Concentration sample analysis and purification process of electronic grade hydrogen peroxide

Abstract

The application discloses a kind of concentration sample analysis and purification process of electronic grade hydrogen peroxide, the process is introduced into electronic grade hydrogen peroxide into ultrahigh purity container, in super-clean atmosphere, using the difference of hydrogen peroxide saturated vapor pressure at different temperatures, control concentration ratio 1:(10-1000), maintain non-boiling state by non-contact heating, combined with surface carrier gas device circulating air to keep laminar flow state, combined with the formation of superfluid medium film by passing into film-forming gas and control condition, 80%-90% impurities are adsorbed and settled, metastable saturated hydrogen peroxide is condensed and precipitated by condenser. Selecting the residual liquid or condensate, concentration sample analysis and purification can be achieved respectively, the metal ion mass content of the obtained ultrahigh purity electronic grade hydrogen peroxide is as low as 0.1 ppt or less, which can achieve high-ratio super-clean concentration analysis sample preparation and high-purity hydrogen peroxide purification effect, meet the needs of high-end fields such as laboratory and semiconductor manufacturing, and lay a foundation for mass production of G6 and G7 products.

Description

Technical Field

[0001] This invention relates to the field of hydrogen peroxide concentration, sample preparation, analysis and purification technology, specifically to a process for the concentration, sample preparation, analysis and purification of electronic-grade hydrogen peroxide. Background Technology

[0002] With the rapid development of my country's semiconductor and electronics industries, ultra-high purity electronic chemicals, as core materials in the industrial chain, directly affect technological breakthroughs in high-end manufacturing fields such as chip manufacturing processes and LCD panel precision. Among them, ultra-high purity electronic-grade hydrogen peroxide is widely used in key processes such as photoresist removal from silicon wafers, precision cleaning and etching of electronic components, and its purity requirements continue to rise as the global semiconductor industry evolves towards processes below 5 nm.

[0003] Currently, the purity detection of electronic-grade hydrogen peroxide mainly relies on ICP-MS (inductively coupled plasma mass spectrometry) technology to analyze trace metal ions, and the performance of the detection equipment directly determines the analytical accuracy. Under Class 10 cleanroom conditions, mainstream equipment such as the Agilent 7900 has a low limit of detection (LOD) of approximately 0.3 ppt, the Thermo Fisher ICAP Qc has an LOD of approximately 0.5 ppt, and the EXPEC 7350 and LabTech Lab MS 5000 both have an LOD of 1 ppt. However, with existing sample preparation techniques, the metal ion content in pure water can only be controlled to below 1 ppt at most, which is insufficient to meet the analytical requirements for even lower LODs, resulting in a technical bottleneck for the accurate detection of ultra-trace impurities.

[0004] Furthermore, with continuous breakthroughs in semiconductor manufacturing processes, G5-grade purity can no longer meet the quality requirements of ultra-high purity hydrogen peroxide for next-generation electronic devices. There is an urgent need to develop a new generation of purification technology with G6-grade and above purity to solve the core problem restricting industrial upgrading.

[0005] In summary, existing analytical techniques suffer from insufficient sample purity and limited detection accuracy, and the purification technology cannot overcome the G5 level bottleneck, making it difficult to meet the urgent demand of the semiconductor industry for ultra-high purity electronic-grade hydrogen peroxide. Therefore, it is imperative to develop a technology for the concentrated sample preparation and analysis of electronic-grade hydrogen peroxide and its purification to a higher purity. Summary of the Invention

[0006] To address the technical challenges of limited purity improvement, incomplete impurity separation, and insufficient detection limits in existing electronic-grade hydrogen peroxide purification processes, this invention aims to provide a concentration, sample preparation, analysis, and purification process for electronic-grade hydrogen peroxide. Through carrier gas purification, superfluid membrane technology, and multi-parameter synergistic control, this process overcomes the purity bottleneck of traditional methods, simultaneously achieving both deep purification and highly efficient concentration. This process demonstrates significant concentration and separation effects, achieving 80%-90% efficient impurity concentration and removal for electronic-grade hydrogen peroxide with an initial metal ion content of 100 ppt to 1 ppt. Ultimately, it reduces 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 of high-end electronic-grade hydrogen peroxide such as G6 and G7.

[0007] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0008] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0009] (1) Electronic grade hydrogen peroxide is introduced into an ultra-high purity container through a liquid distributor. Under non-contact heating and while maintaining the hydrogen peroxide in a non-boiling state, carrier gas is circulated in conjunction with a surface carrier gas device. Controllable purification is carried out in the ultra-high purity container at a temperature of -50 ℃ to 150 ℃ and a pressure of 0.01-1000 kPa, so that the carrier gas and gaseous hydrogen peroxide diffuse upward and exchange gas and liquid with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0010] (2) Adjust the temperature inside the ultra-high purity container to -50 ℃ to -25 ℃ and the pressure to 0.1 to 700 kPa. Blow film-forming gas through the surface carrier gas device to keep the hydrogen peroxide in a superfluid state. Impurities are adsorbed on the surface of the superfluid medium film to achieve concentration and sedimentation. The hydrogen peroxide forms metastable saturated gas and enters the condenser. The film-forming gas is selected from one or more of difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane and carbon tetrafluoride.

[0011] (3) The metastable saturated gas is condensed into liquid by the condenser and collected. The collected liquid hydrogen peroxide is circulated into the 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 separated, compressed and circulated into the ultra-high purity container.

[0012] (4) After concentrating the residual liquid in the ultra-high purity container at a ratio of 1:(10-1000), hydrogen peroxide concentrate is obtained, and the concentration efficiency of impurity ions and total organic carbon (TOC) is 80%-90%.

[0013] This invention discloses a process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, achieving the dual functions of hydrogen peroxide concentration and sample preparation analysis and the 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; maintaining a non-boiling state in an ultra-clean atmosphere by controlling the difference in saturated vapor pressure of hydrogen peroxide at different temperatures using non-contact heating; and maintaining a laminar flow state with a low Reynolds coefficient by circulating gas through a surface carrier gas device—a state that avoids impurity dispersion caused by turbulence. Simultaneously, a liquid film forms on the surface of the packing material within the container, serving as a primary mass transfer interface, increasing both the heat exchange area and the purification speed. The introduction of film-forming gas through the surface carrier gas device ensures that the liquid hydrogen peroxide at the bottom of the container, along with the partially solid hydrogen peroxide surface, maintains a 0.1-100 nm superfluid medium film through gas exchange with the saturated hydrogen peroxide gas. This causes impurities to be adsorbed, concentrated, and precipitated on the surface of this superfluid medium film, and excess energy is dissipated through gas circulation, continuously and efficiently maintaining the stability of the superfluid medium film. By selecting the collection target, a dual function can be achieved: collecting the residual liquid in the ultra-high purity container completes the hydrogen peroxide concentration and sample preparation, while collecting the condensate from the condenser achieves hydrogen peroxide purification.

[0014] The core of this invention lies in the following: the liquid membrane, as the initial mass transfer interface, primarily increases the gas-liquid contact area and accelerates mass transfer efficiency; while the superfluid medium membrane with a thickness of 0.1-100 nm is key to achieving deep purification, its nanoscale structure endowing it with superior impurity adsorption capacity. A simple liquid membrane cannot meet the demands of high-level purification, while the superfluid medium membrane, through its unique interface effect and energy balance mechanism, can achieve directional adsorption and efficient separation of impurities. The superfluid medium membrane, formed by precisely controlling process parameters, can achieve both high-rate ultra-clean sample preparation and concentration, and high-purity purification of hydrogen peroxide, under ultra-clean conditions. After concentration, ICP-MS detection and calculation confirm that the final high-quality, high-value ultra-high purity electronic-grade hydrogen peroxide has a metal ion content as low as below 0.1 ppt, even below 0.01 ppt or 0.005 ppt, providing crucial technical support for the mass production of G6 and G7 grade ultra-high purity electronic-grade hydrogen peroxide.

[0015] Further, 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.

[0016] Furthermore, in step (1), the metal ion mass content of the electronic-grade hydrogen peroxide is less than 100 ppt.

[0017] Furthermore, in step (1), the ultra-high purity container is made of 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. These materials share the common characteristic of extremely low metal leaching (<30 ppt) and resistance to hydrogen peroxide corrosion. If ordinary metal or glass materials are used, the metal ions released from their surfaces will directly contaminate the system, preventing the product purity from exceeding 1 ppt.

[0018] Furthermore, in step (1), the non-contact heating method is infrared heating, microwave heating, or heating through an ultra-high purity PTFE 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 generating local high temperature points, causing hydrogen peroxide decomposition and damaging the superfluid film; while infrared / microwave heating can achieve uniform temperature rise, and the ultra-high purity PTFE heat exchanger transfers heat indirectly through the medium, ensuring that the system temperature fluctuation is <±5 ℃.

[0019] Further, in step (1), the carrier gas is selected from one or more of nitrogen, oxygen, carbon dioxide, air and argon.

[0020] Furthermore, in step (1), before the surface carrier gas device circulates the carrier gas, it first filters the carrier gas to remove impurities such as particulate matter and organic carbon.

[0021] Furthermore, in step (1), the gas velocity of the carrier gas circulated by the surface carrier gas device is 0.01-1000 m. 3 / h, for example, could 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. If the gas velocity is too low, a stable gas-liquid interface cannot be formed, and the liquid film is prone to breakage due to insufficient surface tension; if the gas velocity is too high, it will disrupt the laminar flow state, causing impurities to redisperse.

[0022] Further, in step (1), the temperature inside the ultra-high purity container is -50 ℃ to 150 ℃, for example, it can be -50 ℃, -40 ℃, -30 ℃, -20 ℃, 0 ℃, 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 150 ℃, or any two of these values ​​forming a range.

[0023] Further, in step (1), the pressure inside the ultra-high purity container is 0.01-1000 kPa, for example, it can be 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.

[0024] The matching of temperature and pressure determines the evaporation rate of hydrogen peroxide: low temperature requires low pressure to maintain adequate evaporation and avoid inefficiency caused by slow evaporation; high temperature requires high pressure to suppress violent boiling and prevent liquid film rupture.

[0025] Further, in step (1), the amount of electronic-grade hydrogen peroxide added is 0.01-10000 L / h, for example, it can be 0.01-100 L / h, 0.1-500 L / h, 0.5-800 L / h, 1-1000 L / h, or 10-10000 L / h.

[0026] The balance between gas velocity and the amount added ensures that impurities are fully adsorbed: if the amount added is too large, impurities will be carried into the next process before they are completely settled; if the amount added is too small, the membrane structure will dry out due to excessive evaporation.

[0027] This invention leverages the differential saturated vapor pressure of hydrogen peroxide at different temperatures to maintain the system in a laminar flow state with a low Reynolds coefficient by precisely controlling the purification conditions. In this state, fluid flow is stable and orderly, fundamentally avoiding the impact and damage of turbulence on the membrane structure. Simultaneously, the circulating gas flow process of the surface carrier gas device enhances gas-liquid exchange efficiency by accelerating gas flow: as the carrier gas diffuses upwards, it forms a stable 0.1-100 nm liquid film at the gas-liquid interface with the liquid hydrogen peroxide flowing down from the upper distributor, increasing the gas-liquid exchange area and improving purification efficiency.

[0028] In a specific implementation, in step (1), a certain amount of electronic-grade hydrogen peroxide is evenly distributed through a liquid distributor and then introduced into an ultra-high purity container. Under non-contact heating and while maintaining a non-boiling state, carrier gas is circulated in conjunction with a surface carrier gas device. The gas velocity is controlled (0.01-1000 m / s). 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (-50 ℃~150 ℃), pressure (0.01-1000 kPa), and amount of hydrogen peroxide added (0.01-10000 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0029] Further, in step (2), the temperature inside the ultrapure container is adjusted to -50 ℃ to -25 ℃, for example, it can be -50 ℃, -40 ℃, -35 ℃, -30 ℃, -25 ℃, or any two of these values ​​forming a range.

[0030] Further, in step (2), the pressure inside the ultra-high purity container is adjusted to 0.1-700 kPa, for example, it can be 0.1-100 kPa, 0.5-500 kPa, 1-600 kPa, or 10-700 kPa.

[0031] The low temperature and low pressure environment reduces the saturated vapor pressure of hydrogen peroxide, causing it to change from "easily evaporable" to "metastable", which facilitates subsequent condensation and collection. At the same time, it provides thermodynamic conditions for the transformation of the liquid film into a superfluid medium film.

[0032] Furthermore, in step (2), the gas velocity of the film-forming gas circulated by the surface carrier gas device is 0.01-1000 m / s. 3 / h, for example, could 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.

[0033] By controlling the purification conditions and introducing a film-forming gas, hydrogen peroxide is stably maintained in a superfluid medium membrane state: impurities such as particles and organic carbon are adsorbed and concentrated by the membrane due to surface tension. The thickness of this superfluid medium membrane exhibits dynamic regulation characteristics, determined by the combined gas and liquid velocities: the membrane thickness decreases when the gas velocity increases, and increases when the liquid velocity increases. This dynamic equilibrium has strict boundary conditions—if the membrane thickness is too thin, it will rupture due to excessive surface tension; if it is too thick, it will reduce the impurity adsorption efficiency per unit area. The stability of the superfluid medium membrane is ensured through an energy balance mechanism: the superfluid medium membrane absorbs the energy generated during the evaporation process to maintain its shape, and excess energy is discharged with the carrier gas circulation system. This design not only avoids membrane structure decomposition caused by local overheating, but also significantly increases the gas-liquid contact area through the nanoscale membrane structure, thereby achieving a breakthrough improvement in purification efficiency.

[0034] Fluorine-containing gases such as difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane, and carbon tetrafluoride possess the characteristics of not reacting with hydrogen peroxide, having lower surface tension, and excellent adsorption performance. While maintaining a low Reynolds coefficient, they can more stably support the structural integrity of the superfluid membrane. If gases such as nitrogen from the purification process are continued, a superfluid membrane will not form, and the adsorption of impurities cannot be achieved. Introducing these film-forming gases significantly increases the adsorption energy of impurities on the membrane surface. This is due to the stronger hydrophobic interaction between the fluorine-containing gases and the impurities, thereby enhancing the directional adsorption of impurities and greatly improving the impurity separation efficiency.

[0035] Furthermore, in step (2), the condenser is selected from shell-and-tube condensers, coil condensers, or plate condensers.

[0036] Furthermore, in step (2), the condenser is made of ultra-high purity fluoroplastic or ultra-high purity fluoropolymer-lined material.

[0037] 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.

[0038] Further, in step (3), the condensation temperature of the condenser is -5 ℃ to 25 ℃, for example, it can be -5 ℃, 5 ℃, 0 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, or a range formed by any two values.

[0039] Furthermore, in step (3), the mass concentration of the ultra-high purity electronic-grade hydrogen peroxide is 30%-31.5%.

[0040] Preferably, in step (3), the metal ion mass content of the ultra-high purity electronic-grade hydrogen peroxide is below 0.01 ppt.

[0041] More preferably, in step (3), the metal ion mass content of the ultra-high purity electronic-grade hydrogen peroxide is below 0.005 ppt.

[0042] In a specific implementation, in step (3), the metastable saturated gas is supersaturated and condensed into liquid by a condenser at -5 ℃ to 25 ℃, and collected to obtain ultra-high purity electronic-grade hydrogen peroxide with a metal ion mass content of less than 0.1 ppt; the carrier gas is separated, compressed by a gas compressor, and then circulated into the ultra-high purity container.

[0043] Further, 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 any range of two ratios.

[0044] Furthermore, the concentration, sample preparation, analysis, and purification process for electronic-grade hydrogen peroxide provided by this invention is carried out under ultra-clean conditions.

[0045] Furthermore, the ultra-clean conditions include operation in a Class 10 cleanroom environment.

[0046] Furthermore, the ultra-clean conditions include a metal leaching rate of 30 ppt-50 ppt for all equipment.

[0047] Furthermore, the ultra-clean conditions include a metal leaching rate of 30 ppt-50 ppt for all equipment under heating conditions.

[0048] The beneficial effects of this invention are:

[0049] 1. The ultra-high purity electronic-grade hydrogen peroxide purified by this invention can achieve a mass content of individual metal ions as low as 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 enrichment with superfluid medium membrane, it achieves accurate detection of impurities below 0.1 ppt based on the existing detection limit of ICP-MS analysis, effectively overcoming the limitations of traditional detection equipment and analysis methods in the detection of low-concentration impurities.

[0050] 2. The electronic-grade hydrogen peroxide concentration, sample preparation, analysis, and purification process provided by this invention forms a complete synergistic system involving temperature, pressure, carrier gas circulation, and film-forming gas: the high-temperature and high-pressure conditions of the purification process accelerate liquid film formation and provide power for mass transfer, while the targeted film-forming gas under the low-temperature and low-pressure environment of the concentration process ensures the stability of the superfluid dielectric film. This multi-parameter synergistic effect ensures stable and controllable product purity, accurately adapting to the increasingly stringent requirements for ultra-high purity electronic-grade hydrogen peroxide. It can stably meet the stringent standards for high-purity hydrogen peroxide in 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.

[0051] 3. The core advantage of this invention lies in the deep concentration and efficient separation of impurities in electronic-grade hydrogen peroxide, achieving high-precision analysis of electronic-grade hydrogen peroxide at a concentration of 0.005-0.1 ppt. It also incorporates purity and quality improvement technologies, meeting the stringent requirements of precise sample preparation and analysis in laboratory environments while also being adaptable to large-scale industrial production scenarios. It can be widely applied in various fields such as laboratory purity analysis, semiconductor integrated circuit manufacturing, LCD panel material preparation, electronic material production, and chemical engineering. The concentration, sample preparation, analysis, and purification process for electronic-grade hydrogen peroxide provided by this invention plays a significant role in promoting the purity upgrade of electronic materials and reducing the risk of impurity contamination in high-end manufacturing, possessing extremely high economic, resource utilization, and social value. Detailed Implementation

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0053] This invention provides a process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0054] (1) Electronic grade hydrogen peroxide is introduced into an ultra-high purity container through a liquid distributor. Under non-contact heating and while maintaining the hydrogen peroxide in a non-boiling state, carrier gas is circulated in conjunction with a surface carrier gas device. Controllable purification is carried out in the ultra-high purity container at a temperature of -50 ℃ to 150 ℃ and a pressure of 0.01-1000 kPa, so that the carrier gas and gaseous hydrogen peroxide diffuse upward and exchange gas and liquid with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0055] (2) Adjust the temperature inside the ultra-high purity container to -50 ℃ to -25 ℃ and the pressure to 0.1-700 kPa. Blow in film-forming gas through the surface carrier gas device to keep the hydrogen peroxide in a superfluid state, forming a superfluid medium film. Impurities are adsorbed on the surface of the superfluid medium film and concentrated and settled. The hydrogen peroxide forms a metastable saturated gas and enters the condenser. The film-forming gas is selected from one or more of difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane and carbon tetrafluoride.

[0056] (3) The metastable saturated gas is condensed into liquid by the condenser and collected. The collected liquid hydrogen peroxide is circulated into the 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 separated, compressed and circulated into the ultra-high purity container.

[0057] (4) After concentrating the residual liquid in the ultra-high purity container at a ratio of 1:(10-1000), hydrogen peroxide concentrate is obtained, and the concentration efficiency of impurity ions and total organic carbon (TOC) is 80%-90%.

[0058] The core concept of this invention is as follows: Based on the difference in saturated vapor pressure of hydrogen peroxide at different temperatures, electronic-grade hydrogen peroxide with a metal ion content of less than 100 ppt is concentrated at a ratio of 1:(10-1000) using a non-contact heating method. It is then purified by blowing gas through a surface carrier gas device, and further concentrated by controlling the physical state of the hydrogen peroxide within a combined system through the introduction of film-forming gas. The concentration efficiency of impurity ions can reach 80-90%. This process avoids the violent boiling of hydrogen peroxide in the ultra-high purity container in the form of bubbles and mist, which carries away impurities. 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.

[0059] Compared with traditional purification and analysis techniques, this invention improves the purity of electronic-grade hydrogen peroxide to below 0.1 ppt, and the method is simple, efficient, and highly pure. When applied to the semiconductor industry, it can minimize impurity-induced problems, improve product yield, reduce the catalytic corrosion of equipment by impurities, extend maintenance cycles, and lower production costs; avoid pattern defects caused by impurities, meet the requirements of higher resolution lithography processes, and contribute to the upgrading of related industries.

[0060] The present invention will be further described below with reference to specific embodiments, so that those skilled in the art can better understand and implement the present invention, but the embodiments are not intended to limit the present invention.

[0061] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials, equipment, reagents, etc. used are commercially available.

[0062] In the following examples and comparative examples, the hydrogen peroxide content was analyzed by potassium permanganate titration, the metal ion mass content was detected by inductively coupled plasma mass spectrometry (ICP-MS, Thermo X-7 series), and the anions were detected by liquid ion chromatography (Dionex Aquion IC).

[0063] Example 1

[0064] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0065] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 is 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 in a non-boiling state, oxygen is circulated in conjunction with a surface carrier gas device, and the gas velocity (500 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (150 °C), pressure (800 kPa), and amount of hydrogen peroxide added (100 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0066] (2) Adjust the temperature inside the ultra-high purity container to -40 ℃ and the pressure to 100 kPa. The surface carrier gas device circulates a mixture of carbon tetrafluoride and difluoromethane (volume ratio of 1:1) to maintain the superfluid state of the electronic grade hydrogen peroxide, so that impurities are adsorbed on the surface of the superfluid medium membrane (0.5 nm), concentrated and settled, and the hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0067] (3) The metastable saturated gas is supersaturated and condensed into liquid at 25 °C by condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. According to ICP-MS detection, the metal ion mass content of ultra-high purity electronic grade hydrogen peroxide can reach less than 0.1 ppt. After separation, the carrier gas is compressed by gas compressor and then circulated 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 hydrogen peroxide concentrate with a concentration efficiency of 90%.

[0069] Example 2

[0070] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0071] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 FEP). Under non-contact heating and in a non-boiling state, a mixture of nitrogen and argon is circulated in using a surface carrier gas device, and the gas velocity (700 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (0 °C), pressure (50 kPa), and amount of hydrogen peroxide added (0.01 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0072] (2) Adjust the temperature inside the ultra-high purity container to -25 °C and the pressure to 700 kPa. The surface carrier gas device circulates tetrafluoroethane to convert the liquid film into a superfluid medium film. Impurities are adsorbed on the surface of the superfluid medium film (1 nm), concentrated and settled. Hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0073] (3) The metastable saturated gas is supersaturated and condensed into liquid at -5 °C by a condenser and collected to obtain ultra-high purity electronic-grade hydrogen peroxide. According to 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 is compressed by a gas compressor and then circulated into the ultra-high purity container.

[0074] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain hydrogen peroxide concentrate with a concentration efficiency of 87%.

[0075] Example 3

[0076] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0077] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 PVDF). Under non-contact heating and maintaining a non-boiling state, nitrogen is circulated in conjunction with a surface carrier gas device, and the gas velocity is controlled (0.01 m).3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (-20 °C), pressure (0.1 kPa), and amount of hydrogen peroxide added (0.1 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0078] (2) Adjust the temperature inside the ultra-high purity container to -40 °C and the pressure to 100 kPa. The surface carrier gas device circulates hexafluoroethane to maintain the superfluid state of electronic-grade hydrogen peroxide. Impurities are adsorbed on the surface of the superfluid medium membrane (100 nm), concentrated and settled, and hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0079] (3) The metastable saturated gas is supersaturated and condensed into liquid at 15 °C by condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. According to ICP-MS detection, the metal ion mass content of ultra-high purity electronic grade hydrogen peroxide can reach less than 0.005 ppt. After separation, the carrier gas is compressed by gas compressor and then circulated into the ultra-high purity container.

[0080] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:1000 in the above process to obtain hydrogen peroxide concentrate with a concentration efficiency of 81%.

[0081] Example 4

[0082] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0083] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 maintaining a non-boiling state, carbon dioxide is circulated in conjunction with a surface carrier gas device, and the gas velocity (1000 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (30 °C), pressure (101 kPa), and amount of hydrogen peroxide added (10000 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0084] (2) Adjust the temperature inside the ultra-high purity container to -50 °C and the pressure to 0.1 kPa. The surface carrier gas device circulates a mixture of octafluorocyclobutane and tetrafluoroethane (volume ratio of 1:1) to maintain the superfluid state of the electronic grade hydrogen peroxide. Impurities are adsorbed on the surface of the superfluid medium membrane (0.5 nm), concentrated and settled, and the hydrogen peroxide forms a metastable saturated gas and enters the condenser.

[0085] (3) The metastable saturated gas is supersaturated and condensed into liquid at 25 °C by condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. According to ICP-MS detection, the metal ion mass content of ultra-high purity electronic grade hydrogen peroxide can reach less than 0.1 ppt. After separation, the carrier gas is compressed by gas compressor and then circulated into the ultra-high purity container.

[0086] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:10 in the above process to obtain hydrogen peroxide concentrate with a concentration efficiency of 89%.

[0087] Example 5

[0088] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0089] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 PFA). Under non-contact heating and in a non-boiling state, argon gas is circulated in conjunction with a surface carrier gas device, and the gas velocity is controlled (0.1 m). 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (80 °C), pressure (500 kPa), and amount of hydrogen peroxide added (1000 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0090] (2) Adjust the temperature inside the ultra-high purity container to -30 °C and the pressure to 400 kPa. The surface carrier gas device circulates octafluoropropane to maintain the superfluid state of electronic grade hydrogen peroxide. Impurities are adsorbed on the surface of the superfluid medium membrane (15 nm), concentrated and settled, and hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0091] (3) The metastable saturated gas is supersaturated and condensed into liquid at 10 °C by a condenser and collected to obtain ultra-high purity electronic-grade hydrogen peroxide. According to ICP-MS detection, the metal ion mass content of ultra-high purity electronic-grade hydrogen peroxide can reach less than 0.005 ppt. After separation, the carrier gas is compressed by a gas compressor and then circulated into the ultra-high purity container.

[0092] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain hydrogen peroxide concentrate with a concentration efficiency of 85%.

[0093] Example 6

[0094] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0095] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 maintaining a non-boiling state, air is circulated in conjunction with a surface carrier gas device, and the gas velocity (10 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume ( / h), temperature (-50 ℃), pressure (0.01 kPa), and hydrogen peroxide addition (10 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0096] (2) Adjust the temperature inside the ultra-high purity container to -50 °C and the pressure to 0.1 kPa. The surface carrier gas device circulates a mixture of difluoromethane and octafluoropropane (volume ratio of 1:1) to maintain the superfluid state of the electronic grade hydrogen peroxide. Impurities are adsorbed on the surface of the superfluid medium membrane (0.1 nm), concentrated and settled, and the hydrogen peroxide forms a metastable saturated gas and enters the condenser.

[0097] (3) The metastable saturated gas is supersaturated and condensed into liquid at 25 °C by condenser and collected to obtain ultra-high purity electronic grade hydrogen peroxide. According to 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 is compressed by gas compressor and then circulated into the ultra-high purity container.

[0098] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:1000 in the above process to obtain hydrogen peroxide concentrate with a concentration efficiency of 82%.

[0099] Comparative Example 1

[0100] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0101] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 is 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 in a non-boiling state, argon gas is circulated in conjunction with a surface carrier gas device, and the gas velocity (100 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (170 °C), pressure (1000 kPa), and amount of hydrogen peroxide added (100 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0102] (2) Adjust the temperature inside the ultra-high purity container to -35 °C and the pressure to 300 kPa. The surface carrier gas device circulates octafluoropropane to maintain the superfluid state of electronic-grade hydrogen peroxide, so that impurities are adsorbed on the surface of the superfluid medium membrane (50 nm), concentrated and settled, and hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0103] (3) The metastable saturated gas was supersaturated and condensed into liquid at -35 °C by a condenser and collected to obtain liquid electronic-grade hydrogen peroxide. The metal ion content of the liquid hydrogen peroxide was found to be below 100 ppt by ICP-MS. The carrier gas was separated, compressed by a gas compressor, and then circulated into an ultra-high purity container.

[0104] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain hydrogen peroxide concentrate.

[0105] Comparative Example 2

[0106] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0107] (1) Under ultra-clean conditions (Class 10 clean room, controllable metal leaching, 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 ultra-high purity PFA). Under non-contact heating and in a non-boiling state, the hydrogen peroxide is controlled and purified by controlling the temperature (40 ℃), pressure (200 kPa) and the amount of hydrogen peroxide added (10000 L / h).

[0108] (2) Adjust the temperature inside the ultra-high purity container to -30 ℃ and the pressure to 400 kPa. The hydrogen peroxide forms a metastable saturated gas and enters the condenser along with the carrier gas.

[0109] (3) The metastable saturated gas was supersaturated and condensed into liquid at 5 °C by a condenser and collected to obtain liquid hydrogen peroxide. The metal ion content of the liquid hydrogen peroxide was found to be below 100 ppt by ICP-MS. The carrier gas was separated, compressed by a gas compressor, and then circulated into an ultra-high purity container.

[0110] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:1000 in the above process to obtain hydrogen peroxide concentrate.

[0111] Comparative Example 3

[0112] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0113] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 maintaining a non-boiling state, nitrogen is circulated in conjunction with a surface carrier gas device, and the gas velocity (200 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume of hydrogen peroxide (L / h), temperature (-10 °C), pressure (0.1 kPa), and amount of hydrogen peroxide added (1000 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0114] (2) Adjust the temperature inside the ultra-high purity container to -40 ℃ and the pressure to 100 kPa. Nitrogen gas is circulated into the surface carrier gas device, and hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0115] (3) The metastable saturated gas was supersaturated and condensed into liquid at 15 °C by a condenser and collected to obtain liquid hydrogen peroxide. The metal ion content of the liquid hydrogen peroxide was found to be below 100 ppt by ICP-MS. The carrier gas was separated, compressed by a gas compressor, and then circulated into an ultra-high purity container.

[0116] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:100 in the above process to obtain hydrogen peroxide concentrate.

[0117] Comparative Example 4

[0118] A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, comprising the following steps:

[0119] (1) Under ultra-clean conditions (Class 10 cleanroom, controllable metal leaching, 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 PVDF). Under non-contact heating and maintaining a non-boiling state, nitrogen is circulated in conjunction with a surface carrier gas device, and the gas velocity (400 m) is controlled. 3 The carrier gas and gaseous hydrogen peroxide are controlled and purified by adjusting the volume ( / h), temperature (50 ℃), pressure (300 kPa), and hydrogen peroxide addition (100 L / h) to allow the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film.

[0120] (2) Adjust the temperature inside the ultra-high purity container to 50 °C and the pressure to 300 kPa. The surface carrier gas device circulates carbon tetrafluoride, and hydrogen peroxide forms metastable saturated gas and enters the condenser.

[0121] (3) The metastable saturated gas was supersaturated and condensed into liquid at -5 °C by a condenser and collected to obtain liquid hydrogen peroxide. The metal ion content of the liquid hydrogen peroxide was found to be below 100 ppt by ICP-MS. The carrier gas was separated, compressed by a gas compressor, and then circulated into an ultra-high purity container.

[0122] (4) The residual liquid in the ultra-high purity container is concentrated at a ratio of 1:10 in the above process to obtain hydrogen peroxide concentrate.

[0123] The parameters for the concentration, sample preparation, analysis, and purification process of electronic-grade hydrogen peroxide in Examples 1-5 are shown in Table 1:

[0124] Table 1

[0125]

[0126] The parameters for the concentration, sample preparation, analysis, and purification process of electronic-grade hydrogen peroxide in Examples 6 and Comparative Examples 1-4 are shown in Table 2:

[0127] Table 2

[0128]

[0129] The ion mass content of the ultra-high purity electronic-grade hydrogen peroxide obtained in Examples 1-6 is shown in Table 3:

[0130] Table 3

[0131]

[0132] Continued from Table 3

[0133]

[0134] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art should understand that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A process for the concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide, characterized in that, Includes the following steps: (1) Electronic-grade hydrogen peroxide is introduced into an ultra-high purity container via a liquid distributor. Under non-contact heating and while maintaining the hydrogen peroxide in a non-boiling state, the temperature inside the ultra-high purity container is -50 ℃ to 150 ℃ and the pressure is 0.01-800 kPa. A surface carrier gas device is used to circulate carrier gas to maintain the system in a laminar flow state with a low Reynolds coefficient. This allows the carrier gas and gaseous hydrogen peroxide to diffuse upwards and exchange gas with the liquid hydrogen peroxide flowing down through the liquid distributor to form a liquid film. Inside the ultra-high purity container, low temperature is combined with low pressure, and high temperature is combined with high pressure: the pressure corresponding to a temperature of -50 ℃ is 0.01 kPa, the pressure corresponding to a temperature of 0 ℃ is 50 kPa, the pressure corresponding to a temperature of 80 ℃ is 500 kPa, and the pressure corresponding to a temperature of 150 ℃ is 800 kPa. The gas velocity of the surface carrier gas device circulating carrier gas is 0.01-1000 m / s. 3 / h; (2) Adjust the temperature inside the ultra-high purity container to -50 ℃ to -25 ℃ and the pressure to 0.1-700 kPa. Inject film-forming gas through the surface carrier gas device to maintain the hydrogen peroxide in a superfluid state, forming a superfluid medium film with a thickness of 0.1-100 nm. Impurities are adsorbed onto the surface of the superfluid medium film, achieving concentration and sedimentation. The hydrogen peroxide forms a metastable saturated gas and enters the condenser. The film-forming gas is selected from one or more of difluoromethane, tetrafluoroethane, hexafluoroethane, octafluoropropane, octafluorocyclobutane, and carbon tetrafluoride. The gas velocity of the film-forming gas circulated through the surface carrier gas device is 0.01-1000 m / s. 3 / h; (3) The metastable saturated gas is condensed into liquid by the condenser and collected. The collected liquid hydrogen peroxide is circulated into the 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 separated, compressed and circulated into the ultra-high purity container. (4) After concentrating the residual liquid in the ultra-high purity container at a ratio of 1:(10-1000), hydrogen peroxide concentrate is obtained, and the concentration efficiency of impurity ions and total organic carbon is 80%-90%.

2. The process for concentration, sample preparation, analysis, and purification 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 process for concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide according to claim 1, characterized in that, In step (1), the ultra-high purity container is made of ordinary PTFE, ultra-high purity PVDF, PFA, FEP or ultra-high purity quartz glass.

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

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

6. The process for concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide according to claim 1, characterized in that, In step (1), before the surface carrier gas device circulates the carrier gas, the carrier gas is first filtered to remove impurities, including particulate matter and organic carbon.

7. The process for concentration, sample preparation, analysis, and purification 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.

8. The process for concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide according to claim 1, characterized in that, In step (3), the condensation temperature of the condenser is -5 ℃ to 25 ℃.

9. The process for concentration, sample preparation, analysis, and purification of electronic-grade hydrogen peroxide according to claim 1, characterized in that, Each step is performed under ultra-clean conditions.

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