executing the operation of throwing the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio relation.
5. The method of claim 4, wherein calculating the stirring frequency and the aeration power value required for the neutralized copper-containing etching waste liquid according to the total volume of the charged material comprises:
respectively obtaining a stirring power coefficient value and a stirring power correction coefficient which increase along with the increase of the volume;
adding the product of the multiplied total volume of the materials to be added and the stirring power correction coefficient to calculate the stirring frequency;
respectively obtaining an aeration power coefficient value and an aeration power correction coefficient which increase along with the increase of the volume;
adding the product of the multiplied total volume of the materials to be added and the aeration power correction coefficient to calculate the aeration power value;
and calculating the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization according to the volume of the secondary total put material, wherein the method comprises the following steps:
adding the product of the multiplied total volume of the secondary added material and the stirring power coefficient value to the stirring power correction coefficient to calculate the secondary stirring frequency;
And calculating a pretreatment aeration power value required by the current copper-containing etching waste liquid according to the current copper-containing etching waste liquid volume, wherein the pretreatment aeration power value comprises:
and adding the product obtained by multiplying the current copper-containing etching waste liquid volume by the aeration power coefficient value and the aeration power correction coefficient to calculate the pretreatment aeration power value.
6. The method of claim 1, wherein the method further comprises, after the post-neutralization copper-containing etching waste liquid has been allowed to stand for a period of time, and before the detecting whether the PH of the supernatant of the post-neutralization copper-containing etching waste liquid is within a pass threshold value:
calculating the height of the neutralized copper-containing etching waste liquid by utilizing a volume formula according to the neutralized copper-containing etching waste liquid and the bottom area of a holding device for holding the neutralized copper-containing etching waste liquid;
determining the liquid level position of the neutralized copper-containing etching waste liquid according to the height of the neutralized copper-containing etching waste liquid;
acquiring the PH value at a specified distance below the liquid level; the PH value of the position with the specified distance is the PH value of the supernatant liquid of the neutralized copper-containing etching waste liquid.
7. The method according to any one of claims 1 to 6, wherein calculating the secondary dosage of the alkaline neutralization solution according to the PH deviation value of the supernatant of the neutralized copper-containing etching waste liquid, and adding the alkaline neutralization solution to the current copper-containing etching waste liquid according to the secondary dosage comprises:
by means ofCalculating the hydrogen ion concentration in the neutralized copper-containing etching waste liquid>；
If the PH value of the supernatant of the neutralized copper-containing etching waste liquid is smaller than the minimum value of the qualified threshold range, utilizingCalculating the secondary throwing amount;
the alkaline neutralization solution is added into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
if the PH value of the supernatant of the neutralized copper-containing etching waste liquid is greater than the qualification threshold valueMaximum of the range, usingCalculating the secondary throwing amount;
the acidic neutralization solution is added into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
wherein the saidFor the solution hydrogen ion concentration at a pH value within said qualification threshold range, said +.>The hydrogen ion concentration in the alkaline neutralization solution.
8. A processing system, the processing system comprising:
The first detection unit is used for detecting whether the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution exists or not;
the pretreatment unit is used for pretreating the current copper-containing etching waste liquid when the first detection unit detects that the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralization solution exists, so that the potential value of the current copper-containing etching waste liquid reaches a specified threshold value;
the first throwing unit is used for throwing the alkaline neutralizing solution into the current copper-containing etching waste liquid according to the volume ratio relation;
the first treatment unit is used for sequentially stirring and aerating the neutralized copper-containing etching waste liquid according to the stirring frequency and the aeration power value after calculating the stirring frequency and the aeration power value required by the neutralized copper-containing etching waste liquid according to the total volume of the materials put in;
the second detection unit is used for detecting whether the PH value of the supernatant of the neutralized copper-containing etching waste liquid is within a qualified threshold value range after the neutralized copper-containing etching waste liquid is kept stand for a period of time;
the calculating and adding unit is used for calculating the secondary adding amount of the alkaline neutralization solution according to the pH deviation value of the supernatant of the neutralized copper-containing etching waste liquid when the second detection unit detects that the pH value of the supernatant of the neutralized copper-containing etching waste liquid is not in the qualified threshold range, and adding the alkaline neutralization solution into the neutralized copper-containing etching waste liquid according to the secondary adding amount;
The second treatment unit is used for stirring the copper-containing etching waste liquid after secondary neutralization according to the secondary stirring frequency after calculating the secondary stirring frequency required by the copper-containing etching waste liquid after secondary neutralization according to the total volume of the materials fed in the secondary;
a first determining unit, configured to determine that the current copper-containing etching waste liquid treatment process is completed if the PH value of the supernatant of the copper-containing etching waste liquid after the secondary neutralization is within the acceptable threshold value range after the copper-containing etching waste liquid after the secondary neutralization is left for a period of time;
the first calculating unit is used for calculating a target PH value required by metal hydroxide precipitation of the current copper-containing etching waste liquid when the first detecting unit detects that the volume ratio relation of the current copper-containing etching waste liquid and the alkaline neutralizing solution does not exist;
the second calculating unit is used for calculating the volume ratio relation between the current copper-containing etching waste liquid and the alkaline neutralizing solution according to an acid-base volume ratio formula and the target PH value;
and the execution unit is used for executing the operation of preprocessing the current copper-containing etching waste liquid so as to enable the potential value of the current copper-containing etching waste liquid to reach a specified threshold value.
9. The processing system of claim 8, wherein the first computing unit comprises:
a first calculating subunit, configured to calculate a minimum PH value of metal hydroxide precipitation required by the current copper-containing etching waste liquid;
the second calculating subunit is used for calculating a PH temperature compensation value required by the current copper-containing etching waste liquid by using a surface fitting algorithm after the current voltage value and the current temperature value of the current copper-containing etching waste liquid are obtained;
and the determining subunit is used for combining the lowest PH value of the metal hydroxide precipitation and the PH temperature compensation value to determine the target PH value.
10. A processing system, the processing system comprising:
a memory storing executable program code;
a processor coupled to the memory;
the processor invokes the executable program code stored in the memory to perform the intelligent treatment method of copper-containing etching waste liquid as claimed in any one of claims 1 to 7.
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