CN115999998A - Device and method for cleaning arsenic and phosphorus-containing pollutant component in smokeless mode - Google Patents
Device and method for cleaning arsenic and phosphorus-containing pollutant component in smokeless mode Download PDFInfo
- Publication number
- CN115999998A CN115999998A CN202211674113.0A CN202211674113A CN115999998A CN 115999998 A CN115999998 A CN 115999998A CN 202211674113 A CN202211674113 A CN 202211674113A CN 115999998 A CN115999998 A CN 115999998A
- Authority
- CN
- China
- Prior art keywords
- cleaning
- phosphorus
- arsenic
- circulating
- fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 161
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 72
- 239000011574 phosphorus Substances 0.000 title claims abstract description 72
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 59
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 30
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000007788 liquid Substances 0.000 claims abstract description 83
- 239000000356 contaminant Substances 0.000 claims abstract description 33
- CTNCAPKYOBYQCX-UHFFFAOYSA-N [P].[As] Chemical compound [P].[As] CTNCAPKYOBYQCX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012530 fluid Substances 0.000 claims description 72
- 238000011010 flushing procedure Methods 0.000 claims description 27
- 230000001590 oxidative effect Effects 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000008399 tap water Substances 0.000 claims description 15
- 235000020679 tap water Nutrition 0.000 claims description 15
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000779 smoke Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000002159 abnormal effect Effects 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 3
- 238000004880 explosion Methods 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- 230000001502 supplementing effect Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 17
- 238000002485 combustion reaction Methods 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- 239000005708 Sodium hypochlorite Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- 239000013589 supplement Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 208000012260 Accidental injury Diseases 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 101100204059 Caenorhabditis elegans trap-2 gene Proteins 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002637 fluid replacement therapy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Landscapes
- Cleaning By Liquid Or Steam (AREA)
Abstract
The application discloses a device and method of smokeless cleaning arsenic phosphorus pollutant part, the device of smokeless cleaning arsenic phosphorus pollutant part includes: a cleaning tank connected to at least one cleaning liquid supply device; the circulating water pump is connected with the cleaning tank through a pipeline to form a circulating cleaning loop, wherein the arsenic and phosphorus-containing pollutant component is connected in the pipeline of the circulating cleaning loop through an interface; alternatively, the arsenic and phosphorus-containing contaminant component is placed in the cleaning tank; and a PLC (programmable logic controller) system which controls the operation of the cleaning liquid supply device and the circulating water pump through the valve element so as to circularly clean the arsenic-and-phosphorus-containing pollutant components in the circulating cleaning loop. In the whole cleaning process, personnel basically have no contact, no smoke, dust and toxic substances leak in the running process of the equipment, the abnormal conditions such as open fire, explosion and the like are avoided in the reaction process, and the cleaning process is safe and pollution-free.
Description
Technical Field
The application belongs to the technical field of pollutant treatment, and particularly relates to a cleaning device and a cleaning method for an arsenic-phosphorus-containing pollutant component.
Background
In the epitaxy process of organic metal chemical vapor deposition using gallium arsenide as a substrate, excessive arsine, phosphane, silane, aluminum, gallium, indium, magnesium and other organic metal compounds are added, so that a large amount of phosphorus, arsenic and pyrophoricity organic metals are trapped in the cooling and filtering sections of the tail gas filter, the valve and the like. There are three conventional cleaning methods:
the method of mixing hydrogen peroxide with ammonia water is adopted to burn the internal components of the component in the air.
Reaction combustion by adding ammonia water: the arsenic-phosphorus particle catcher is placed in ammonia water, the shell of the arsenic-phosphorus particle catcher is separated into an upper half body and a lower half body, and then the two half bodies are respectively added into the ammonia water for reaction and combustion.
In the patent with the authority of CN 110449405B, a cleaning method of an arsenic-phosphorus particle catcher is proposed, the method uses high temperature water at about 60 ℃ to wash a filter to dissolve phosphorus in the arsenic-phosphorus filter, then disassembles and transfers the washed arsenic-phosphorus filter to high-temperature vibration cleaning equipment, and hydrogen peroxide is used for high-temperature vibration cleaning.
The direct combustion in the first way has the following problems: a. the combustion process is accompanied by huge flame and knocking; b. in the combustion process of phosphorus, arsenic and the like, a large amount of white smoke is generated, and the white smoke is mixed with fine particles after the combustion of the phosphorus and the arsenic, so that the risk of air pollution and even water source pollution in factories and the periphery can be caused; c. in order to reduce the flame and knocking, the valve opening is small and the combustion time is very long.
The reaction combustion by adding ammonia water in the second mode has the following problems: a. the combustion process is accompanied by huge flame and knocking; b. the combustion process of phosphorus, arsenic and the like generates a large amount of white smoke, and the white smoke is generatedThe white smoke contains fine particles after the combustion of phosphorus and arsenic, which can cause the risks of air pollution and even water source pollution in factories and surrounding areas; c. ammonia itself has strong pungent taste, which may cause respiratory discomfort for the user and diseases of respiratory tract if the operation is careless for a long time; d. harm of white smoke generated by reaction combustion to human body: 4P+4As+10O 2 (combustion in air) - - - -2P 2 O 5 +2As 2 O 5 Most of white smoke components generated by combustion of the arsenic-phosphorus filter are phosphorus pentoxide and arsenic pentoxide, and particles of the smoke have great toxicity to human bodies.
The cleaning in the third mode has the following problems: a. three cleaning devices are needed to finish the cleaning process, and the occupied area is large; b. the filter needs to be disassembled, transported and transferred in the cleaning process, so that the workload is high; c. after the filter is circulated by using a circulating cleaning machine, the phosphorus cannot be completely dissolved, and when the filter is disassembled and transferred to an ultrasonic cleaning tank, the risk of smoking still exists; c. by using the method for cleaning, the hydrogen peroxide can not be fully mixed for reaction, the cleaning is incomplete, and the subsequent processing is still needed; d. the solution consumption and the equipment power are larger, and the cleaning cost is high.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a method for cleaning components containing arsenic and phosphorus pollutants in a smokeless manner, which solves the problems that huge flame, knocking, toxic dense smoke, pungent smell and the like are generated in the arsenic and phosphorus cleaning process, reduces human body contact in the cleaning process, simplifies the cleaning process and reduces the manual operation process.
In one aspect, embodiments of the present application provide an apparatus for smokeless cleaning of arsenic and phosphorus contaminant components, comprising:
a cleaning tank connected to at least one cleaning liquid supply device;
the circulating water pump is connected with the cleaning tank through a pipeline to form a closed circulating cleaning loop, wherein the arsenic and phosphorus-containing pollutant component is connected in the pipeline of the circulating cleaning loop through an interface; alternatively, the arsenic and phosphorus-containing contaminant component is placed in the cleaning tank; and
and a PLC (programmable logic controller) system, wherein the PLC control system controls the operation of the cleaning liquid supply device and the circulating water pump through the valve so as to circularly clean the arsenic and phosphorus-containing pollutant components in the circulating cleaning loop.
According to some embodiments of the present application, the apparatus for smokeless cleaning of arsenic and phosphorus contaminant components further comprises: and the cold trap groove is connected to the water outlet of the circulating water pump and is used for receiving the cleaning liquid discharged from the circulating cleaning loop, and a refrigerating device is arranged in the cold trap groove.
According to some embodiments of the present application, the at least one cleaning liquid supply device includes a first cleaning liquid supply device that supplies one or more of ionized water, ultrapure water, tap water, and a second cleaning liquid supply device that supplies an oxidizing solution capable of oxidizing contaminants in the arsenic-phosphorous contaminant component.
According to some embodiments of the present application, a heating device is disposed in the cleaning tank for heating the cleaning liquid in the cleaning tank to a predetermined temperature.
Another aspect of an embodiment of the present application provides a method of smokeless cleaning of an arsenic phosphorus contaminant component, comprising:
connecting the arsenic and phosphorus-containing contaminant unit to a cycle cleaning loop of the apparatus for smokeless cleaning of an arsenic and phosphorus-containing contaminant unit according to claim 1, such that a portion of the arsenic and phosphorus-containing contaminant unit to be cleaned is in sufficient contact with the cleaning liquid;
circulating a first fluid in a circulating cleaning loop by using a circulating water pump, and performing a first round of circulating cleaning on the arsenic and phosphorus-containing pollutant component, wherein the first fluid is heated to a preset temperature capable of dissolving pollutants;
replacing the first fluid with a second fluid, circulating the second fluid in a circulating cleaning loop by using a circulating water pump, and continuously performing a second round of circulating cleaning on the arsenic and phosphorus-containing pollutant component, wherein the second fluid contains an oxidizing solution capable of oxidizing the pollutant, and the second fluid is also heated to a preset temperature; and
and replacing the second fluid with a third fluid, and using a circulating water pump to enable the third fluid to circulate in a circulating cleaning loop so as to continuously perform third-round circulating flushing on the arsenic and phosphorus-containing pollutant component, wherein the third fluid is normal-temperature fluid.
According to some embodiments of the present application, the first round of cyclic flushing has a duration of each cyclic flushing of T1, a number of cycles of N1, T1 between 30 minutes and 120 minutes, n1+.gtoreq.1;
the duration of each cycle of the second cycle of cyclic flushing is T2, the cycle times are N2, the T2 is between 60 minutes and 480 minutes, and N2 is not less than 1;
the duration of each cycle of the third cycle of flushing is T3, the cycle times are N3, T3 is between 10 minutes and 120 minutes, and N3 is not less than 1.
According to some embodiments of the present application, the first fluid is one or more of ionized water, ultrapure water, tap water, the second fluid is a fluid formed by adding an oxidizing solution to the first fluid, and the third fluid is one or more of ionized water, ultrapure water, tap water.
According to some embodiments of the present application, the oxidizing solution is hydrogen peroxide or hypochlorite or a hydrogen peroxide and ammonia water mixture.
According to some embodiments of the application, the oxidizing solution is present in the second fluid at a ratio of 5% to 80%.
According to some embodiments of the present application, the temperature of the first fluid and the second fluid is greater than or equal to 45 degrees celsius.
According to the device and the method for cleaning the arsenic and phosphorus-containing pollutant component in the smokeless manner, compared with the prior art, only one high-temperature circulating cleaning device is needed in the operation process, and the cleaning process is automatically carried out: the parts are washed by using a first high-temperature fluid, most of phosphorus is dissolved, the content of pyrophoric substances such as phosphorus, organic metal and the like in the parts is reduced, and then, the parts are circularly washed again by using a second high-temperature fluid containing an oxidant, so that the residual substances such as phosphorus, arsenic and the like in the parts are reduced; thereafter, the parts were again rinsed at room temperature using the third fluid. Pumps are used to thoroughly mix the fluids during this process, accelerating the reaction process. In the whole cleaning process, personnel basically have no contact, no smoke, dust and toxic substances leak in the running process of the equipment, and abnormal conditions such as open fire, explosion and the like are avoided in the reaction process. In the cleaning process, no human participation is needed, and the cleaning process is safe and pollution-free.
Drawings
Fig. 1 is a schematic view of a basic structure of a cleaning machine according to an embodiment of the present invention.
FIG. 2 is a schematic diagram of a process flow for automatically operating a cleaning machine according to an embodiment of the present invention.
Reference numerals illustrate:
1. semiconductor refrigerating sheet 2, cold trap tank 3, drain pipe 4, drain valve 5, circulating water pump 6, heating device 7, stainless steel water tank 8, material to be cleaned 9, liquid medicine pump 10, pneumatic circulating water valve 11, liquid medicine barrel 12, pneumatic liquid supplementing valve 13, pneumatic liquid supplementing valve II 14, liquid medicine barrel 2 15, liquid medicine pump II 16, thermometer 17, PH meter 18, pneumatic liquid draining valve 19, material to be cleaned 2 20, thermometer 21, pneumatic water supplementing valve 22, liquid level meter 23, electric cabinet and control system
Detailed Description
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below. In the drawings, the same or similar reference numerals are used for the same or similar functional components. Also, some components not directly related to the inventive concept may be omitted from illustration. The drawings and descriptions of specific embodiments are presented only to provide a better understanding of the invention and the invention is not limited to the embodiments illustrated in the drawings and described in the specification.
Technical or scientific terms used herein should be given the ordinary meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The use of the terms "comprising" or "includes" and the like in this specification is intended to be open-ended terms that do not exclude other elements, components, parts, or items than those explicitly listed. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, which may also be changed when the absolute position of the object to be described is changed. "first," "second," etc. are used for the purpose of distinguishing between different elements and not necessarily for a specific order.
Fig. 1 is a schematic view of a basic structure of a cleaning machine according to an embodiment of the present application. The cleaning machine comprises a cold trap tank 2, a circulating water pump 5, a stainless steel water tank 7, an electric cabinet and PLC control system 23, a liquid supply unit, a heating and temperature control module. The circulating water pump 5 and the stainless steel water tank 7 are connected into a closed circulating cleaning loop through a pipeline. Specifically, one side of the stainless steel water tank 7 is externally connected with a water inlet of a circulating water pump 7, a water outlet of the water pump 7 is connected with a water draining pneumatic valve 4 through a three-way pipe and is discharged into the cold trap tank 2, and one way is connected with a circulating pneumatic valve 10 and then is connected with an interface of a material piece 8 to be cleaned; the other side of the stainless steel water tank 7 is connected with the other port of the material piece 8 to be cleaned by using a corrugated pipe after being connected with a circulating pneumatic valve 10. Or the material piece 19 to be cleaned is directly placed into the stainless steel water tank 7, one end of the pipeline is connected to the outlet of the water pump, and one end of the pipeline is connected to the other side of the stainless steel water tank 7 to form a circulation loop.
The wall of the stainless steel water tank 7 can be stuck with a heating device 6, a PH meter 17, a thermometer 16 and an electronic liquid level meter 22 (which can be replaced by an upper limit liquid level switch and a lower limit liquid level switch) are arranged in the tank, a stainless steel cover plate is arranged, a fixed exhaust pipe is arranged on the tank body, and a material piece 19 to be cleaned can be placed in the water tank 7 for cleaning. A PLC (programmable logic controller) system 23 controls the operation of the liquid supply unit and the circulating water pump 5 through the valve member to perform the circulating cleaning of the arsenic and phosphorus-containing contaminant component 8 or 19 in the circulating cleaning circuit.
The liquid supply unit includes a first cleaning liquid supply device and a second cleaning liquid supply device. The first cleaning liquid supply device supplies one or more of ionized water, ultrapure water, and tap water, and in the embodiment shown in fig. 1, the first cleaning liquid is tap water. The second cleaning liquid supply device supplies an oxidizing solution capable of oxidizing the contaminants in the arsenic-phosphorus-containing contaminant component. In fig. 1, the second cleaning liquid supply means includes liquid replenishing liquid pumps 9 and 15, liquid medicine tanks 11 and 14, and pneumatic liquid replenishing valves 12 and 13 for replenishing the circulation fluid to the water tank 7.
The groove wall of the cold trap groove 2 can be stuck with a semiconductor refrigerating sheet 1 for refrigeration, and the refrigerating effect can reduce the temperature of the solution in the water groove from 70 ℃ to 5 ℃ within 2 hours; after reaching a certain time or temperature, the cold trap tank is drained to the lowest liquid level, and the lowest liquid level is preferably 30cm away from the bottom of the tank body; the cold trap tank body can be independently disassembled and replaced. The purpose of the cold trap 2 is to cool the waste liquid, which also causes some contaminants to precipitate and sediment.
A pneumatic circulating water valve 10, preferably two, is arranged on the circulating flushing pipeline; a pneumatic drain valve 4 is arranged on the connection path of the circulating flushing pipeline and the cold trap tank. The circulating water pump 5, preferably a diaphragm pump or a pneumatic pump, has a water pump power of not less than 1.1KW. The heating and control system comprises a heating device 6, a temperature control module and a control system, wherein the temperature control accuracy is not more than 1 ℃; the heating power is not lower than 8KW, and the water temperature is not lower than 60 ℃ within 20 minutes.
As shown in fig. 2, the following cleaning steps are performed in the high temperature cycle cleaning apparatus as shown in fig. 1:
firstly, connecting an arsenic and phosphorus-containing pollutant component with high-temperature circulating cleaning equipment or placing the arsenic and phosphorus-containing pollutant component into the high-temperature circulating cleaning equipment, so that a part of the arsenic and phosphorus-containing pollutant component to be cleaned is fully contacted with cleaning liquid;
next, a cleaning process is performed, which requires the following three steps:
the method comprises the steps that firstly, a circulating water pump is utilized to enable a first high-temperature fluid to circulate in cleaning equipment, and the first high-temperature fluid is used for circularly flushing components containing arsenic and phosphorus pollutants so as to dissolve phosphorus in an arsenic and phosphorus filter; flushing time T1, and cycle number is N; preferably, T1 is between 30 minutes and 120 minutes; n1 is equal to or greater than 1. Preferably, the first high-temperature fluid is one or more of ionized water, ultrapure water and tap water, and the ionized water, the ultrapure water and the tap water are heated to form a high-temperature fluid with a preset temperature.
Principle of the first step: taking phosphorus as an example of a contaminant, the melting point of elemental phosphorus is 45 ℃. Therefore, after the arsenic and phosphorus pollutant component is connected with the cleaning machine by using the physical characteristics, high-temperature pure water or tap water or ionized water with the temperature higher than 45 ℃ is used for dissolving phosphorus in the material to be cleaned, meanwhile, part of organic metal particles are dissolved, the fluid is circulated by a pump, a high-pressure fluid is generated to pass through the material to be cleaned, the material is washed by the high-temperature fluid, and the material is discharged after the phosphorus is dissolved.
Changing fluid, using a circulating water pump to enable second high-temperature fluid to circulate in the cleaning equipment, and using the second high-temperature fluid to continuously circularly wash the component containing the arsenic and phosphorus pollutants; flushing time T2, and cycle number is N2; preferably, T2 is between 60 minutes and 480 minutes; the number of the cyclic flushing times N2 is not less than 1; the second high temperature fluid contains an oxidizing solution capable of oxidizing the contaminant. For example, the second high temperature fluid is formed by adding an oxidizing solution to the first high temperature fluid, and the ratio of the oxidizing solution to the high temperature fluid is 5% -80%. The contamination is oxidized by the increase in oxidizing solution, cleaning the parts more thoroughly. Preferably, the temperature of the second high-temperature fluid is higher than 45 ℃, and the oxidizing solution is hydrogen peroxide or hypochlorite or a mixture of hydrogen peroxide and ammonia. Principle of the second step: the arsenic-phosphorus contaminant reacts chemically with the oxidizing agent to form soluble species, dissolving arsenic and the like and further dissolving phosphorus.
Removing the second high-temperature fluid, injecting a third cleaning solution, circulating the third cleaning solution in the cleaning equipment by using a circulating water pump, and circularly flushing and cleaning the parts; time T3, the number of times of cyclic flushing is N3; preferably, T3 is between 10 minutes and 120 minutes, and the number of circulating flushing times is N ∈ 1; preferably, the third cleaning liquid is ionized water, ultrapure water or tap water.
Preferably, in the process of cleaning by using ionized water, ultrapure water or tap water, the cycle cleaning frequency is the frequency of fluid replacement. In the second high-temperature fluid cleaning process, the circulating cleaning times are the solution supplementing times. The number of cycles may be increased or decreased during the cleaning process depending on the actual condition of the component.
Finally, the component is detached from the high temperature cycle cleaning apparatus and removed.
Preferably, the above components may be filters or valves, irregular material pieces, pipe pieces.
The cleaning process of the present application will be described below by way of specific examples.
Example 1
In this example, the arsenic and phosphorus filter was used as a cleaning target and H2O2 was used as an oxidizing agent.
The specific process of using the cleaning equipment for cleaning comprises the following steps:
during cleaning, the material 8 to be cleaned is connected between two pneumatic circulation valves 10 at the outlet of the water pump.
1. The PLC 23 is started up, the pneumatic water supplementing valve 21 is connected with tap water, after the stainless steel water tank 7 starts to automatically supplement water to the set liquid level, the liquid supplementing is stopped, and the temperature control module controls the heating device 6 to start heating. After the thermometer 16 detects that the water temperature is raised to more than 45 ℃, the water pump 5 and the two pneumatic circulation valves 10 are simultaneously opened, and the inside of the arsenic-phosphorus filter is flushed by using high-temperature fluid.
The high temperature fluid will dissolve the phosphorus blocks and organic metals in the arsenic-phosphorus filter, and after dissolution, the fluid will be carried out of the filter into the stainless steel water tank 7. The water tank is internally provided with a layered structure, phosphorus blocks, particle residues and the like which are flushed into the water tank are retained in the first layer of the water tank, and fluid is pumped out again by the water pump and flushed into the arsenic-phosphorus filter.
After the arsenic and phosphorus filter is rinsed by the high-temperature fluid for a limited time T1 (the time is determined according to the condition of the material to be cleaned and is between 30 and 120 minutes). If the phosphorus content in the environment of the filter is higher, the circulation times can be increased according to the use condition, namely, the pneumatic drain valve 4 is opened, the pneumatic circulation valve 10 is closed, the water pump 5 discharges the solution in the water tank 7 into the cold trap tank 2, after the liquid level is discharged to the lowest safe liquid level range, the pneumatic drain valve 4 and the circulating water pump 5 are stopped, the pneumatic water supplementing valve 21 is opened to automatically supplement water to the set liquid level, the water tank is started for heating, and the water pump is started, so that the action is repeated to the set times.
2. After the circulation times are reached, the liquid medicine pump 9 and the pneumatic supplement are carried outThe liquid valve 12 is started to automatically supplement H into the water tank 2 O 2 . The liquid supplementing speed is adjustable, and when the liquid supplementing amount reaches the set amount, the liquid supplementing is stopped. The water pump continues to flush the arsenic-phosphorus filter.
After the regular flushing, the solution in the water tank is acidic, and the PH value is detected to be below 4 by a PH meter. According to the service cycle and specification type of the arsenic-phosphorus filter, H can be increased as required 2 O 2 The liquid supplementing times.
H 2 O 2 The cleaning principle is as follows: h 2 O 2 The reaction is aggravated by heating, active oxygen is released to react with GaAs in the arsenic-phosphorus filter to form oxide Ga of arsenic and gallium 2 O 3 And As 2 O 3 . Due to Ga 2 O 3 And As 2 O 3 All are weak acidic amphoteric oxides, forming soluble gallates and arsenates, and dissolving in solution. The high-pressure fluid is generated by the circulating pump, and the solution is fully mixed so as to fully react with sediment in the filter.
Through H 2 O 2 After the solution is washed, according to the pH value condition in the water tank, a liquid medicine pump 15 and a pneumatic liquid supplementing valve 13 are started, and NH is automatically supplemented in the water tank 3 Or NaOH to control the PH value in the water tank. After the quantitative liquid medicine is supplemented, the water pump carries out water circulation mixing, and the solution undergoes acid-base neutralization reaction. After the PH value is adjusted to be within 6.5 to 7.5, the pneumatic drain valve 4 is opened, the pneumatic circulation valve 10 is closed, and the water pump discharges the solution in the water tank to the cold trap tank 2.
3. After the liquid level is discharged to the lowest safe liquid level range, the pneumatic drain valve 4 and the circulating water pump 5 are stopped, the pneumatic water supplementing valve 21 is opened to automatically supplement water to the set liquid level, the water tank can be selectively opened for heating, the water pump is opened for flushing the arsenic-phosphorus filter, and normal-temperature flushing can be also selected.
The temperature of the solution in the tank body 7 is detected by the thermometer 20 in the cold trap tank 2, after the temperature exceeds the set temperature, the refrigerating plate 1 is started to cool, the solution in the tank is cooled to 20 ℃, cooling is stopped, and the water discharge valve 18 can be automatically opened according to the condition of the solution or the condition of the solution, so that the solution is discharged to a limited liquid level.
After the flushing is finished, the circulating water pump 5 and the pneumatic circulating valve 10 are automatically closed, and the arsenic and phosphorus filter is cleaned. And (3) detaching the filter from the water tank, disassembling the cleaning machine, checking and cleaning the interior of the filter cartridge, and drying.
The cleaning solution may be used to clean modular components with access ports, such as arsenic-phosphorous filters, and the like.
Example 2
In this example, sodium hypochlorite was used as the oxidizing agent for the cleaning.
The equipment used and the steps mainly passed by the equipment in the operation process are the same as those in example 1, except that the oxidant used in step 2 is sodium hypochlorite, and the specific operation process of step 2 is as follows:
after the number of circulation times is reached, the liquid medicine pump 9 and the pneumatic liquid replenishing valve 12 are started to automatically replenish sodium hypochlorite into the water tank. The liquid supplementing speed is adjustable, and when the liquid supplementing amount reaches the set amount, the liquid supplementing is stopped. The water pump continues to flush the arsenic-phosphorus filter.
Optionally, during the sodium hypochlorite supplementing process, the PH is controlled to be 3-10, and phosphoric acid is adopted to adjust the PH of the sodium hypochlorite. Preferably pH 5-8, for flushing arsenic contaminants, oxidation is optimized.
According to the service cycle and specification model of the arsenic-phosphorus filter, the number of sodium hypochlorite liquid replenishing times can be increased as required.
After the regular flushing, according to the pH value condition in the water tank, the liquid medicine pump 15 and the pneumatic liquid supplementing valve 13 are started, naOH or phosphoric acid is automatically supplemented in the water tank, and the pH value in the water tank is controlled. After the quantitative liquid medicine is supplemented, the water pump carries out water circulation mixing, and the solution undergoes acid-base neutralization reaction. Is convenient for the treatment of the waste water at the rear end.
Example 3
During cleaning, the material to be cleaned is directly placed into the circulating water tank 7, and the two pneumatic circulating valves 10 are directly in butt joint. The device is started on the PLC, the pneumatic water supplementing valve 21 is opened, after the water tank starts to automatically supplement water to the set liquid level, the liquid supplementing is stopped, and the heating plate 6 starts to heat. After the thermometer 16 detects that the water temperature is raised to more than 45 ℃, the circulating water pump 5 and the two pneumatic circulating valves 10 are simultaneously opened, and the inside of the arsenic-phosphorus filter is flushed by using high-temperature fluid. Then, the chemical pump 9 and the pneumatic liquid replenishing valve 12 are started to automatically replenish the inside of the water tank with an oxidizing agent such as H2O2 or sodium hypochlorite. The liquid supplementing speed is adjustable, and when the liquid supplementing amount reaches the set amount, the liquid supplementing is stopped. The water pump continues to flush the arsenic-phosphorus filter.
After the cleaning device is subjected to the timed flushing, the heating plate 6 is closed, the pneumatic drain valve 4 is opened, the pneumatic circulation valve 10 is closed, the water pump discharges the solution in the water tank into the cold trap tank 2, after the liquid level is discharged to the lowest safe liquid level range, the ion water, the ultrapure water and tap water can be selected to be circularly flushed in the cleaning device according to the size of the material, or the material can be directly taken out from the cleaning tank, and the cleaning device can be normally used after being flushed and baked.
The cleaning mode is used for cleaning irregular material parts, pipe fittings or valve parts and the like with arsenic and phosphorus on the surface, such as ball valves, stainless steel pipes or disassembled arsenic and phosphorus filter tanks and the like.
In the operation process of the invention, only water is used as a medium, no flame, knocking and dense smoke are generated, and the cleaning equipment cleans the arsenic-phosphorus filter in a circulating solution under a closed condition, so that the arsenic-phosphorus filter is prevented from being directly contacted with personnel to cause accidental injury. The control cabinet is internally provided with a control unit and a power supply unit, so that the realization of the functions of the circulating cleaning machine such as cleaning fluid temperature, circulating times, cleaning time and the like is controlled by the control unit, and the realization of the control cabinet belongs to the conventional technology for the technicians in the electrical field, so that the detailed description is omitted.
Compared with the prior art, the invention uses a high-temperature circulating cleaning device in the operation process to automatically carry out the cleaning process: firstly, flushing the component by using high-temperature fluid, dissolving most of phosphorus, reducing the content of pyrophoric substances such as phosphorus, organic metal and the like in the component, and then, automatically discharging the solution to a cold trap tank for cooling; after liquid discharge, replenishing the solution (comprising water and oxidant) in the equipment, circularly cleaning again to reduce the residual substances such as phosphorus, arsenic and the like, and then draining the water again to a cold trap tank, and flushing the parts by using clear water; the cold trap tank can automatically cool and drain water according to the temperature and water level in the tank. Pumps are used to thoroughly mix the fluids during this process, accelerating the reaction process. In the whole cleaning process, personnel basically have no contact, no smoke, dust and toxic substances leak in the running process of the equipment, and abnormal conditions such as open fire, explosion and the like are avoided in the reaction process. In the cleaning process, no human participation is needed, and the cleaning process is simple, convenient, safe and pollution-free.
The foregoing embodiments are merely illustrative of the principles and configurations of the present invention, and are not intended to be limiting, it will be appreciated by those skilled in the art that any changes and modifications may be made without departing from the general inventive concept. The protection scope of the present invention should be defined as the scope of the claims of the present application.
Claims (10)
1. An apparatus for smokeless cleaning of arsenic and phosphorus contaminant-containing components, comprising:
a cleaning tank connected to at least one cleaning liquid supply device;
the circulating water pump is connected with the cleaning tank through a pipeline to form a closed circulating cleaning loop, wherein the arsenic and phosphorus-containing pollutant component is connected in the pipeline of the circulating cleaning loop through an interface; alternatively, the arsenic and phosphorus-containing contaminant component is placed in the cleaning tank; and
and a PLC (programmable logic controller) system, wherein the PLC control system controls the operation of the cleaning liquid supply device and the circulating water pump through the valve so as to circularly clean the arsenic and phosphorus-containing pollutant components in the circulating cleaning loop.
2. The apparatus for smokeless cleaning of arsenic and phosphorus contaminant components according to claim 1, further comprising:
and the cold trap groove is connected to the water outlet of the circulating water pump and is used for receiving the cleaning liquid discharged from the circulating cleaning loop, and a refrigerating device is arranged in the cold trap groove.
3. The apparatus for smokeless cleaning of arsenic-phosphorus-containing contaminant components according to claim 1, wherein the at least one cleaning liquid supply comprises a first cleaning liquid supply that supplies one or more of ionized water, ultrapure water, tap water, and a second cleaning liquid supply that supplies an oxidizing solution capable of oxidizing contaminants in the arsenic-phosphorus-containing contaminant components.
4. The apparatus for smokeless cleaning of arsenic and phosphorus contaminant components according to claim 1, wherein a heating means is provided in the cleaning tank for heating the cleaning liquid in the cleaning tank to a predetermined temperature.
5. A method of smokeless cleaning of components containing arsenic and phosphorus contaminants, comprising:
connecting the arsenic and phosphorus-containing contaminant unit to a cycle cleaning loop of the apparatus for smokeless cleaning of an arsenic and phosphorus-containing contaminant unit according to claim 1, such that a portion of the arsenic and phosphorus-containing contaminant unit to be cleaned is in sufficient contact with the cleaning liquid;
circulating a first fluid in a circulating cleaning loop by using a circulating water pump, and performing a first round of circulating cleaning on the arsenic and phosphorus-containing pollutant component, wherein the first fluid is heated to a preset temperature capable of dissolving pollutants;
replacing the first fluid with a second fluid, circulating the second fluid in a circulating cleaning loop by using a circulating water pump, and continuously performing a second round of circulating cleaning on the arsenic and phosphorus-containing pollutant component, wherein the second fluid contains an oxidizing solution capable of oxidizing the pollutant, and the second fluid is also heated to a preset temperature; and
and replacing the second fluid with a third fluid, and using a circulating water pump to enable the third fluid to circulate in a circulating cleaning loop so as to continuously perform third-round circulating flushing on the arsenic and phosphorus-containing pollutant component, wherein the third fluid is normal-temperature fluid.
6. The method of smokeless cleaning components comprising arsenic and phosphorus according to claim 5, wherein,
the duration of each cycle of the first cycle of cyclic flushing is T1, the cycle times are N1, the T1 is between 30 minutes and 120 minutes, and the N1 is not less than 1;
the duration of each cycle of the second cycle of cyclic flushing is T2, the cycle times are N2, the T2 is between 60 minutes and 480 minutes, and N2 is not less than 1;
the duration of each cycle of the third cycle of flushing is T3, the cycle times are N3, T3 is between 10 minutes and 120 minutes, and N3 is not less than 1.
7. The method of smokeless cleaning an arsenic and phosphorus contaminant unit according to claim 5, wherein the first fluid is one or more of ionized water, ultrapure water, tap water, the second fluid is a fluid formed by adding an oxidizing solution to the first fluid, and the third fluid is one or more of ionized water, ultrapure water, tap water.
8. The method of smokeless cleaning of arsenic and phosphorus contaminant components according to claim 7, wherein the oxidizing solution is hydrogen peroxide or hypochlorite or a hydrogen peroxide and ammonia water mixture.
9. The method of smokeless cleaning of arsenic and phosphorus contaminant components according to claim 7, wherein the oxidizing solution comprises from 5% to 80% of the second fluid.
10. The method of smokeless cleaning of arsenic and phosphorus contaminant components according to claim 5, wherein the first fluid and the second fluid have a temperature of 45 degrees celsius or greater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211674113.0A CN115999998A (en) | 2022-12-26 | 2022-12-26 | Device and method for cleaning arsenic and phosphorus-containing pollutant component in smokeless mode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211674113.0A CN115999998A (en) | 2022-12-26 | 2022-12-26 | Device and method for cleaning arsenic and phosphorus-containing pollutant component in smokeless mode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115999998A true CN115999998A (en) | 2023-04-25 |
Family
ID=86029198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211674113.0A Pending CN115999998A (en) | 2022-12-26 | 2022-12-26 | Device and method for cleaning arsenic and phosphorus-containing pollutant component in smokeless mode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115999998A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295504A (en) * | 1998-02-25 | 2001-05-16 | 伽马精度技术公司 | Apparatus and method for cleaning semiconductor wafers |
| KR20010056346A (en) * | 1999-12-15 | 2001-07-04 | 박진구 | Apparatus for cleaning semiconductor and method thereof |
| KR20110082730A (en) * | 2010-01-12 | 2011-07-20 | 주식회사 엘지실트론 | Wafer cleaning apparatus and cleaning method |
| CN109270251A (en) * | 2018-11-02 | 2019-01-25 | 中国科学院广州地球化学研究所 | A kind of on-line extraction formula life residence thermal simulation experiment device and method |
| CN110449405A (en) * | 2019-08-14 | 2019-11-15 | 苏州首翔系统工程科技有限公司 | A kind of cleaning method of arsenic phosphorus particle trapper |
| CN114787981A (en) * | 2019-12-03 | 2022-07-22 | 罗伯特·博世有限公司 | Device and method for processing at least one semiconductor substrate |
-
2022
- 2022-12-26 CN CN202211674113.0A patent/CN115999998A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295504A (en) * | 1998-02-25 | 2001-05-16 | 伽马精度技术公司 | Apparatus and method for cleaning semiconductor wafers |
| KR20010056346A (en) * | 1999-12-15 | 2001-07-04 | 박진구 | Apparatus for cleaning semiconductor and method thereof |
| KR20110082730A (en) * | 2010-01-12 | 2011-07-20 | 주식회사 엘지실트론 | Wafer cleaning apparatus and cleaning method |
| CN109270251A (en) * | 2018-11-02 | 2019-01-25 | 中国科学院广州地球化学研究所 | A kind of on-line extraction formula life residence thermal simulation experiment device and method |
| CN110449405A (en) * | 2019-08-14 | 2019-11-15 | 苏州首翔系统工程科技有限公司 | A kind of cleaning method of arsenic phosphorus particle trapper |
| CN114787981A (en) * | 2019-12-03 | 2022-07-22 | 罗伯特·博世有限公司 | Device and method for processing at least one semiconductor substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100390932C (en) | Semiconductor manufacturing device and chemical reagent exchange method | |
| KR20010053300A (en) | Method and apparatus for immersion treatment of semiconductor and other devices | |
| KR20200075822A (en) | Cooker fume treatment system and cooker | |
| TWI581827B (en) | Gas handling device | |
| CN115999998A (en) | Device and method for cleaning arsenic and phosphorus-containing pollutant component in smokeless mode | |
| KR100336164B1 (en) | Method and Apparatus for Scrubbing Toxic Gas | |
| JP3545672B2 (en) | Substrate processing method and substrate processing apparatus | |
| JP2010023000A (en) | Waste gas detoxification apparatus | |
| KR100710009B1 (en) | Plasma Gas Scrubber for Hazardous Gas Treatment and Its Control Method | |
| CN214182502U (en) | Exhaust gas purification system with self-checking device | |
| CN114688547A (en) | Exhaust gas treatment device | |
| CN209646224U (en) | A kind of more combustion room environmental Protection cremators | |
| US20230390694A1 (en) | Exhaust gas treatment facility | |
| CN215276522U (en) | Automatic cycle control's acid mist absorbing device | |
| CN110449405B (en) | Cleaning method of arsenic-phosphorus particle catcher | |
| CN213160129U (en) | Organic waste gas treatment device based on internet | |
| KR100412579B1 (en) | Gas Scrubber Apparatus | |
| JPH02152233A (en) | Cleaning apparatus | |
| JP2003010802A (en) | Engine cleaning system and method | |
| CN111167808A (en) | Semiconductor processing procedure pipeline belt cleaning device | |
| CN212663115U (en) | Active carbon regeneration exhaust treatment device | |
| CN202253679U (en) | Silane tail gas combustion purification equipment | |
| JP2004057992A (en) | Method and apparatus for purifying contaminated soil | |
| CN215626887U (en) | Self-evaporation type cleaning water treatment equipment for QPQ (quench-Polish-quench) process | |
| CN220071139U (en) | Silicon carbide ceramic high-temperature flue gas treatment device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |