Concentration sample preparation analysis and purification process of electronic grade hydrogen peroxide

Abstract

The invention discloses an electronic-grade hydrogen peroxide concentration sample preparation analysis and purification process, which comprises the following steps: introducing electronic-grade hydrogen peroxide into an ultra-pure container, controlling the concentration ratio to be 1: (10-1000) in an ultra-clean atmosphere by utilizing the saturated vapor pressure difference of hydrogen peroxide at different temperatures, and maintaining a non-boiling state through non-contact heating, a laminar flow state is kept in combination with circulating air blowing of a surface gas carrying device, a superfluid state dielectric film is formed in combination with introduced film forming gas and control conditions, 80%-90% of impurities are adsorbed and settled by the superfluid state dielectric film, and metastable saturated hydrogen peroxide is condensed and separated out through a condenser. By selecting and collecting residual liquid or condensation materials, concentration sample preparation analysis and purification can be respectively realized, the mass content of metal ions of the obtained ultra-pure electronic-grade hydrogen peroxide is as low as 0.1 ppt or below, high-magnification and ultra-clean concentration analysis sample preparation and high-purity purification effects of hydrogen peroxide can be achieved, the requirements of high-end fields such as laboratories and semiconductor manufacturing are met, and the method is suitable for industrial production. And a foundation is laid for mass production of G6 and G7-grade products.

Description

Technical Field

[0001] The invention relates to the technical field of concentrated sample preparation analysis and purification of hydrogen peroxide, and in particular to a concentrated sample preparation analysis and purification process of electronic-grade hydrogen peroxide. Background Art

[0002] With the rapid development of my country's semiconductor and electronics industries, ultra-high-purity electronic chemicals, as key materials at the heart of the industry chain, have become increasingly important. Their purity and quality directly impact technological breakthroughs in high-end manufacturing fields, such as chip manufacturing and LCD panel precision. Ultra-high-purity electronic-grade hydrogen peroxide is widely used in key processes such as photoresist removal from silicon wafers, precision cleaning of electronic components, and etching. Purity requirements continue to rise as the global semiconductor industry evolves toward sub-5nm processes.

[0003] Currently, the purity testing of electronic-grade hydrogen peroxide primarily relies on ICP-MS (inductively coupled plasma mass spectrometry) technology to analyze trace metal ions. The performance of the detection equipment directly determines the accuracy of the analysis. Under Class 10 ultra-clean conditions, mainstream equipment such as the Agilent 7900 has a detection limit of approximately 0.3 ppt for low-mass elements, while the Thermo Fisher ICAP Qc has a detection limit of approximately 0.5 ppt for low-mass elements. The Spectrum Technology EXPEC 7350 and Labtech Lab MS 5000 both have a detection limit of 1 ppt for low-mass elements. However, existing sample preparation techniques can only control the metal ion content in pure water to below 1 ppt at most, making it difficult to meet the analytical requirements for lower detection limits. This has led to a technical bottleneck in the accurate detection of ultra-trace impurities.

[0004] Moreover, with the continuous breakthroughs in semiconductor manufacturing processes, G5-level purity can no longer meet the quality requirements of ultra-high-purity hydrogen peroxide for the next generation of electronic devices. It is urgent to develop a new generation of purification technology with G6-level and above purity to solve the core problems that restrict industrial upgrading.

[0005] In summary, the existing analytical technologies have insufficient sample preparation purity, limited detection accuracy, and the purification technology cannot break through the G5 level bottleneck, making it difficult to meet the semiconductor industry's urgent demand for ultra-high-purity electronic-grade hydrogen peroxide. Therefore, there is an urgent need to develop a concentrated sample preparation analysis and higher-purity purification technology for electronic-grade hydrogen peroxide. Summary of the Invention

[0006] To address technical issues such as limited purity improvement, incomplete impurity separation, and insufficient equipment detection limits in existing electronic-grade hydrogen peroxide purification processes, the present invention provides a process for concentrated sample preparation, analysis, and purification of electronic-grade hydrogen peroxide. By utilizing carrier gas refining, superfluidic membrane technology, and coordinated multi-parameter control, this process overcomes the purity bottlenecks of traditional processes and simultaneously achieves the dual benefits of deep purification and efficient concentrated sample preparation. This process achieves remarkable concentration and separation results. For electronic-grade hydrogen peroxide with an initial metal ion content of 100 ppt to 1 ppt, 80%-90% of impurities can be efficiently concentrated and removed, ultimately reducing the metal ion content in the product to an ultra-high purity level of 0.1 ppt to 0.005 ppt, fully meeting the stringent standards for high-end electronic-grade hydrogen peroxide, such as G6 and G7 grades.

[0007] The above-mentioned object of the present invention is achieved through the following technical solutions: A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Electronic grade hydrogen peroxide is introduced into an ultra-high purity container through a liquid distributor, and carrier gas is circulated and blown in combination with a surface carrier device under non-contact heating and maintaining the hydrogen peroxide in a non-boiling state, and controllably refined under the conditions of a temperature of -50°C to 150°C and a pressure of 0.01-1000 kPa in the ultra-high purity container, so that the carrier gas and gaseous hydrogen peroxide diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film; (2) adjusting the temperature in the ultra-high purity container to -50°C~-25°C and the pressure to 0.1~700 kPa, blowing film-forming gas through the surface carrier gas device to keep the hydrogen peroxide in a superfluid state, and the impurities are adsorbed on the surface of the superfluid medium membrane to achieve concentration and sedimentation, and the hydrogen peroxide forms a metastable saturated gas and enters the condenser; wherein the film-forming gas is selected from one or more of difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane and carbon tetrafluoride; (3) condensing the metastable saturated gas into liquid form through the condenser and collecting the collected liquid hydrogen peroxide, circulating the collected liquid hydrogen peroxide into an ultra-high purity container until ultra-high purity electronic grade hydrogen peroxide with a metal ion mass content of less than 0.1 ppt is collected; the carrier gas is compressed and circulated into the ultra-high purity container after separation; (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:(10-1000) to obtain a hydrogen peroxide concentrate, and the concentration efficiency of impurity ions and total organic carbon (TOC) is 80%-90%.

[0008] The disclosed process for concentrating, sampling, analyzing, and purifying electronic-grade hydrogen peroxide achieves the dual functions of concentrated hydrogen peroxide sampling and analysis and purification of higher-purity electronic-grade hydrogen peroxide. The process is characterized by introducing electronic-grade hydrogen peroxide into an ultra-high-purity container via a liquid distributor. In an ultra-clean atmosphere, non-contact heating is used to maintain a non-boiling state by regulating the difference in saturated vapor pressure of hydrogen peroxide at different temperatures. Circulating air is then pumped through a surface gas carrier to maintain a laminar flow state with a low Reynolds coefficient. This state avoids impurity dispersion caused by turbulence. Simultaneously, a liquid film forms on the surface of the container's packing material, serving as the primary mass transfer interface, increasing the heat exchange area and improving the refining rate. Film-forming gas is introduced through the surface gas carrier, allowing the liquid hydrogen peroxide at the bottom of the container to exchange with the saturated hydrogen peroxide gas on the surface of the partially solid hydrogen peroxide, maintaining a 0.1-100 nm superfluid film. Impurities are adsorbed on the surface of this superfluid film, where they concentrate and settle. Excess energy is then dissipated through gas aeration, effectively maintaining the stability of the superfluid film. By selecting the collection object, dual functions can be achieved - collecting the residual liquid in the ultra-high purity container to complete the hydrogen peroxide concentration sample preparation, and collecting the condensed material in the condenser to achieve hydrogen peroxide purification.

[0009] The core of this invention lies in the fact that the liquid membrane, serving as the initial mass transfer interface, primarily increases the gas-liquid contact area and accelerates mass transfer efficiency. The superfluid membrane, with a thickness of 0.1-100 nm, is key to achieving deep purification, its nanoscale structure endowing it with exceptionally strong impurity adsorption capabilities. While liquid membranes alone cannot meet the demands of radical purification, superfluid membranes, through their unique interfacial effects and energy balance mechanisms, enable targeted adsorption and efficient separation of impurities. Formed by precisely controlling process parameters, the superfluid membrane enables both high-rate ultraclean sample preparation and concentration, and high-purity purification of hydrogen peroxide under ultraclean conditions. After concentration, ICP-MS analysis and calculation confirmation reveal that the resulting high-quality, high-value, ultrahigh-purity electronic-grade hydrogen peroxide can contain metal ions as low as below 0.1 ppt, or even below 0.01 ppt or 0.005 ppt, providing key technical support for the mass production of ultrahigh-purity electronic-grade hydrogen peroxides, such as G6 and G7 grades.

[0010] Furthermore, in step (1), the mass concentration of the electronic grade hydrogen peroxide is 30%-32%, for example, it can be 30%, 31.5%, 32%, or a range formed by any two values.

[0011] Furthermore, in step (1), the metal ion mass content of the electronic grade hydrogen peroxide is less than 100 ppt.

[0012] Furthermore, in step (1), the material of the ultra-high purity container is ordinary PTFE (polytetrafluoroethylene), PFA (perfluoroalkoxy resin, which can also be ultra-high purity PFA), ultra-high purity PVDF (polyvinylidene fluoride), FEP (fluorinated ethylene propylene copolymer) or ultra-high purity quartz glass. The common characteristics of these materials are that the metal dissolution amount is extremely low (<30 ppt) and they are resistant to hydrogen peroxide corrosion. If ordinary metal or glass materials are used, the metal ions released from their surface will directly contaminate the system, resulting in the product purity being unable to exceed the 1 ppt level.

[0013] Furthermore, in step (1), the non-contact heating method is infrared heating, microwave heating, or heating through an ultra-high purity polytetrafluoroethylene heat exchanger. The core advantage of non-contact heating is to avoid direct contact between the heat source and hydrogen peroxide: traditional contact heating is prone to produce local high temperature spots, causing hydrogen peroxide to decompose and destroy the superfluid film; while infrared / microwave heating can achieve uniform temperature increase, and the ultra-high purity polytetrafluoroethylene heat exchanger indirectly transfers heat through the medium, ensuring that the system temperature fluctuation is less than ±5 °C.

[0014] Furthermore, in step (1), the carrier gas is selected from one or more of nitrogen, oxygen, carbon dioxide, air and argon.

[0015] Furthermore, in step (1), before circulating the carrier gas through the surface carrier gas device, the carrier gas is first filtered to remove impurities such as particulate matter and organic carbon.

[0016] Furthermore, in step (1), the surface gas carrier device circulates the carrier gas at a velocity of 0.01-1000 m 3 / h, for example, it can be 0.01-0.1 m 3 / h, 0.01-900 m 3 / h, 0.1-700 m 3 / h, 1-1000 m 3 If the gas velocity is too low, a stable gas-liquid interface cannot be formed, and the liquid film is easily broken due to insufficient surface tension; if the gas velocity is too high, the laminar flow state will be destroyed, causing the impurities to be redispersed.

[0017] Furthermore, in step (1), the temperature in the ultrahigh purity container is -50°C to 150°C, for example, it can be -50°C, -40°C, -30°C, -20°C, 0°C, 20°C, 40°C, 60°C, 80°C, 100°C, 150°C, or a range formed by any two values.

[0018] Furthermore, in step (1), the pressure in the ultrahigh purity container is 0.01-1000 kPa, for example, 0.01-500 kPa, 0.1-500 kPa, 0.1-600 kPa, 1-700 kPa, 0.01-800 kPa, 10-800 kPa, or 20-1000 kPa.

[0019] The matching of temperature and pressure determines the evaporation rate of hydrogen peroxide: low temperature requires low pressure to maintain moderate evaporation and avoid inefficiency caused by too slow evaporation; high temperature requires high pressure to suppress violent boiling and prevent liquid film rupture.

[0020] Furthermore, in step (1), the amount of electronic-grade hydrogen peroxide added is 0.01-10000 L / h, for example, 0.01-100 L / h, 0.1-500 L / h, 0.5-800 L / h, 1-1000 L / h, or 10-10000 L / h.

[0021] The balance between gas velocity and addition amount ensures sufficient adsorption of impurities: if the addition amount is too large, the impurities will be carried into the next process before they are completely settled; if the addition amount is too small, the membrane structure will dry up due to excessive evaporation.

[0022] This invention leverages the differential saturated vapor pressure of hydrogen peroxide at different temperatures. By precisely controlling refining conditions, the system maintains a laminar flow state with a low Reynolds coefficient. This state ensures smooth and orderly fluid flow, fundamentally minimizing the impact and damage to the membrane structure caused by turbulent flow. Furthermore, the surface gas carrier's circulating aeration process accelerates gas flow to enhance gas-liquid exchange efficiency. As the carrier gas diffuses upward, it forms a stable 0.1-100 nm liquid film at the gas-liquid interface with the liquid hydrogen peroxide flowing down from the distributor above, increasing the gas-liquid exchange area and improving refining efficiency.

[0023] In a specific embodiment, in step (1), a certain amount of electronic grade hydrogen peroxide is uniformly distributed through a liquid distributor and then introduced into an ultra-high purity container. Under non-contact heating and maintained in a non-boiling state, a surface gas carrier device is combined to circulate the carrier gas, and the gas velocity is controlled (0.01-1000 m / s). 3 / h), temperature (-50 ℃ ~ 150 ℃), pressure (0.01-1000 kPa) and hydrogen peroxide addition amount (0.01-10000 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0024] Furthermore, in step (2), the temperature in the ultrahigh purity container is adjusted to -50°C to -25°C, for example, -50°C, -40°C, -35°C, -30°C, -25°C, or a range formed by any two values.

[0025] Furthermore, in step (2), the pressure in the ultrahigh purity container is adjusted to 0.1-700 kPa, for example, 0.1-100 kPa, 0.5-500 kPa, 1-600 kPa, or 10-700 kPa.

[0026] The low temperature and low pressure environment reduces the saturated vapor pressure of hydrogen peroxide, causing it to change from "easy to evaporate" to "metastable state", facilitating subsequent condensation and collection, while providing thermodynamic conditions for the transformation of liquid film into superfluid medium film.

[0027] Furthermore, in step (2), the surface gas carrier device circulates the film-forming gas at a speed of 0.01-1000m 3 / h, for example, it can be 0.01-0.1 m 3 / h, 0.01-900 m 3 / h, 0.1-700 m 3 / h, 1-1000 m 3 / h.

[0028] By controlling the refining conditions and introducing a film-forming gas, hydrogen peroxide is stably maintained in a superfluid medium membrane state: particles, organic carbon, and other impurities are adsorbed by the membrane due to surface tension and settle and concentrate. The thickness of the superfluid medium membrane exhibits dynamic control characteristics, determined by the coordinated gas and liquid speeds: the membrane thickness decreases when the gas speed increases, and increases when the liquid speed increases. This dynamic balance has strict boundary conditions: if the membrane thickness is too thin, it will rupture due to excessive surface tension, while if it is too thick, the impurity adsorption efficiency per unit area will be reduced. The stability of the superfluid medium membrane is guaranteed by an energy balance mechanism: the superfluid medium membrane absorbs the energy generated by the evaporation process to maintain its own form, and the excess energy is discharged with the carrier gas circulation system. This design not only avoids the decomposition of the membrane structure caused by local overheating, but also significantly increases the gas-liquid contact area through the nano-scale membrane structure, thereby achieving a breakthrough improvement in refining efficiency.

[0029] Fluorine-containing gases such as difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane, and carbon tetrafluoride do not react with hydrogen peroxide, have lower surface tension, and exhibit excellent adsorption properties. While maintaining a low Reynolds coefficient, they can more stably support the structural integrity of the superfluid dielectric membrane. If gases such as nitrogen from the refining process continue to be used, a superfluid dielectric membrane will not form, and the adsorption of impurities will not be achieved. The introduction of these membrane-forming gases significantly increases the adsorption capacity of impurities on the membrane surface. This is due to the stronger hydrophobic interaction between the fluorine-containing gas and the impurities, which in turn strengthens the directional adsorption of impurities and significantly improves impurity separation efficiency.

[0030] Furthermore, in step (2), the condenser is selected from a shell and tube condenser, a coil condenser or a plate condenser.

[0031] Furthermore, in step (2), the material of the condenser is ultra-high purity fluoroplastic or ultra-high purity fluorine-lined material.

[0032] Furthermore, in step (3), the condenser is provided with a cooling medium passage, a carrier gas passage and a material passage, as well as a carrier gas outlet and a condensation outlet.

[0033] Furthermore, in step (3), the condensing temperature of the condenser is -5°C to 25°C, for example, it can be -5°C, 5°C, 0°C, 10°C, 15°C, 20°C, 25°C, or a range formed by any two values.

[0034] Furthermore, in step (3), the mass concentration of the ultra-high purity electronic grade hydrogen peroxide is 30%-31.5%.

[0035] Preferably, in step (3), the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide is below 0.01 ppt.

[0036] More preferably, in step (3), the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide is below 0.005 ppt.

[0037] In a specific embodiment, in step (3), the metastable saturated gas is supersaturated and condensed into a liquid by a condenser at -5°C to 25°C and collected to obtain ultra-high purity electronic grade hydrogen peroxide with a metal ion mass content of less than 0.1 ppt; after separation, the carrier gas is compressed by a gas compressor and recycled into the ultra-high purity container.

[0038] Furthermore, in step (4), the concentration ratio is 1:(10-1000), for example, it can be 1:10, 1:100, 1:500, 1:700, 1:1000, or a range formed by any two ratios.

[0039] Furthermore, the concentrated sample preparation, analysis and purification process of the electronic-grade hydrogen peroxide provided by the present invention is carried out under ultra-clean conditions.

[0040] Furthermore, the ultra-clean conditions include operating in a Class 10 clean room environment.

[0041] Furthermore, the ultra-clean conditions include a metal dissolution rate of 30 ppt-50 ppt for all equipment.

[0042] Furthermore, the ultra-clean conditions include that the metal dissolution amount of all equipment under heating conditions is 30 ppt-50 ppt.

[0043] The beneficial effects of the present invention are: 1. The ultra-high-purity electronic-grade hydrogen peroxide purified by the present invention can reduce the mass content of each individual metal ion to below 0.1 ppt, or even below 0.01 ppt or 0.005 ppt, breaking through the 1 ppt bottleneck of traditional processes. At the same time, through high-rate concentration and superfluid medium membrane enrichment, accurate detection of less than 0.1 ppt is achieved on the basis of the existing ICP-MS analysis detection limit, effectively overcoming the limitations of traditional detection equipment and analytical methods in detecting low-concentration impurities.

[0044] 2. The present invention's concentrated sample preparation, analysis, and purification process for electronic-grade hydrogen peroxide employs a comprehensive synergistic system of temperature, pressure, carrier gas circulation, and film-forming gas. The high temperature and high pressure of the refining process accelerates liquid film formation and provides momentum for mass transfer. The targeted film-forming gas during the low temperature and low pressure of the concentration process ensures the stability of the superfluid dielectric film. This multi-parameter synergy ensures stable and controllable product purity, precisely adapting to the increasing purity requirements of ultra-high-purity electronic-grade hydrogen peroxide. It can consistently meet the stringent high-purity hydrogen peroxide standards required by key processes such as electronic component cleaning, chip cleaning and etching, and silicon wafer photoresist removal, providing solid technical support for core processes in the electronic information industry.

[0045] 3. The core advantage of the process of the present invention lies in the deep concentration and efficient separation of impurities in electronic-grade hydrogen peroxide, which can achieve high-precision analysis of electronic-grade hydrogen peroxide at 0.005-0.1ppt. At the same time, it involves purity quality improvement technology, which can not only meet the stringent requirements of precise sample preparation and analysis and testing in laboratory environments, but also adapt to industrial large-scale production scenarios. It can be widely used in laboratory purity analysis, semiconductor integrated circuit manufacturing, liquid crystal panel material preparation, electronic material production and chemical industry, etc. The electronic-grade hydrogen peroxide concentration, sample preparation, analysis and purification process provided by the present invention plays an outstanding role in promoting the purity upgrade of electronic materials and reducing the risk of impurity contamination in high-end manufacturing, and has extremely high economic value, resource utilization value and social value. DETAILED DESCRIPTION

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this invention pertains. The terms used in this specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0047] The present invention provides a concentrated sample preparation analysis and purification process for electronic-grade hydrogen peroxide, comprising the following steps: (1) Electronic grade hydrogen peroxide is introduced into an ultra-high purity container through a liquid distributor, and carrier gas is circulated and blown in combination with a surface carrier device under non-contact heating and maintaining the hydrogen peroxide in a non-boiling state, and controllably refined under the conditions of a temperature of -50°C to 150°C and a pressure of 0.01-1000 kPa in the ultra-high purity container, so that the carrier gas and gaseous hydrogen peroxide diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film; (2) adjusting the temperature in the ultra-high purity container to -50°C~-25°C and the pressure to 0.1-700 kPa, and blowing film-forming gas through the surface carrier gas device so that the hydrogen peroxide always maintains a superfluid medium film in a superfluid state, impurities are adsorbed on the surface of the superfluid medium membrane to achieve concentration and sedimentation, and the hydrogen peroxide forms a metastable saturated gas and enters the condenser; wherein the film-forming gas is selected from one or more of difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane and carbon tetrafluoride; (3) condensing the metastable saturated gas into liquid form through the condenser and collecting the collected liquid hydrogen peroxide, circulating the collected liquid hydrogen peroxide into an ultra-high purity container until ultra-high purity electronic grade hydrogen peroxide with a metal ion mass content of less than 0.1 ppt is collected; the carrier gas is compressed and circulated into the ultra-high purity container after separation; (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:(10-1000) to obtain a hydrogen peroxide concentrate, and the concentration efficiency of impurity ions and total organic carbon (TOC) is 80%-90%.

[0048] The core concept of the present invention is to utilize the differences in saturated vapor pressure of hydrogen peroxide at different temperatures to concentrate electronic-grade hydrogen peroxide with a metal ion content of less than 100 ppt at a ratio of 1:(10-1000) using a non-contact heating method. The solution is then purified by aeration using a surface gas carrier device. Furthermore, the concentration is achieved by injecting a film-forming gas combined with physical state control of the hydrogen peroxide within the system. The impurity ion concentration efficiency can reach 80-90%. This process prevents the hydrogen peroxide in the ultra-high-purity container from violently boiling and discharging impurities in the form of bubbles or mist. The metastable saturated hydrogen peroxide is collected by a condenser to obtain ultra-high-purity electronic-grade hydrogen peroxide with a metal ion content of less than 0.1 ppt.

[0049] Compared to traditional purification analysis and purification techniques, this invention improves the purity of electronic-grade hydrogen peroxide to below 0.1 ppt, with a simple, efficient, and high-purity method. When applied to the semiconductor industry, it can minimize impurity-induced issues, improving product yields; reduce catalytic corrosion of equipment by impurities, extending maintenance cycles and reducing production costs; and avoid impurity-induced pattern defects, meeting the demands of higher-resolution photolithography processes and contributing to the upgrading of related industries.

[0050] The present invention will be further described below with reference to specific examples so that those skilled in the art can better understand the present invention and implement it, but the examples are not intended to limit the present invention.

[0051] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials, equipment, reagents, etc. used are all commercially available unless otherwise specified.

[0052] In the following examples and comparative examples, the hydrogen peroxide content was analyzed by potassium permanganate titration, the metal ion mass content was determined by inductively coupled plasma mass spectrometry (ICP-MS, Thermo X-7 series), and the anion content was determined by liquid ion chromatography (Dionex Aquion IC).

[0053] Example 1 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 31.5% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity PFA). Under non-contact heating and maintained in a non-boiling state, oxygen was circulated in a surface gas carrier device. By controlling the gas velocity (500 m / s), the hydrogen peroxide was heated to a constant temperature and then heated to a constant temperature. 3 / h), temperature (150 °C), pressure (800 kPa) and hydrogen peroxide addition amount (100 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0054] (2) The temperature in the ultra-high purity container was adjusted to -40 °C and the pressure to 100 kPa. A mixture of carbon tetrafluoride and difluoromethane (volume ratio of 1:1) was circulated through the surface carrier gas device to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities were adsorbed on the surface of the superfluid medium membrane (0.5 nm) and concentrated and precipitated. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0055] (3) The metastable saturated gas is supersaturated and condensed into liquid at 25 °C through a condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide can reach below 0.1ppt; after separation, the carrier gas is compressed by a gas compressor and recycled into the ultra-high purity container.

[0056] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:10 in the above process to obtain a hydrogen peroxide concentrate with a concentration efficiency of 90%.

[0057] Example 2 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 30% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of FEP). Under non-contact heating and maintained in a non-boiling state, a mixture of nitrogen and argon was circulated in a surface gas carrier device. The gas velocity was controlled (700 m / s). 3 / h), temperature (0 ℃), pressure (50 kPa) and hydrogen peroxide addition amount (0.01 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0058] (2) The temperature in the ultra-high purity container was adjusted to -25 °C and the pressure to 700 kPa. Tetrafluoroethane was circulated through the surface carrier gas device to transform the liquid film into a superfluid medium film. Impurities were adsorbed on the surface of the superfluid medium film (1 nm) and concentrated and precipitated. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0059] (3) The metastable saturated gas was supersaturated at -5 °C through a condenser and condensed into liquid and collected to obtain ultra-high purity electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of ultra-high purity electronic grade hydrogen peroxide can reach below 0.01 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0060] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain a hydrogen peroxide concentrate with a concentration efficiency of 87%.

[0061] Example 3 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 30% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity PVDF). Under non-contact heating and maintained in a non-boiling state, nitrogen was circulated in a surface gas carrier device. By controlling the gas velocity (0.01 m 3 / h), temperature (-20 ℃), pressure (0.1 kPa) and hydrogen peroxide addition amount (0.1 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0062] (2) The temperature in the ultra-high purity container was adjusted to -40 °C and the pressure to 100 kPa. Hexafluoroethane was circulated through the surface carrier gas device to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities were adsorbed on the surface of the superfluid medium membrane (100 nm) and concentrated and settled. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0063] (3) The metastable saturated gas was supersaturated at 15 °C through a condenser and condensed into liquid and collected to obtain ultra-high purity electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide can reach below 0.005 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0064] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:1000 in the above process to obtain a hydrogen peroxide concentrate with a concentration efficiency of 81%.

[0065] Example 4 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 32% and a metal ion mass content of less than 100 ppt is evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ordinary PTFE). Under non-contact heating and maintained in a non-boiling state, carbon dioxide is circulated and blown into the container in combination with a surface gas carrier device. By controlling the gas velocity (1000 m / s), the gas flow rate is continuously increased. 3 / h), temperature (30 °C), pressure (101 kPa) and hydrogen peroxide addition amount (10000 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0066] (2) The temperature in the ultra-high purity container was adjusted to -50 °C and the pressure to 0.1 kPa. A mixture of octafluorocyclobutane and tetrafluoroethane (volume ratio of 1:1) was circulated through the surface carrier gas device to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities were adsorbed on the surface of the superfluid medium membrane (0.5 nm) and concentrated and precipitated. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0067] (3) The metastable saturated gas is supersaturated and condensed into liquid at 25 °C through a condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide can reach below 0.1ppt; after separation, the carrier gas is compressed by a gas compressor and recycled into the ultra-high purity container.

[0068] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:10 in the above process to obtain a hydrogen peroxide concentrate with a concentration efficiency of 89%.

[0069] Example 5 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controlled metal dissolution, and controlled impurity content), electronic grade hydrogen peroxide with a mass concentration of 32% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of PFA). Under non-contact heating and maintained in a non-boiling state, argon gas was circulated in a surface gas carrier device. By controlling the gas velocity (0.1 m 3 / h), temperature (80 ℃), pressure (500 kPa) and hydrogen peroxide addition amount (1000 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0070] (2) The temperature in the ultra-high purity container was adjusted to -30 °C and the pressure to 400 kPa. Octafluoropropane was circulated through the surface carrier gas device to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities were adsorbed on the surface of the superfluid medium membrane (15 nm) and concentrated and settled. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0071] (3) The metastable saturated gas was supersaturated at 10 °C through a condenser and condensed into liquid and collected to obtain ultra-high purity electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide can reach below 0.005 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0072] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain a hydrogen peroxide concentrate with a concentration efficiency of 85%.

[0073] Example 6 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 31% and a metal ion mass content of less than 100 ppt is evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity quartz glass). Under non-contact heating and maintained in a non-boiling state, air is circulated in a surface gas carrier device. By controlling the gas velocity (10 m 3 / h), temperature (-50 ℃), pressure (0.01 kPa) and hydrogen peroxide addition amount (10 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0074] (2) The temperature in the ultra-high purity container was adjusted to -50 °C and the pressure to 0.1 kPa. A mixture of difluoromethane and octafluoropropane (volume ratio of 1:1) was circulated through the surface carrier gas device to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities were adsorbed on the surface of the superfluid medium membrane (0.1 nm) and concentrated and precipitated. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0075] (3) The metastable saturated gas was supersaturated and condensed into liquid at 25 °C through a condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the ultra-high purity electronic grade hydrogen peroxide can reach below 0.01 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0076] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:1000 in the above process to obtain a hydrogen peroxide concentrate with a concentration efficiency of 82%.

[0077] Comparative Example 1 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 31.5% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity PFA). Under non-contact heating and maintained in a non-boiling state, argon gas was circulated in a surface gas carrier device. By controlling the gas velocity (100 m / s), the argon gas was continuously injected into the container. 3 / h), temperature (170 ℃), pressure (1000 kPa) and hydrogen peroxide addition amount (100 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0078] (2) The temperature in the ultra-high purity container was adjusted to -35 °C and the pressure to 300 kPa. Octafluoropropane was circulated through the surface carrier gas device to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities were adsorbed on the surface of the superfluid medium membrane (50 nm) and concentrated and precipitated. The hydrogen peroxide formed a metastable saturated gas and entered the condenser.

[0079] (3) The metastable saturated gas was supersaturated and condensed into liquid at -35 °C through a condenser and collected to obtain liquid electronic grade hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the liquid hydrogen peroxide was less than 100 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0080] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain a hydrogen peroxide concentrate.

[0081] Comparative Example 2 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic-grade hydrogen peroxide with a mass concentration of 32% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity PFA). Under non-contact heating and maintained in a non-boiling state, controllable refining was performed by controlling the temperature (40 °C), pressure (200 kPa), and the amount of hydrogen peroxide added (10,000 L / h).

[0082] (2) Adjust the temperature in the ultra-high purity container to -30 °C and the pressure to 400 kPa. The hydrogen peroxide forms a metastable saturated gas and enters the condenser along with the carrier gas.

[0083] (3) The metastable saturated gas was supersaturated and condensed into liquid at 5 °C through a condenser and collected to obtain liquid hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the liquid hydrogen peroxide was less than 100 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0084] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:1000 in the above process to obtain a hydrogen peroxide concentrate.

[0085] Comparative Example 3 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 30% and a metal ion mass content of less than 100 ppt is evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity quartz glass). Under non-contact heating and maintained in a non-boiling state, nitrogen is circulated in a surface gas carrier device. By controlling the gas velocity (200 m / s), the hydrogen peroxide is heated to a constant temperature and then heated to a constant temperature. 3 / h), temperature (-10 ℃), pressure (0.1 kPa) and hydrogen peroxide addition amount (1000 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0086] (2) Adjust the temperature in the ultra-high purity container to -40 °C and the pressure to 100 kPa. Nitrogen is circulated through the surface carrier gas device, and hydrogen peroxide forms a metastable saturated gas and enters the condenser.

[0087] (3) The metastable saturated gas was supersaturated at 15 °C through a condenser and condensed into a liquid state and collected to obtain liquid hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the liquid hydrogen peroxide was less than 100 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0088] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain a hydrogen peroxide concentrate.

[0089] Comparative Example 4 A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide comprises the following steps: (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal dissolution, and controllable impurity content), electronic grade hydrogen peroxide with a mass concentration of 31% and a metal ion mass content of less than 100 ppt was evenly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity PVDF). Under non-contact heating and maintained in a non-boiling state, nitrogen was circulated in a surface gas carrier device. By controlling the gas velocity (400 m / s), the hydrogen peroxide was uniformly distributed through a liquid distributor and then introduced into an ultra-high purity container (made of ultra-high purity PVDF). 3 / h), temperature (50 °C), pressure (300 kPa) and hydrogen peroxide addition amount (100 L / h) are controllably refined to allow the carrier gas and gaseous hydrogen peroxide to diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0090] (2) Adjust the temperature in the ultra-high purity container to 50 °C and the pressure to 300 kPa. The surface carrier gas device circulates carbon tetrafluoride, and the hydrogen peroxide forms a metastable saturated gas and enters the condenser.

[0091] (3) The metastable saturated gas was supersaturated and condensed into liquid at -5 °C through a condenser and collected to obtain liquid hydrogen peroxide. After ICP-MS detection, the metal ion mass content of the liquid hydrogen peroxide was less than 100 ppt; after separation, the carrier gas was compressed by a gas compressor and recycled into the ultra-high purity container.

[0092] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:10 in the above process to obtain a hydrogen peroxide concentrate.

[0093] The parameters of the concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide in Examples 1-5 are shown in Table 1: Table 1

[0094] The parameters of the concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide in Example 6 and Comparative Examples 1-4 are shown in Table 2: Table 2

[0095] The ion mass content of the ultra-high-purity electronic-grade hydrogen peroxide obtained by purification in Examples 1-6 is shown in Table 3: Table 3

[0096] Table 3

[0097] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the claims of the present invention.

Claims

1. A concentrated sample preparation analysis and purification process for electronic grade hydrogen peroxide, characterized in that: The following steps are involved: (1) Electronic grade hydrogen peroxide is introduced into an ultra-high purity container through a liquid distributor, and carrier gas is circulated and blown into the container through a surface carrier gas device under non-contact heating and while maintaining the hydrogen peroxide in a non-boiling state. Controllable refining is performed under the conditions of a temperature of -50°C to 150°C and a pressure of 0.01-1000 kPa in the ultra-high purity container, so that the carrier gas and gaseous hydrogen peroxide diffuse upward and undergo gas-liquid exchange with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film; (2) Adjusting the temperature in the ultra-high purity container to -50°C~-25°C and the pressure to 0.1-700 kPa, blowing film-forming gas through the surface carrier gas device to keep the hydrogen peroxide in a superfluid state, and adsorbing impurities on the surface of the superfluid medium membrane to achieve concentration and sedimentation, and the hydrogen peroxide forms a metastable saturated gas and enters the condenser; wherein the film-forming gas is selected from one or more of difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane and carbon tetrafluoride; (3) condensing the metastable saturated gas into liquid form through the condenser and collecting the collected liquid hydrogen peroxide, circulating the collected liquid hydrogen peroxide into an ultra-high purity container until ultra-high purity electronic grade hydrogen peroxide with a metal ion mass content of less than 0.1 ppt is collected; the carrier gas is compressed and circulated into the ultra-high purity container after separation; (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:(10-1000) to obtain a hydrogen peroxide concentrate, and the concentration efficiency of impurity ions and total organic carbon is 80%-90%.

2. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, characterized in that, In step (1), the metal ion mass content of the electronic grade hydrogen peroxide is less than 100 ppt.

3. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, wherein In step (1), the material of the ultra-high purity container is ordinary PTFE, ultra-high purity PVDF, PFA, FEP or ultra-high purity quartz glass.

4. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, wherein In step (1), the non-contact heating method is infrared heating, microwave heating or heating through an ultra-high purity tetrafluoroethylene heat exchanger.

5. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, wherein In step (1), the carrier gas is selected from one or more of nitrogen, oxygen, carbon dioxide, air and argon.

6. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, characterized in that, In step (1), the surface gas carrier device circulates the carrier gas at a velocity of 0.01-1000 m 3 / h.

7. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, characterized in that, In step (1), before circulating the carrier gas through the surface carrier gas device, the carrier gas is first filtered to remove impurities, wherein the impurities include particulate matter and organic carbon.

8. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, characterized in that, In step (1), the amount of electronic grade hydrogen peroxide added is 0.01-10000 L / h.

9. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, characterized in that, In step (3), the condensation temperature of the condenser is -5°C~25°C.

10. The concentrated sample preparation analysis and purification process of electronic grade hydrogen peroxide according to claim 1, characterized in that: Each step is carried out under ultra-clean conditions.

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