Process and device for continuously producing high-purity electronic-grade hydrogen peroxide

Abstract

The application discloses a kind of processes for continuously preparing high-purity electronic grade hydrogen peroxide, it is related to the technical field of hydrogen peroxide preparation, including the following steps: operator injects corresponding extraction liquid into equipment, then the oxidizing liquid in the oxidizing liquid tank and the high salt water of reverse osmosis mechanism are sent to the bottom of extraction tower body through pipeline, the extraction tower body is filtered by setting multiple groups of sieve plates and chelating resin discs inside the body to impurities in the extraction process, the liquid outlet valve and liquid inlet valve at the outer end of extraction tower body are connected with the corresponding purification tower body, reverse osmosis mechanism and oxidizing liquid tank around; the oxidizing liquid and high salt water from the bottom of extraction tower body enter the top of purification tower body by virtue of the difference in position. During the installation of sieve plate or filter element, directly pass through the circular limiting ring and multiple vertical guide grooves for clamping connection, to avoid the loosening of the connection between sieve plate and vertical guide groove due to repeated flushing of liquid during use.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of hydrogen peroxide preparation, in particular to a process and device for continuously preparing high-purity electronic-grade hydrogen peroxide. BACKGROUND

[0002] In the electronic industry, electronic-grade hydrogen peroxide is mainly used for producing batteries and electronic components, and can be used for cleaning and removing dirt and grease on the surface of electronic components to ensure the performance and quality of the electronic components, and can also be used for producing high-end battery products such as lithium ion batteries.

[0003] Electronic-grade hydrogen peroxide can also be used for medical disinfection, food industry and other industries, and has a very wide range of uses. Super-clean high-purity electronic chemicals are key integrated raw materials for super-large scale integrated circuit manufacturing. Electronic-grade hydrogen peroxide is mainly used for semiconductor silicon wafer cleaning agents, etching agents and photoresist remover, and its purity and cleanliness have a very important influence on the yield, electrical performance and reliability of the finished product.

[0004] The current extraction separator and dilute product separator have large equipment size and long settling residence time. In the operation process, if the sieve plate fails, the equipment shell needs to be opened, and even the main shaft and other parts need to be disassembled to maintain the filter disc. If individual filter discs need to be replaced, and the concentration ratio of the extraction liquid is different, the spacing of the sieve plate cannot be adjusted, which will affect the filtration efficiency of the liquid extraction, and will cause the problems of labor and time consumption, and serious problems such as work stoppage and production stoppage of the user using such equipment. SUMMARY

[0005] The application aims to provide a process and device for continuously preparing high-purity electronic-grade hydrogen peroxide to solve the above-mentioned defects in the prior art.

[0006] A process for continuously preparing high-purity electronic-grade hydrogen peroxide comprises the following steps:

[0007] A: The operator pours the corresponding extraction liquid into the device, and then sends the oxidizing liquid in the oxidizing liquid tank and the high-salinity water of the reverse osmosis mechanism to the bottom of the extraction tower body through pipelines. The extraction tower body is provided with multiple groups of sieve plates and chelating resin discs inside to filter and treat the impurities in the extraction process. The liquid outlet valve and the liquid inlet valve at the outer end of the extraction tower body are connected with the corresponding purification tower body, reverse osmosis mechanism and oxidizing liquid tank through pipelines.

[0008] B: Oxidizing liquid containing hydrogen peroxide and high-salt water from the bottom of the extraction tower body are dispersed into countless small oil beads by multiple groups of sieve plates and floated to the top of the tower, while the pure water supply device sends the mixed pure water and phosphoric acid solution to the top of the extraction tower body for extraction water, and the pure water and phosphoric acid solution are injected into the annular spray pipe at the bottom end through the liquid inlet pipeline, and the annular spray pipe is used for uniformly spraying the pure water and phosphoric acid solution;

[0009] C: The water phase in the tower is communicated up and down through the downcomer of each sieve plate and continuously flows downward, while the chelating resin disc is used for countercurrent extraction of the upward floating oxidizing liquid and high-salt water, in the extraction process, water is the continuous phase, and the oxidizing liquid and high-salt water are the dispersed phase, in which the content of hydrogen peroxide gradually increases, and finally flows out from the bottom of the tower, which is called extraction liquid;

[0010] D: The oxidizing liquid and high-salt water entering the top of the purification tower body by virtue of the potential difference, in the process of dispersing and floating upward, the content of hydrogen peroxide gradually decreases, and finally flows out from the top of the extraction tower body, the purification tower body selects a filler structure to filter impurities, and the purification tower body is filled with C9 and C10 heavy aromatic hydrocarbons, and the extraction liquid entering from the top of the tower flows downward in the tower;

[0011] E: C9 and C10 heavy aromatic hydrocarbons are sent to the bottom of the purification tower body by an aromatic pump, and form countercurrent extraction with the extraction liquid to remove organic impurities in hydrogen peroxide, and the organic matter in the reverse osmosis high-salt water is removed, in this process, heavy aromatic hydrocarbons are the continuous phase, and the extraction liquid is the dispersed phase, and the purified hydrogen peroxide flows out from the bottom of the purification tower body, and the hydrogen peroxide is extracted by the extraction pump, and the hydrogen peroxide is injected into the hydrogen peroxide storage tank through the pipe on one side of the output end of the extraction pump.

[0012] Preferably, the extraction tower body comprises a vertical guide groove, a vertical fastening rod, a sieve plate, a circular limiting ring, an auxiliary protrusion and a chelating resin disc, the vertical guide groove is arranged in the interior of the extraction tower body in a rectangular distribution, the interior of the vertical guide groove is provided with the vertical fastening rod, the outer side of the vertical fastening rod is connected with the circular limiting ring at equal intervals in penetration, the periphery of the circular limiting ring is connected with the auxiliary protrusion, and the outer side of the circular limiting ring is connected with the sieve plate and the chelating resin disc, respectively.

[0013] Preferably, the extraction tank cover is connected with the top end of the annular spray pipe through the liquid inlet pipeline penetratingly connected with the top end.

[0014] Preferably, the extraction tower body is connected with the circular limiting ring through the internally arranged vertical guide groove.

[0015] Preferably, the lifting mechanism comprises a ring sleeve, vertical guide rods, a horizontal lifting frame and fastening through holes, the ring sleeve is connected to the outside of the extraction tower body, vertical guide rods are distributed around the extraction tower body, the horizontal lifting frame is connected to the outside of the vertical guide rods, and fastening through holes are distributed in a rectangular shape on the outside of the horizontal lifting frame.

[0016] Preferably, the ring sleeve is connected to the bottom end of the reverse osmosis mechanism through the horizontal lifting frame arranged on the outside.

[0017] Preferably, the extraction tower body is connected to the output end of the oxidizing liquid tank through the liquid inlet valve arranged on the outside.

[0018] Preferably, the circular limiting ring is locked by a nut with the vertical fastening rod, and the diameter of the circular limiting ring is smaller than that of the chelating resin disc.

[0019] Compared with the prior art, the present application has the following advantages:

[0020] 1. During the installation of the screen plate or filter core, the circular limiting ring is directly connected to the multiple vertical guide grooves, avoiding the loosening or even collision of the screen plate and the vertical guide groove caused by repeated liquid washing during the installation of the multiple filter cores and screen plates, and ensuring the screening of the liquid during the up-down extraction of the multiple screen plates and filter cores.

[0021] 2. The chelating resin disc, anion exchange resin and cation exchange resin are used for adsorption in sequence, further improving the purity of hydrogen peroxide, the vertical guide rod is used for guiding the downward direction of the horizontal lifting frame, the vertical guide rod and the horizontal lifting frame are connected and positioned by bolts, and the ring sleeve and the horizontal lifting frame are vertically adjusted.

[0022] 3. The selected chelating resin disc can selectively remove high-valence metal ions, avoiding the accumulation of Fe3+ and other transition metal ions, which may cause safety hazards such as decomposition of hydrogen peroxide and heat release, and creating safe and efficient conditions for the next step of purifying low-valence ions. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a structural schematic diagram of the whole application.

[0024] Figure 2 It is a structural schematic diagram of the extraction tower body in the application.

[0025] Figure 3 It is a structural schematic diagram of the extraction tower body in the application.

[0026] Figure 4 It is a structural schematic diagram of the extraction tower body in the application.

[0027] Figure 5 This is a top view of the extraction tower structure in this invention.

[0028] Figure 6 This is a three-dimensional structural diagram of the circular limiting ring in this invention.

[0029] Figure 7 This is a schematic diagram of the cross-section of the extraction tower body in this invention.

[0030] in:

[0031] 1. Extraction tower body; 101. Vertical guide channel; 102. Vertical fastening rod; 103. Sieve plate; 104. Circular limiting ring; 105. Auxiliary protrusion; 106. Chelating resin disc; 2. Liquid inlet pipe; 3. Extraction tank cover; 4. Oxidation liquid tank; 5. Lifting mechanism; 51. Annular sleeve; 52. Vertical guide rod; 53. Horizontal lifting frame; 54. Fastening through hole; 6. Hydrogen peroxide storage tank; 7. Purification tower body; 8. Reverse osmosis mechanism; 9. Annular spray pipe; 10. Liquid outlet valve; 11. Liquid inlet valve; 12. Extraction pump. Detailed Implementation

[0032] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0033] like Figures 1 to 7 As shown, a process for continuously preparing high-purity electronic-grade hydrogen peroxide includes the following steps:

[0034] A: The operator injects the corresponding extract into the equipment, and then sends the oxidizing liquid in the oxidation tank 4 and the high brine of the reverse osmosis mechanism 8 through the pipeline to the bottom of the extraction tower 1. The extraction tower 1 filters the impurities in the extraction process by setting multiple sets of sieve plates 103 and chelating resin discs 106 inside. The outlet valve 10 and inlet valve 11 set at the outer end of the extraction tower 1 are connected to the surrounding purification tower 7, reverse osmosis mechanism 8 and oxidation tank 4 through pipe fittings.

[0035] B: After the oxidizing liquid containing hydrogen peroxide and the high brine enter from the bottom of the extraction tower 1, they are dispersed into countless small oil droplets by multiple sets of sieve plates 103 and float to the top of the tower. At the same time, the pure water supply device mixes pure water and phosphoric acid solution and sends extraction water to the top of the extraction tower 1. The pure water and phosphoric acid solution are injected into the bottom ring spray pipe 9 through the liquid inlet pipe 2. The pure water and phosphoric acid solution are uniformly sprayed using the ring spray pipe 9.

[0036] C: The liquid descending pipe of each layer sieve plate 103 is connected with the water phase in the tower, and the chelating resin disc 106 is used to extract the upward floating oxidizing liquid and high salt water in countercurrent, in the extraction process, the water is the continuous phase, and the oxidizing liquid and high salt water are the dispersed phase, the hydrogen peroxide content gradually increases, and finally flows out from the bottom of the tower, which is called crude hydrogen peroxide;

[0037] D: The oxidizing liquid and high salt water from the bottom of the extraction tower body 1 enter the top of the purification tower body 7 by virtue of the potential difference, and the hydrogen peroxide content gradually decreases in the process of dispersing upward floating, and finally flows out from the top of the extraction tower body 1, the purification tower body 7 is selected to filter the impurities, and the purification tower body 7 is filled with C9 and C10 heavy aromatic hydrocarbons, and the extraction liquid entering from the top of the tower flows downward in the tower;

[0038] E: C9 and C10 heavy aromatic hydrocarbons are pumped into the bottom of the purification tower body 7, and form countercurrent extraction with the extraction liquid to remove organic impurities in hydrogen peroxide, and the organic matter in reverse osmosis high salt water is removed, in this process, the heavy aromatic hydrocarbons are the continuous phase, and the extraction liquid is the dispersed phase, the purified hydrogen peroxide flows out from the bottom of the purification tower body 7, the extraction pump 12 is used to extract hydrogen peroxide, and the pipe on one side of the output end of the extraction pump 12 is used to inject hydrogen peroxide into the hydrogen peroxide storage tank 6.

[0039] In the embodiment, the extraction tower body 1 comprises a vertical guide groove 101, a vertical fastening rod 102, a sieve plate 103, a circular limiting ring 104, an auxiliary protrusion 105 and a chelating resin disc 106, the vertical guide groove 101 is arranged in the interior of the extraction tower body 1 in a rectangular distribution, the vertical guide groove 101 is internally provided with the vertical fastening rod 102, the outer side of the vertical fastening rod 102 is externally and equidistantly penetrated and connected with the circular limiting ring 104, the circular limiting ring 104 is peripherally connected with the auxiliary protrusion 105, and the outer side of the circular limiting ring 104 is respectively connected with the sieve plate 103 and the chelating resin disc 106, the sieve plate 103 is used to filter and screen the materials, so as to reduce the impurity content of the raw materials.

[0040] In the embodiment, the extraction tank cover 3 is connected with the annular spray pipe 9 at the top end through the penetrating connection of the liquid inlet pipeline 2 at the top end, the annular spray pipe 9 is used to uniformly spray the liquid, so as to improve the uniformity of liquid spraying and reaction.

[0041] In the embodiment, the extraction tower body 1 is connected with the circular limiting ring 104 through the internally arranged vertical guide groove 101, the circular limiting ring 104 is limited by the vertical guide groove 101, so as to avoid the deviation of the circular limiting ring 104.

[0042] In the embodiment, the lifting mechanism 5 comprises a ring sleeve 51, vertical guide rods 52, a horizontal lifting frame 53 and fastening through holes 54. The ring sleeve 51 is connected to the outside of the extraction tower body 1. The vertical guide rods 52 are distributed around the extraction tower body 1. The horizontal lifting frame 53 is connected to the outside of the vertical guide rods 52. The fastening through holes 54 are distributed in a rectangular shape on the outside of the horizontal lifting frame 53.

[0043] In the embodiment, the ring sleeve 51 is connected to the bottom end of the reverse osmosis mechanism 8 through the horizontal lifting frame 53 arranged on the outside. The horizontal lifting frame 53 is used to connect the bottom end of the equipment, which is convenient for connecting equipment with different heights or sizes.

[0044] In the embodiment, the extraction tower body 1 is connected to the output end of the oxidizing liquid tank 4 through the liquid inlet valve 11 arranged on the outside. The oxidizing liquid tank 4 guides the raw materials and controls the amount of liquid.

[0045] In the embodiment, the circular limiting ring 104 is locked through a nut with the vertical fastening rod 102. The diameter of the circular limiting ring 104 is smaller than that of the chelating resin disc 106. The chelating resin disc 106 is used to filter the hydrogen peroxide raw materials moving upward.

[0046] The 35% industrial hydrogen peroxide solution is treated according to the method in the embodiment. The empty column rate is 8h-1, the exchange column is 100L, and the exchange temperature is controlled at 20℃. The test method of the total carbon content and the nitrate content in the hydrogen peroxide is tested according to GB1616-2003 industrial hydrogen peroxide, and the organic carbon purification rate before and after treatment is calculated. The total carbon content in the hydrogen peroxide before treatment is 320ppm, and the nitrate content is 350ppm.

[0047] Nitrate content (ppm) Total carbon removal (%) Example 1 12 99.9 Example 2 18 99.7 Example 3 20 99.5 Comparative Example 1 147 79.3 Comparative Example 2 96 90.9 Comparative Example 3 91 90.1 Comparative Example 4 228 62.7

[0048] Example 1 proves that the quality of hydrogen peroxide needs high-quality electronic grade, and the single metal ion is less than 1ppt, and the total metal ion content is less than 100ppt.

[0049] Example 2 proves that the surface foam is formed by the residual organic solvent in the macropore of the organic carbon adsorption resin in the production process. Therefore, the residual solvent on the surface needs to be cleaned out, so as to improve the adsorption and removal effect of the resin on organic carbon.

[0050] Example 3 proves that the resin is cleaned at a specific temperature. Due to the increase of temperature, the activity of the resin is improved, the activity of the substance is improved, the ion mobility is improved, and the exchange and adsorption effect of organic carbon is improved.

[0051]

[0052] The process and device for continuously producing high-purity electronic-grade hydrogen peroxide include the following working contents in practical application:

[0053] Step 1: The operator first connects the annular sleeve 51 with the sieve plate 103 and the chelating resin disc 106, and connects the annular sleeve 51 with the chelating resin disc 106 and the sieve plate 103 through the through hole on the outside of the annular sleeve 51, vertically connects the annular sleeve 51 with the vertical fastening rod 102, and locks the annular sleeve 51 and the vertical fastening rod 102 by setting a nut inside the vertical fastening rod 102, to avoid the chelating resin disc 106 and the annular sleeve 51 from deviating, and sets a plurality of sieve plates 103 and chelating resin discs 106 with different mesh numbers and filtering distances;

[0054] Step 2: The operator pulls the annular sleeve 51 according to the specifications and sizes of the equipment, so that the annular sleeve 51 slides outside the extraction tower body 1, guides the downward direction of the horizontal lifting frame 53 by using the vertical guide rod 52, and vertically adjusts the annular sleeve 51 and the horizontal lifting frame 53 by connecting and positioning the vertical guide rod 52 and the horizontal lifting frame 53 by using the bolt, so that the oxidation liquid tank 4 and the hydrogen peroxide storage tank 6 are installed outside the horizontal lifting frame 53, and the horizontal lifting frame 53 and the corresponding equipment are connected by the fastening through hole 54;

[0055] Step 3: The liquid outlet valve 10 and the liquid inlet valve 11 at the outer end of the extraction tower body 1 are connected with the surrounding corresponding purification tower body 7, reverse osmosis mechanism 8 and oxidation liquid tank 4 by pipes, and the pure water supply device mixes pure water and phosphoric acid solution and sends the extraction water to the top of the extraction tower body 1, and the pure water and phosphoric acid solution are injected into the annular spray pipe 9 at the bottom end through the liquid inlet pipeline 2, and the pure water and phosphoric acid solution are uniformly sprayed by the annular spray pipe 9;

[0056] Step 4: The oxidation liquid and high-salt water entering from the bottom of the extraction tower body 1 gradually reduce the content of hydrogen peroxide during the process of dispersing and floating upward, thereby completing the extraction and reaction of the material;

[0057] Step 5: The water phase in the tower flows continuously downward through the downcomer of each sieve plate 103, and the chelating resin disc 106 is used for countercurrent extraction of the oxidation liquid and high-salt water floating upward, and the purified hydrogen peroxide flows out from the bottom of the purification tower body 7, the extraction pump 12 is used for extracting the hydrogen peroxide, and the hydrogen peroxide is injected into the hydrogen peroxide storage tank 6 through the pipe connected to the output side of the extraction pump 12, thereby completing the production of electronic-grade hydrogen peroxide.

[0058] Thus, the embodiments disclosed above are merely exemplary, and nothing that is only an example. All changes within the scope of the invention or equivalent to the scope of the invention are included in the invention.

Claims

1. A process for the continuous preparation of high-purity electronic-grade hydrogen peroxide, characterized in that: Includes the following steps: A: The operator injects the corresponding extract into the equipment, and then sends the oxidizing liquid in the oxidation tank (4) and the high saline solution in the reverse osmosis mechanism (8) through the pipeline to the bottom of the extraction tower (1). The extraction tower (1) filters the impurities in the extraction process by setting multiple sets of sieve plates (103) and chelating resin discs (106) inside. The outlet valve (10) and inlet valve (11) set at the outer end of the extraction tower (1) are connected to the surrounding purification tower (7), reverse osmosis mechanism (8) and oxidation tank (4) through pipe fittings. B: After the oxidizing liquid containing hydrogen peroxide and the high brine enter from the bottom of the extraction tower (1), they are dispersed into countless small oil droplets by multiple sets of sieve plates (103) and float to the top of the tower. At the same time, the pure water supply device mixes the pure water and the phosphoric acid solution and sends the extraction water to the top of the extraction tower (1). The pure water and the phosphoric acid solution are injected into the ring spray pipe (9) at the bottom through the liquid inlet pipe (2). The pure water and the phosphoric acid solution are uniformly sprayed using the ring spray pipe (9). C: The water phase in the tower is connected vertically through the downcomer tubes of each sieve plate (103) and flows continuously downward. At the same time, the chelating resin plate (106) is used to countercurrently extract the upward floating oxidizing liquid and high brine. During the extraction process, water is the continuous phase, and oxidizing liquid and high brine are the dispersed phases. The hydrogen peroxide content gradually increases and finally flows out from the bottom of the tower, which is called the extract, i.e. crude hydrogen peroxide. D: The extract enters the top of the purification tower (7) by means of the position difference, while the oxidizing liquid and high saline solution that enter from the bottom of the extraction tower (1) gradually decrease in hydrogen peroxide content as they disperse and float upwards, and finally flow out from the top of the extraction tower (1). The purification tower (7) uses a packing structure to filter impurities. The purification tower (7) is filled with C9 and C10 heavy aromatics. The extract that enters from the top of the tower flows downwards inside the tower. E:C9 and C10 heavy aromatics are pumped into the bottom of the purification tower (7) by the aromatics pump and form a countercurrent extraction with the extractant to remove organic impurities in hydrogen peroxide. Organic matter in the reverse osmosis high brine is removed. In this process, heavy aromatics are the continuous phase and the extractant is the dispersed phase. The purified hydrogen peroxide flows out from the bottom of the purification tower (7) and is extracted by the extraction pump (12). The hydrogen peroxide is injected into the hydrogen peroxide storage tank (6) through the pipe fitting on one side of the output end of the extraction pump (12).

2. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 1, characterized in that: The extraction tower body (1) includes a vertical guide groove (101), a vertical fastening rod (102), a sieve plate (103), a circular limiting ring (104), an auxiliary protrusion (105), and a chelating resin disc (106). The vertical guide groove (101) is rectangularly distributed inside the extraction tower body (1). The vertical guide groove (101) is provided with a vertical fastening rod (102) inside. The circular limiting ring (104) is connected to the outer side of the vertical fastening rod (102) at equal intervals. The auxiliary protrusion (105) is connected around the circular limiting ring (104). The sieve plate (103) and the chelating resin disc (106) are respectively connected to the outer side of the circular limiting ring (104).

3. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 2, characterized in that: The upper end of the extraction tower body (1) is provided with an extraction tank cover (3), and the extraction tank cover (3) is connected to the top end of the annular spray pipe (9) through the liquid inlet pipe (2) that is connected through the top end.

4. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 1, characterized in that: The extraction tower body (1) is connected to the circular limiting ring (104) through the internally provided vertical guide groove (101).

5. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 1, characterized in that: The extraction tower body (1) is provided with a lifting mechanism (5) on the outside. The lifting mechanism (5) includes an annular sleeve (51), a vertical guide rod (52), a horizontal lifting frame (53), and a fastening through hole (54). The annular sleeve (51) is connected to the outside of the extraction tower body (1). The vertical guide rod (52) is distributed around the extraction tower body (1). The horizontal lifting frame (53) is connected through the outside of the vertical guide rod (52). The fastening through hole (54) is rectangularly distributed on the outside of the horizontal lifting frame (53).

6. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 5, characterized in that: The annular sleeve (51) is connected to the bottom end of the reverse osmosis mechanism (8) via a horizontal support frame (53) provided on the outside.

7. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 1, characterized in that: The extraction tower (1) is connected to the output end of the oxidation tank (4) through the liquid inlet valve (11) set on the outside.

8. The apparatus used in the continuous preparation process of high-purity electronic-grade hydrogen peroxide according to claim 2, characterized in that: The circular limiting ring (104) and the vertical fastening rod (102) are locked together by a nut. The diameter of the circular limiting ring (104) is smaller than the diameter of the chelating resin disc (106).

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