Self-adaptive mixed resin efficient purification method for trace impurities in ultrapure water

Abstract

The invention discloses a self-adaptive mixed resin high-efficiency purification method for trace impurities in ultrapure water, which comprises the following steps: pre-mixing various functional resins such as fluorine-removing resin, boron-removing resin, silicon-removing resin and iron-removing resin according to a specific mass ratio of 1: 2: 3: 0.5 through a targeted proportion design to construct a'full-spectrum adsorption 'capability, and in the purification process, the total-spectrum adsorption capacity is improved; a pH-conductivity linkage system is used for regulating and controlling the pH value and the flow velocity of inlet water in real time, the pH value is 4.5-6.5, the flow velocity is 0.5-2 BV / h, and the selectivity of the resin to trace ions is improved through surface chemical modification. Compared with the prior art, the self-adaptive mixed resin efficient purification method for the trace impurities in the ultrapure water has the advantages that the self-adaptive mixed resin efficient purification method for the trace impurities in the ultrapure water is convenient to operate and use, and the self-adaptive mixed resin efficient purification requirement for the trace impurities in the ultrapure water is met.

Description

Technical Field

[0001] This invention relates to, specifically, a highly efficient purification method for trace impurities in ultrapure water using an adaptive mixed resin. Background Technology

[0002] Traditional ultrapure water trace impurity purification methods have many problems. The graded treatment mode of "single resin for single impurity" requires multiple stages of treatment to remove multiple impurities. The process is complicated and inefficient, and it is difficult to achieve the simultaneous removal of multiple trace ions in a single stage.

[0003] Competition for adsorption of different impurity ions can lead to resin performance degradation, triggering a single ion saturation penetration effect and affecting the purification effect.

[0004] In addition, traditional resins have insufficient adsorption efficiency for low-concentration ions, such as silicon and boron, which cannot meet the production requirements of high-precision ultrapure water and restricts the development of industries with stringent water quality requirements, such as semiconductors. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a method for efficient purification of trace impurities in ultrapure water using an adaptive mixed resin that is easy to operate and use, and meets the requirements for efficient purification of trace impurities in ultrapure water.

[0006] To solve the above-mentioned technical problems, the technical solution provided by the present invention is: an adaptive mixed resin high-efficiency purification method for trace impurities in ultrapure water, comprising the following steps:

[0007] Step 1: Premix various functional resins in a certain proportion to construct a single-stage mixed bed with full-spectrum adsorption capacity;

[0008] The multifunctional resins include at least fluoride removal resin, boron removal resin, silicone removal resin and iron removal resin;

[0009] Step 2: Pass the ultrapure water to be purified through the premixed resin bed described above;

[0010] Step 3: During the purification process, the pH value and flow rate of the influent are adjusted in real time using a pH-conductivity linkage system, with the pH value in the range of 4.5-6.5 and the flow rate in the range of 0.5-2 BV / h.

[0011] Step 4: Improve the selectivity of the resin for trace ions through surface chemical modification.

[0012] As an improvement, in step 1, the defluorinating resin, boron-removing resin, silicone-removing resin and iron-removing resin are premixed in a mass ratio of 1:2:3:0.5.

[0013] This includes using micron-sized resin mixing, with a resin particle size distribution deviation of <5%.

[0014] As an improvement, the pH-conductivity linkage system includes an integrated online multi-parameter sensor for monitoring pH, conductivity, and ion concentration;

[0015] The PID algorithm is used to dynamically adjust the parameters.

[0016] As an improvement, the regulation of the pH-conductivity linkage system includes:

[0017] When the boron ion concentration is >0.005 ppb, the pH is automatically lowered to 4.8 to enhance the affinity of the boron removal resin;

[0018] When the iron ion concentration is >0.002 ppb, increase the flow rate to 1.5 BV / h to reduce the contact time.

[0019] As an improvement, the surface chemical modification in step 4 includes:

[0020] Amino-functionalized modification of silicone resin by grafting -NH2 groups increases its adsorption capacity for SiO32- to 5 mg / g.

[0021] La loaded with boron-removing resin 3 +, the boron removal rate was reduced to <0.003 ppb through lanthanum-boron complexation reaction.

[0022] As an improvement, synchronous compensation for resin regeneration is also included;

[0023] During the periodic regeneration of the mixed resin bed, the loss of each resin is replenished in proportion.

[0024] The advantages of this invention compared with the prior art are as follows: This invention breaks through the traditional graded treatment mode of "single resin corresponding to single impurity" in polishing mixed beds. Through targeted ratio design, multiple functional resins such as fluoride removal resin, boron removal resin, silicon removal resin, and iron removal resin are premixed in a specific ratio such as 1:2:3:0.5 by mass, which builds a "full spectrum adsorption" capability. This allows a single-stage mixed bed to remove multiple trace ions simultaneously, which greatly improves the purification efficiency.

[0025] To address the performance degradation caused by competitive adsorption of different impurity ions, a pH-conductivity linkage control system was developed. This system can adjust the influent pH value in real time, controlling it within the range of 4.5-6.5, and the flow rate, maintaining it at 0.5-2 BV / h. This maintains the resin adsorption selectivity, effectively avoids the penetration effect caused by single ion saturation, and ensures the stability of the purification effect.

[0026] By employing surface chemical modification, the selectivity of the resin for specific trace ions is improved. Traditional resins have insufficient adsorption efficiency for low-concentration ions, such as silicon and boron. The modification method of this invention can solve this problem, improve the adsorption capacity for these low-concentration ions, and meet the production requirements of high-precision ultrapure water.

[0027] A method for calculating the resin mass ratio based on an adsorption kinetic model is proposed, such as a fluoride:boron:silicon:iron ratio of 1:2:3:0.5. This method forms a "composite adsorption network" covering the full spectrum of trace ions, enabling more efficient removal of various trace ions.

[0028] A uniform charge layer with a surface potential of +5mV is formed on the resin surface using an electrostatic spray coating process. Electrostatic repulsion counteracts the gravitational settling effect, ensuring that the resin maintains its initial mixed state after long-term operation, with a stratification index of <0.1.

[0029] pH-conductivity linkage control algorithm: Based on a neural network model, a mapping relationship between influent water quality (pH, conductivity, ion concentration) and resin adsorption efficiency is established to achieve dynamic parameter adjustment with a response time of <10s, which can reduce the risk of penetration, such as reducing boron ion penetration rate by 90%.

[0030] An online resin loss monitoring system was developed, which can monitor resin loss by weighing or capacitive sensors and add specific resin in proportion with an accuracy of ±0.5%, ensuring that the mixing ratio deviation is <2% after long-term operation, which is much smaller than the >10% of traditional methods. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of a highly efficient purification method using an adaptive mixed resin for trace impurities in ultrapure water.

[0032] Figure 2 This is a schematic diagram of a highly efficient purification method for trace impurities in ultrapure water using adaptive mixed resins. Detailed Implementation

[0033] The present invention will now be described in further detail with reference to the accompanying drawings.

[0034] Combined with appendix Figure 1 As shown, an adaptive mixed resin high-efficiency purification method for trace impurities in ultrapure water is proposed. Through targeted ratio design, multiple functional resins such as fluoride removal resin, boron removal resin, silicon removal resin, and iron removal resin are premixed in a specific ratio of 1:2:3:0.5 by mass. This method constructs a "full-spectrum adsorption" capability, which enables a single-stage mixed bed to remove multiple trace ions simultaneously, greatly improving the purification efficiency.

[0035] To address the performance degradation caused by competitive adsorption of different impurity ions, a pH-conductivity linkage control system was developed. This system can adjust the influent pH value in real time, controlling it within the range of 4.5-6.5, and the flow rate, maintaining it at 0.5-2 BV / h. Through such adjustments, the resin adsorption selectivity can be maintained, effectively avoiding the penetration effect caused by single-ion saturation and ensuring the stability of the purification effect.

[0036] The surface chemical modification method is used to improve the selectivity of the resin for specific trace ions.

[0037] Based on the target water quality requirements, such as TOC < 5 ppb and metal ion < 0.001 ppb for semiconductor ultrapure water, the optimal ratio of each resin is calculated using an adsorption kinetic model. This ensures that the adsorption capacity and selectivity of different resins are complementary; for example, the fluoride removal resin preferentially adsorbs F-, while the boron removal resin subsequently captures B(OH)4. - To achieve highly efficient purification, the process employs micron-level resin mixing technology to control particle size distribution deviation to <5%. This technology avoids resin stratification and ensures that each resin has an equal probability of contact when water flows through, making the purification process more uniform and efficient.

[0038] The integrated online multi-parameter sensor can monitor parameters such as pH, conductivity, and ion concentration. Through a PID algorithm, the influent pH and flow rate are dynamically adjusted. When boron ion penetration (>0.005 ppb) is detected, the pH is automatically lowered to 4.8 to enhance the boron removal resin's effect on B(OH)4. - The affinity of Fe; when the iron ion concentration increases (>0.002 ppb), increasing the flow rate to 1.5 BV / h reduces Fe 3+ Contact time with resin;

[0039] A resin regeneration synchronous compensation mechanism was designed to replenish the lost amount of each resin proportionally during the periodic regeneration of the mixed bed. For example, when the loss rate of the defluorination resin is >15%, it is added first to ensure the stability of the resin ratio after long-term operation and maintain the purification effect.

[0040] Amino-functionalization was applied to the silicone-removing resin, grafting -NH2 groups to enhance its integration ability with SiO32-, increasing its adsorption capacity to 5 mg / g, far exceeding the <2 mg / g of traditional resins. Lanthanide metal ions, such as La, were loaded onto the boron-removing resin. 3+ By utilizing the lanthanum-boron complexation reaction to improve boron removal rate, it can be reduced to <0.003 ppb, which is better than the <0.008 ppb of traditional resins.

[0041] In the specific implementation of this invention, when implementing the adaptive mixed resin high-efficiency purification method for trace impurities in ultrapure water, the optimal ratio of each resin is first calculated using an adsorption kinetic model based on the target water quality requirements. Resins for fluoride removal, boron removal, silicon removal, and iron removal are premixed in specific proportions. Micron-level resin mixing technology is employed to ensure that the particle size distribution deviation is less than 5%, preventing resin stratification.

[0042] It integrates online multi-parameter sensors to monitor pH, conductivity, and ion concentration in real time. Through a PID algorithm and a pH-conductivity linkage control system, it dynamically adjusts the influent pH and flow rate. When an abnormal concentration of a specific ion is detected, corresponding measures are taken promptly, such as lowering the pH to enhance the affinity of the boron removal resin and increasing the flow rate to reduce the contact time with iron ions.

[0043] During the periodic regeneration of the mixed bed resin, a resin regeneration synchronous compensation mechanism is activated, and the lost resin is replenished proportionally using an online monitoring system. Simultaneously, amino-functionalized modified silica-removing resin and boron-removing resin loaded with lanthanide metal ions are used to enhance the adsorption capacity for specific ions.

[0044] The contents not described in detail in this specification are existing technologies known to those skilled in the art.

[0045] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0046] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0047] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature being directly above or diagonally above the second feature, or simply indicates that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature includes the first feature being directly below or diagonally below the second feature, or simply indicates that the first feature is at a lower horizontal level than the second feature.

[0048] The present invention and its embodiments have been described above. This description is not restrictive, and the accompanying drawings are only one embodiment of the present invention; the actual structure is not limited thereto. In conclusion, if those skilled in the art are inspired by this description and design similar structures and embodiments without departing from the spirit of the invention, such designs should fall within the protection scope of the present invention.

Claims

1. A highly efficient purification method for trace impurities in ultrapure water using adaptive mixed resins. The feature includes the following steps: Step 1: Premix various functional resins in a certain proportion to construct a single-stage mixed bed with full-spectrum adsorption capacity; The multifunctional resins include at least fluoride removal resin, boron removal resin, silicone removal resin and iron removal resin; Step 2: Pass the ultrapure water to be purified through the premixed resin bed described above; Step 3: During the purification process, the pH value and flow rate of the influent are adjusted in real time using a pH-conductivity linkage system, with the pH value in the range of 4.5-6.5 and the flow rate in the range of 0.5-2 BV / h. Step 4: Improve the selectivity of the resin for trace ions through surface chemical modification.

2. The method for efficient purification of trace impurities in ultrapure water using adaptive mixed resin according to claim 1, characterized in that: In step 1, the fluoride removal resin, boron removal resin, silicone removal resin and iron removal resin are premixed in a mass ratio of 1:2:3:0.

5. This includes using micron-sized resin mixing, with a resin particle size distribution deviation of <5%.

3. The method for efficient purification of trace impurities in ultrapure water using adaptive mixed resin according to claim 1, characterized in that: The pH-conductivity linkage system includes an integrated online multi-parameter sensor for monitoring pH, conductivity, and ion concentration. The PID algorithm is used to dynamically adjust the parameters.

4. The method for efficient purification of trace impurities in ultrapure water using adaptive mixed resin according to claim 3, characterized in that: The regulation of the pH-conductivity linkage system includes: When the boron ion concentration is >0.005 ppb, the pH is automatically lowered to 4.8 to enhance the affinity of the boron removal resin; When the iron ion concentration is >0.002 ppb, increase the flow rate to 1.5 BV / h to reduce the contact time.

5. The method for efficient purification of trace impurities in ultrapure water using adaptive mixed resin according to claim 1, characterized in that: The surface chemical modification in step 4 includes: Amino-functionalized modification of silicone resin by grafting -NH2 groups increases its adsorption capacity for SiO32- to 5 mg / g. La loaded with boron-removing resin 3 +, the boron removal rate was reduced to <0.003 ppb through lanthanum-boron complexation reaction.

6. The method for efficient purification of trace impurities in ultrapure water using adaptive mixed resin according to claim 1, characterized in that: It also includes synchronous compensation for resin regeneration; During the periodic regeneration of the mixed resin bed, the loss of each resin is replenished in proportion.

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