Large-scale rapid detection method for COD in copper acid etching solution and application of large-scale rapid detection method

Abstract

The invention discloses a large-scale rapid detection method for COD (chemical oxygen demand) in copper acid etching liquid and application, and the method comprises the following steps: S1, diluting the copper acid etching liquid as a standard solution; s2, testing the sugar degree of the standard solution; s3, testing the COD value of the standard solution; s4, fitting the sugar degree and the COD value of the standard solution into a linear curve; and S5, testing the sugar degree of the to-be-tested copper acid etching liquid, and corresponding the sugar degree to the linear curve to obtain the COD value of the to-be-tested copper acid etching liquid. According to the method, reagents do not need to be consumed, the sample does not need to be pretreated, and for the copper acid etching liquid sample, COD detection is low in cost, free of pollution and environmentally friendly. After the fitting curve is established, only the sugar degree in the copper acid etching liquid sample needs to be measured in the later period, the COD content can be obtained by substituting the sugar degree into the fitting equation, consumed time is short, and detection is rapid.

Description

Technical Field

[0001] The present invention relates to the field of testing or analyzing materials by measuring the chemical properties of materials, and in particular to a method for rapid mass detection of COD in copper acid etching solution and application thereof. Background Art

[0002] Copper acid etching solution contains a large amount of substances such as cupric chloride, cuprous chloride, hydrogen peroxide and hydrochloric acid. The chemical oxygen demand of waste liquid treatment is high. It usually needs to be treated by neutralization, precipitation, filtration, etc. to remove some oxides and reduce oxygen consumption to meet the discharge standard. Factories need to conduct a large number of COD tests before discharging wastewater. Because the COD value of copper acid etching solution is high and the digestion time is long, the COD value test of copper acid etching solution is time-consuming. Therefore, it is crucial to develop a detection method that can quickly and massively detect the COD value of copper acid etching solution.

[0003] Chinese invention patent CN110320299B discloses a rapid detection method for COD in organic wastewater. Under gas chromatograph detection conditions, organic wastewater is completely vaporized, and various types of organic matter have a strong response in the form of combined peaks on the hydrogen flame detector. The method has high sensitivity and stable response. The measurement time is within 5 minutes, and the measurement speed is fast. However, using a gas chromatograph for detection is expensive in terms of instrumentation, and long-term detection of heavily contaminated samples by the gas chromatograph can reduce sensitivity. Chinese invention patent application CN109696411A discloses a rapid detection method for soluble COD in purified terephthalic acid (PTA) wastewater. By analyzing the ultraviolet spectral fingerprint characteristics of PTA wastewater, combining statistical analysis to find the PTA characteristic spectrum, and establishing a linear relationship with soluble COD, the time cost of COD detection can be greatly reduced. However, using a UV-visible spectrophotometer to measure absorbance still requires a long time. Summary of the Invention

[0004] In order to develop a detection method that can quickly and in large quantities detect the COD value of copper acid etching solution, a first aspect of the present invention provides a large-scale rapid detection method for COD in copper acid etching solution, comprising the following steps:

[0005] S1: prepare standard solution of copper acid etching solution;

[0006] S2: sugar content of test standard solution;

[0007] S3: COD value of test standard solution;

[0008] S4: Fit the sugar content and COD value of the standard solution into a linear curve;

[0009] S5: testing the sugar content of the copper acid etching solution to be tested, and corresponding it to the linear curve to obtain the COD value of the copper acid etching solution to be tested.

[0010] As an embodiment, the mass concentration of the solute in the standard solution is 0-30%, excluding 0.

[0011] As an embodiment, the solute in the standard solution includes but is not limited to at least one of an organic acid, an organic base, and hydrogen peroxide.

[0012] As an implementation manner, the linear curve is y=11288x.

[0013] As an embodiment, the x value in the linear curve is the sugar content, and the sugar content is expressed in percentage, and the value before the percentage sign is substituted.

[0014] As an embodiment, the R of the linear curve 2 =0.9881.

[0015] As an embodiment, the sugar content is obtained by testing with a digital sugar meter, the content is expressed as a percentage, and the result is rounded to one decimal place.

[0016] As an embodiment, the method for testing the COD value of the standard solution in step S3 includes at least one of potassium dichromate method, rapid digestion spectrophotometry, rapid digestion-colorimetry, potassium permanganate index method, electrochemical method, and biosensor method.

[0017] As an embodiment, the specific detection steps of the rapid digestion spectrophotometry are:

[0018] Prepare digestion solution;

[0019] Mix the copper acid etching solution to be tested with the digestion solution and digest at 160-170℃ for 15-20min;

[0020] After digestion, put it into the spectrophotometer to test the COD value.

[0021] As an embodiment, the COD detection time of the copper acid etching solution to be tested in step S5 is ≤1 min.

[0022] As an embodiment, the values of sugar content and COD value in the fitting curve are shown in Table 1.

[0023] Table 1

[0024]

[0025]

[0026]

[0027]

[0028] The fitting curve obtained from the data in Table 1 is shown in Figure 1 .

[0029] During the experiment, the inventors discovered that the COD detection method for copper acid etching solution is cumbersome, requiring pre-treatment such as dilution, digestion, and cooling, resulting in poor timeliness. Furthermore, the detection process also requires the use of chemicals such as oxidants and color developers, leading to serious chemical pollution. During the experiment, the inventors discovered that the COD content of the copper acid etching solution can be quickly determined by detecting the sugar content of the copper acid etching solution. The sugar content and COD value in the copper acid etching solution are linearly related, y = 11288x. Using a digital sugar meter, the COD value of the copper acid etching solution can be directly determined by fitting the "sugar content-COD" curve. This method has low deviation, is simple to detect, and is time-efficient.

[0030] As an embodiment, the copper acid etching solution includes an etching solution used in a copper process for panel manufacturing.

[0031] As an embodiment, the copper acid etching solution also includes waste liquid after copper process etching.

[0032] The second aspect of the present invention provides an application of a large-scale rapid detection method for COD in copper acid etching solutions, which is applied to the detection of large quantities of copper acid etching solutions, with the detection quantity being ≥50.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The method for rapid mass detection of COD in copper acid etching solution of the present invention does not require consumption of reagents and sample pretreatment. For copper acid etching solution samples, COD detection cost is low, pollution-free, and environmentally friendly.

[0035] (2) In the method for rapid mass detection of COD in copper acid etching solution of the present invention, after the fitting curve is established, it is only necessary to determine the sugar content in the copper acid etching solution sample and substitute it into the fitting equation to obtain the COD content, which is time-consuming and rapid.

[0036] (3) Compared with the traditional COD detection method, the large-scale rapid detection method of COD in the copper acid etching solution of the present invention does not require pre-treatment such as dilution, digestion, and cooling, does not require chemical reagents such as oxidants and color developers, and does not cause environmental pollution.

[0037] (4) In the method for rapid mass detection of COD in the copper acid etching solution of the present invention, the sugar content is measured using a digital sugar meter. The instrument has low cost and is easy to use. The instrument only needs to be rinsed with clean water before and after detection. The instrument has low cost. In addition, the digital sugar meter is simple to use, has low learning cost, is not easy to damage, and has low maintenance cost.

[0038] (5) The method for rapid mass detection of COD in copper acid etching solution of the present invention is highly applicable to factory-produced sample detection with high COD values. The COD determination process is direct and simple, and the COD value can be obtained within one minute. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The figure is a fitting curve of COD and sugar content in the copper acid etching solution of the present invention. DETAILED DESCRIPTION

[0040] Example

[0041] A method for rapid mass detection of COD in copper acid etching solution comprises the following steps:

[0042] S1: prepare standard solution of copper acid etching solution;

[0043] S2: sugar content of test standard solution;

[0044] S3: COD value of test standard solution;

[0045] S4: Fit the sugar content and COD value of the standard solution into a linear curve;

[0046] S5: testing the sugar content of the copper acid etching solution to be tested, and corresponding it to the linear curve to obtain the COD value of the copper acid etching solution to be tested.

[0047] The mass concentration of the solute in the standard solution is 0-30%, excluding 0.

[0048] The linear curve is y=11288x; R 2 =0.9881, fitting curve see Figure 1 .

[0049] The method for testing the COD value of the standard solution in step S3 is a rapid digestion spectrophotometric method, and the specific detection steps are: (refer to HJ / T 399-2007 standard method)

[0050] Prepare digestion solution;

[0051] Mix the copper acid etching solution to be tested with the digestion solution and digest at 165℃ for 20min;

[0052] After digestion, put it into the spectrophotometer to test the COD value.

[0053] The copper acid etching solution is an etching solution used in the copper manufacturing process of panel manufacturing.

[0054] Performance Testing

[0055] 1. Test the sugar content of a 10,000 mg / L potassium hydrogen phthalate standard solution, which is 0.9%. Substituting this into the fitting curve, the COD value is 10,159 mg / L. The relative deviation is +1.6%.

[0056] 2. The sugar content of three different concentrations of copper acid etching solutions was measured and substituted into the fitting curve to obtain the COD value. The COD values of the three different concentrations of copper acid etching solutions were then measured using the rapid digestion spectrophotometric method (referring to the HJ / T 399-2007 standard method). The test results are shown in Table 2.

[0057] Table 2

[0058]

[0059]

[0060] The test results show that the deviation between the rapid digestion spectrophotometry method and the fitting curve method of the present invention is not large, and the detection requirements of the field are met. The fitting curve method of the present invention is not much different from the actual COD value, and can meet the detection requirements of the field.

Claims

1. A method for rapid detection of COD in copper acid etching solution in large quantities, characterized in that: The following steps are involved: S1: prepare standard solution of copper acid etching solution; S2: sugar content of test standard solution; S3: COD value of test standard solution; S4: Fit the sugar content and COD value of the standard solution into a linear curve; S5: testing the sugar content of the copper acid etching solution to be tested, and corresponding it to the linear curve to obtain the COD value of the copper acid etching solution to be tested.

2. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 1, it is characterized in that, The mass concentration of the solute in the standard solution is 0-30%, excluding 0.

3. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 1, it is characterized in that, The linear curve is y=11288x.

4. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 3, it is characterized in that, The x value in the linear curve is the sugar content, which is expressed in percentage and is substituted into the value before the percentage sign.

5. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 1, it is characterized in that, The linear curve R 2 =0.9881.

6. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 1, it is characterized in that, The method for testing the COD value of the standard solution in step S3 includes at least one of a potassium dichromate method, a rapid digestion spectrophotometric method, a rapid digestion-colorimetric method, a potassium permanganate index method, an electrochemical method, and a biosensor method.

7. according to the large-scale rapid detection method of COD in the copper acid etching solution of claim 6, it is characterized in that, The specific detection steps of the rapid digestion spectrophotometry are: Prepare digestion solution; Mix the copper acid etching solution to be tested with the digestion solution and digest at 160-170℃ for 15-20min; After digestion, put it into the spectrophotometer to test the COD value.

8. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 1, it is characterized in that, The COD detection time of the copper acid etching solution to be tested in step S5 is ≤1 min.

9. according to the large-scale rapid detection method of COD in the described copper acid etching solution of claim 1, it is characterized in that, The copper acid etching solution includes the etching solution used in the copper process of panel manufacturing.

10. An application of the method for rapid mass detection of COD in the copper acid etching solution according to any one of claims 1 to 9, characterized in that: Applicable to the detection of large quantities of copper acid etching solution, the detection quantity is ≥50.

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