CN105174233B - A kind of production method of ultra-clean and high-purity sulphuric acid - Google Patents
A kind of production method of ultra-clean and high-purity sulphuric acid Download PDFInfo
- Publication number
- CN105174233B CN105174233B CN201510620848.9A CN201510620848A CN105174233B CN 105174233 B CN105174233 B CN 105174233B CN 201510620848 A CN201510620848 A CN 201510620848A CN 105174233 B CN105174233 B CN 105174233B
- Authority
- CN
- China
- Prior art keywords
- ultra
- clean
- group
- microfiltration membranes
- continuous rectification
- 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.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of production method of ultra-clean and high-purity sulphuric acid, methods described comprises the following steps：（1）Removal of impurities：Technical grade sulfuric acid is injected to add under treatment trough, mechanical agitation after cleaner, standing and filtered；（2）Rectifying：By step（1）In filtrate be introduced into through negative pressure in continuous rectification apparatus, whne liquid level be slightly above heating furnace silk when, electrified regulation continuous rectification；1.8L ~ 2.0L is fed every time；（3）Fractionation：Collection step（2）In midbarrel, cut temperature range be 332 DEG C ~ 342 DEG C；（4）Ultra-clean filtering：By step（3）The cut of collection introduces ultra-clean filter through negative pressure and carries out ultra-clean filtering；（5）Ultra-clean packing：Step（4）Middle product quality, which is detected, to be reached after requirement, ultra-clean packing.The present invention can realize the impurity that efficient oxidation is gone in sulfuric acid；Efficiently intercepted using four road filter membranes simultaneously, product quality indicator is more than SEMI C12 standards.
Description
Technical field
The present invention relates to a kind of production technology for producing ultra-clean and high-purity sulphuric acid.Ultra-clean and high-purity sulphuric acid is mainly used on a large scale
It is used in the industries such as integrated circuit, semi-conductor discrete device as highly acid cleaning corrosive agent.Belong to micron Electric Chemical Reagent skill
Art field.
Background technology
With developing rapidly for semiconductor technology, the requirement more and more higher to ultra-clean and high pure chemical reagent.In integrated circuit（IC）
Process in, ultra-clean and high pure chemical reagent is mainly used in cleaning and the etching on chip and silicon wafer surface, its purity and cleanliness factor
There is very great influence to the yield rate of integrated circuit, electrical property and reliability.Ultra-clean and high-purity sulphuric acid is used as one kind weight
The micro-electronics chemicals wanted have been widely used for the side such as cleaning, dry in semiconductor, large scale integrated circuit process
Face.Nanometer era is marched toward with IC processing dimension, from 28nm to the 14nm techniques currently captured, matched is surpassed
Net high-purity sulphuric acid proposes very high requirement, it is desirable to which particle and impurity content reduce by 1 ~ 3 order of magnitude, reach international semiconductor
The SEMI C12 standards that equipment and material structure are formulated, wherein metal cation content are less than 0.1ppb, and granular size control exists
Less than 0.5 μm.
At present, ultra-clean and high-purity sulphuric acid is generally purified using technical grade sulfuric acid as raw material rectifying and filters refined form.Rectifying
It is to industrialize the main method for purifying sulfuric acid, including azeotropic distillation, extracting rectifying etc..But for the super of micro-electronics chemicals industry
Net requirement of the high-purity sulphuric acid to wherein metals content impurity, granular size content and anion-content is quite harsh, from mistake
The ppm limitations gone bring up to current ppb limitations, or even ppt limitations, the dust granules in product have also been made clearly
Ask, existing production technology can not meet requirement.
The content of the invention
For above weak point, the present invention propose it is a kind of can realize impurity that efficient oxidation gone in sulfuric acid, into
This is low, can industrialized mass production ultra-clean and high-purity sulphuric acid production method.
Technical scheme is as follows：
A kind of production method of ultra-clean and high-purity sulphuric acid, methods described comprises the following steps：
（1）Removal of impurities：Technical grade sulfuric acid is injected to add under treatment trough, mechanical agitation after cleaner, standing and filtered；
（2）Rectifying：By step（1）In filtrate be introduced into through negative pressure in continuous rectification apparatus, treat liquid level slightly above heating furnace
During silk, electrified regulation continuous rectification；1.8L ~ 2.0L is fed every time；
（3）Fractionation：Collection step（2）In midbarrel, cut temperature range be 332 DEG C ~ 342 DEG C；
（4）Ultra-clean filtering：By step（3）The cut of collection introduces ultra-clean filter through negative pressure and carries out ultra-clean filtering；
（5）Ultra-clean packing：Step（4）Middle product quality, which is detected, to be reached after requirement, ultra-clean packing.
Step（1）Described in cleaner be KMnO4And K2S2O8Mixture, weight ratio be 3 ~ 5:1, it is intended to pass through oxidation
Arsenic that reduction reaction is gone in sulfuric acid etc. is difficult to the impurity removed.
Step（2）In continuous rectification apparatus for pure quartz glass or inside lining anti-corrosive material stainless steel.
Step（3）In be less than 332 DEG C or the cut higher than 342 DEG C back flowed back into through pipeline in continuous rectification apparatus, then
Secondary rectifying, while adjusting acid inlet valve addition raw material, keeps the liquid level ± 5cm in continuous rectification apparatus, keeps continuous production.
Step（4）In ultra-clean filtering be that under the protection of dry nitrogen, and granularity is more than 0.5 μm of particle in atmosphere
Carried out under hundred grades of environment purifications no more than 100.
Step（4）In ultra-clean filter be provided with some dismountable microfiltration membranes and NF membrane, it is intended to ensure quality
It is stable, and easy cleaning replacing, do not influence quantity-produced to carry out.
Further, step（4）Middle microfiltration membranes are set to the microfiltration membranes at least differed by 2 groups of pore sizes, and at least
One group of micro-filtration membrane aperture is 0.1 ~ 0.2 μm；NF membrane is set to the NF membrane at least differed by 2 groups of pore sizes, and at least
One group of nanofiltration membrane aperture is 0.2 ~ 0.5nm.
The kind that microfiltration membranes are used is Polyvinylidene type or polysulfones type or PTFE Type.
The kind that NF membrane is used is cellulose acetate or SPSF or PTFE Type.
Step（5）In ultra-clean packing be that under the protection of dry nitrogen, and granularity is more than 0.5 μm of particle in atmosphere
Carried out under hundred grades of environment purifications no more than 100.
As method for optimizing, the microfiltration membranes are set and NF membrane is each provided with two groups.First group of microfiltration membranes is used
Polyvinylidene fluoride type；Second group of microfiltration membranes uses PTFE Type；What first group and second group of NF membrane were used is all
PTFE Type.
Compared with prior art, beneficial effects of the present invention：
1st, using strong oxidizer composition KMnO4And K2S2O8Mixture as cleaner, efficient oxidation is gone in sulfuric acid
Nonmetallic inclusion and beavy metal impurity；
2nd, distillation process is strictly controlled, and low boiling and high boiling fraction are through secondary rectifying, it is ensured that the conversion ratio of raw material；
3rd, four roads are combined using microfiltration membranes and NF membrane to intercept, efficiently intercepts impurity, product quality indicator is more than SEMI-
C12 standards.
4th, using dismountable microfiltration membranes and NF membrane, facilitate cleaning replacement, continuous production operation will not be impacted.
Invention achieves high-quality, efficient, low cost, the purpose of industrialized mass production ultra-clean and high-purity sulphuric acid.
Embodiment
The present invention is described further in conjunction with production technology.
Embodiment 1
A kind of production method of ultra-clean and high-purity sulphuric acid, methods described step is as follows：
（1）Removal of impurities：Technical grade sulfuric acid is injected to add under treatment trough, mechanical agitation after cleaner, standing and filtered.It is described to remove
Miscellaneous dose is KMnO4And K2S2O8Mixture, weight ratio be 3:1, it is intended to the difficulty such as arsenic gone by redox reaction in sulfuric acid
With the impurity of removal.
（2）Rectifying：By step（1）In filtrate be introduced into through negative pressure in continuous rectification apparatus, treat liquid level slightly above heating furnace
During silk, electrified regulation continuous rectification；1.8L is fed every time.The material of continuous rectification apparatus is the stainless steel of inside lining anti-corrosive material.
（3）Fractionation：Collection step（2）In midbarrel, cut temperature range be 332 DEG C ~ 342 DEG C.Less than 332 DEG C
Or the cut higher than 342 DEG C is back flowed back into continuous rectification apparatus through pipeline, rectifying again, while it is former to adjust acid inlet valve addition
Material, keeps the liquid level ± 5cm in continuous rectification apparatus, keeps continuous production.
（4）Ultra-clean filtering：By step（3）The cut of collection introduces ultra-clean filter through negative pressure and carries out ultra-clean filtering.It is super
Net filtering is that under the protection of dry nitrogen, and granularity is more than hundred grade purifications of 0.5 μm of the particle no more than 100 in atmosphere
Carried out under environment.Ultra-clean filter is provided with some dismountable microfiltration membranes and NF membrane, it is intended to ensure steady quality, and easily
Cleaning replacement, does not influence quantity-produced to carry out.Microfiltration membranes are set to：First group of micro-filtration membrane aperture is 0.5 μm；Second group of micro-filtration
Membrane aperture is 0.1 μm；NF membrane is set to：First group of nanofiltration membrane aperture is 0.5nm, and second group of nanofiltration membrane aperture is 0.2nm.
First group of microfiltration membranes uses polyvinylidene fluoride type；Second group of microfiltration membranes uses PTFE Type；
What first group and second group of NF membrane were used is all PTFE Type.
（5）Ultra-clean packing：Under nitrogen protection, using 1mL syringe aspiration steps（4）In a small amount of liquid detected,
After product quality detection reaches requirement, ultra-clean packing.
It is ultra-clean packing be under the protection of dry nitrogen, and in atmosphere granularity be more than 0.5 μm particle be no more than 100
Hundred grades of environment purifications under carry out.
Sulfuric acid molecule formula：H2SO4, relative molecular mass：98.08g/mol.
Fusing point：10.371℃；Boiling point：338℃；Density：1.83g/cm3
Individual protection：Wearing complete suit prevents chemical contact；Must be according to the danger in specific working environment
Dangerous material concentration selects the type of safeguard with amount.
Respiratory system protection：Risk assessment shows that air-purifying respirator is adapted to use full shape of face protector, is used as engineering control
That makes is standby, and it carries multifunctional combination type（The U.S.）Or ABEK types（EN 14387）Respirator filter core；
If breathing mask is the unique conditional of protection, tunneling boring breathing mask is used.Use such as NIOSH（The U.S.）Or
CEN（Europe）The breathing mask and part tested and verified etc. government standard.
Environmental exposure is controlled：Product is forbidden to flow into sewer.
Embodiment 2
A kind of production method of ultra-clean and high-purity sulphuric acid, methods described step is as follows：
（1）Removal of impurities：Technical grade sulfuric acid is injected to add under treatment trough, mechanical agitation after cleaner, standing and filtered.It is described to remove
Miscellaneous dose is KMnO4And K2S2O8Mixture, weight ratio be 4:1, it is intended to the difficulty such as arsenic gone by redox reaction in sulfuric acid
With the impurity of removal.
（2）Rectifying：By step（1）In filtrate be introduced into through negative pressure in continuous rectification apparatus, treat liquid level slightly above heating furnace
During silk, electrified regulation continuous rectification；2.0L is fed every time.The material of continuous rectification apparatus is pure quartz glass.
（3）Fractionation：Collection step（2）In midbarrel, cut temperature range be 332 DEG C ~ 342 DEG C.Less than 332 DEG C
Or the cut higher than 342 DEG C is back flowed back into continuous rectification apparatus through pipeline, rectifying again, while it is former to adjust acid inlet valve addition
Material, keeps the liquid level ± 5cm in continuous rectification apparatus, keeps continuous production.
（4）Ultra-clean filtering：By step（3）The cut of collection introduces ultra-clean filter through negative pressure and carries out ultra-clean filtering.It is super
Net filtering is that under the protection of dry nitrogen, and granularity is more than hundred grade purifications of 0.5 μm of the particle no more than 100 in atmosphere
Carried out under environment.Ultra-clean filter is provided with some dismountable microfiltration membranes and NF membrane, it is intended to ensure steady quality, and easily
Cleaning replacement, does not influence quantity-produced to carry out.Microfiltration membranes are set to：First group of micro-filtration membrane aperture is 0.8 μm；Second group of micro-filtration
Membrane aperture is 0.2 μm；NF membrane is set to：First group of nanofiltration membrane aperture is 1.0nm, and second group of nanofiltration membrane aperture is 0.5nm.
First group of microfiltration membranes uses polyvinylidene fluoride type；Second group of microfiltration membranes uses PTFE Type；
What first group and second group of NF membrane were used is all PTFE Type.
（5）Ultra-clean packing：Under nitrogen protection, using 1mL syringe aspiration steps（4）In a small amount of liquid detected,
After product quality detection reaches requirement, ultra-clean packing.
It is ultra-clean packing be under the protection of dry nitrogen, and in atmosphere granularity be more than 0.5 μm particle be no more than 100
Hundred grades of environment purifications under carry out.
The present invention is described in detail by reference to specific embodiment.It may be evident, however, that in the essence without departing substantially from the present invention
In the case of god, those skilled in the art can perform to embodiment and change and replace.In other words, the shape that the present invention illustrates
Formula is disclosed, rather than is explained with being limited.Judge idea of the invention, it is contemplated that appended claim.
Claims (2)
1. a kind of production method of ultra-clean and high-purity sulphuric acid, it is characterised in that methods described step is as follows：
（1）Removal of impurities：Technical grade sulfuric acid is injected to add under treatment trough, mechanical agitation after cleaner, standing and filtered；The cleaner
For KMnO4And K2S2O8Mixture, weight ratio be 3:1；
（2）Rectifying：By step（1）In filtrate be introduced into through negative pressure in continuous rectification apparatus, whne liquid level be slightly above heating furnace silk when,
Electrified regulation continuous rectification；1.8L is fed every time, and the material of continuous rectification apparatus is the stainless steel of inside lining anti-corrosive material；
（3）Fractionation：Collection step（2）In midbarrel, cut temperature range is 332 DEG C ~ 342 DEG C, less than 332 DEG C or high
Back flow back into continuous rectification apparatus, again rectifying, while adjusting acid inlet valve addition raw material, protected through pipeline in 342 DEG C of cuts
Liquid level ± the 5cm in continuous rectification apparatus is held, continuous production is kept；
（4）Ultra-clean filtering：By step（3）The cut of collection introduces ultra-clean filter through negative pressure and carries out ultra-clean filtering, ultra-clean mistake
Filter is that under the protection of dry nitrogen, and granularity is more than 0.5 μm of particle and is no more than hundred grades of environment purifications of 100 in atmosphere
Lower to carry out, ultra-clean filter is provided with some dismountable microfiltration membranes and NF membrane, and microfiltration membranes are set to：First group of microfiltration membranes
Aperture is 0.5 μm；Second group of micro-filtration membrane aperture is 0.1 μm；NF membrane is set to：First group of nanofiltration membrane aperture is 0.5nm, second
Group nanofiltration membrane aperture is 0.2nm；
First group of microfiltration membranes uses polyvinylidene fluoride type；Second group of microfiltration membranes uses PTFE Type；
What first group and second group of NF membrane were used is all PTFE Type；
（5）Ultra-clean packing：Under nitrogen protection, using 1mL syringe aspiration steps（4）In a small amount of liquid detected, work as production
Quality, which is detected, to be reached after requirement, ultra-clean packing；
It is ultra-clean packing be under the protection of dry nitrogen, and in atmosphere granularity be more than 0.5 μm particle be no more than 100 hundred
Carried out under level environment purification.
2. a kind of production method of ultra-clean and high-purity sulphuric acid, it is characterised in that methods described step is as follows：
（1）Removal of impurities：Technical grade sulfuric acid is injected to add under treatment trough, mechanical agitation after cleaner, standing and filtered；The cleaner
For KMnO4And K2S2O8Mixture, weight ratio be 4:1；
（2）Rectifying：By step（1）In filtrate be introduced into through negative pressure in continuous rectification apparatus, whne liquid level be slightly above heating furnace silk when,
Electrified regulation continuous rectification；2.0L is fed every time, and the material of continuous rectification apparatus is pure quartz glass；
（3）Fractionation：Collection step（2）In midbarrel, cut temperature range is 332 DEG C ~ 342 DEG C, less than 332 DEG C or high
Back flow back into continuous rectification apparatus, again rectifying, while adjusting acid inlet valve addition raw material, protected through pipeline in 342 DEG C of cuts
Liquid level ± the 5cm in continuous rectification apparatus is held, continuous production is kept；
（4）Ultra-clean filtering：By step（3）The cut of collection introduces ultra-clean filter through negative pressure and carries out ultra-clean filtering, ultra-clean mistake
Filter is that under the protection of dry nitrogen, and granularity is more than 0.5 μm of particle and is no more than hundred grades of environment purifications of 100 in atmosphere
Lower to carry out, ultra-clean filter is provided with some dismountable microfiltration membranes and NF membrane, and microfiltration membranes are set to：First group of microfiltration membranes
Aperture is 0.8 μm；Second group of micro-filtration membrane aperture is 0.2 μm；NF membrane is set to：First group of nanofiltration membrane aperture is 1.0nm, second
Group nanofiltration membrane aperture is 0.5nm；
First group of microfiltration membranes uses polyvinylidene fluoride type；Second group of microfiltration membranes uses PTFE Type；
What first group and second group of NF membrane were used is all PTFE Type；
（5）Ultra-clean packing：Under nitrogen protection, using 1mL syringe aspiration steps（4）In a small amount of liquid detected, work as production
Quality, which is detected, to be reached after requirement, ultra-clean packing；
It is ultra-clean packing be under the protection of dry nitrogen, and in atmosphere granularity be more than 0.5 μm particle be no more than 100 hundred
Carried out under level environment purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510620848.9A CN105174233B (en) | 2015-09-25 | 2015-09-25 | A kind of production method of ultra-clean and high-purity sulphuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510620848.9A CN105174233B (en) | 2015-09-25 | 2015-09-25 | A kind of production method of ultra-clean and high-purity sulphuric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105174233A CN105174233A (en) | 2015-12-23 |
| CN105174233B true CN105174233B (en) | 2017-07-28 |
Family
ID=54896775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510620848.9A Active CN105174233B (en) | 2015-09-25 | 2015-09-25 | A kind of production method of ultra-clean and high-purity sulphuric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105174233B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485022A (en) * | 2019-01-21 | 2019-03-19 | 苏州晶瑞化学股份有限公司 | A kind of method that combined films method prepares ultra-pure sulfuric acid |
| CN110155955B (en) * | 2019-04-01 | 2021-07-23 | 岷山环能高科股份公司 | Production method for preparing electronic-grade sulfuric acid by using non-ferrous smelting flue gas |
| CN112079337B (en) * | 2020-09-19 | 2023-08-15 | 韶关高科祥高新材料有限公司 | Production method of electronic grade high-purity ultra-clean sulfuric acid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102009957A (en) * | 2010-11-20 | 2011-04-13 | 江阴市润玛电子材料有限公司 | Method for purifying high-yield superclean high-purity hydrofluoric acid |
| CN202945063U (en) * | 2012-11-15 | 2013-05-22 | 宜昌瑞特精细化工有限公司 | Ultra-clean sulfuric acid of high-purity production device |
| CN103172037A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using activated-carbon filter screen |
| CN104163403A (en) * | 2013-05-16 | 2014-11-26 | 江阴江化微电子材料股份有限公司 | Making method for ultra-pure sulfuric acid |
-
2015
- 2015-09-25 CN CN201510620848.9A patent/CN105174233B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105174233A (en) | 2015-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101362675B (en) | Method for preparing super-clean and high-purity isopropanol and apparatus thereof | |
| JP5071611B2 (en) | Method of cleaning silicon for semiconductor material, polycrystalline silicon lump, and cleaning apparatus | |
| JP5780411B2 (en) | Hydrogen peroxide aqueous solution purification method and apparatus | |
| CN113371683B (en) | Electronic grade hydrogen peroxide production method | |
| JP5800436B2 (en) | Boric acid recovery method and recovery apparatus | |
| JP3797390B2 (en) | Method for producing purified hydrogen peroxide | |
| CN105174233B (en) | A kind of production method of ultra-clean and high-purity sulphuric acid | |
| JP2012062300A (en) | Method for producing ultra-high purity electronic grade chemical reagent | |
| CN101264869B (en) | Continuous producing technique for ultra-high pure nitric acid | |
| EP0739228A1 (en) | Recycling of wafer cleaning substances | |
| CN102485642A (en) | Method for producing ultra-pure hydrogen peroxide | |
| US11242253B2 (en) | Method for producing polycrystalline silicon | |
| CN110589770A (en) | Preparation method of electronic-grade hydrofluoric acid | |
| CN112723316A (en) | Purification method for removing TOC in hydrogen peroxide at low temperature | |
| CN111574326A (en) | Purification method of semiconductor grade isopropanol | |
| CN201901654U (en) | Continuous purifying device of ultraclean high-purity isopropanol | |
| CN201280528Y (en) | Ultra-clean high-purity isopropyl alcohol preparation apparatus | |
| CN102502530A (en) | Method for producing electronic-grade sulfuric acid by static fusion crystallization | |
| JP2013095629A (en) | Method and apparatus for recovering hydrofluoric acid | |
| CN201190105Y (en) | Apparatus for continuous production of ultra-pure nitric acid | |
| CN110121480A (en) | Refine the manufacturing method and manufacture system of aqueous hydrogen peroxide solution | |
| CN109485022A (en) | A kind of method that combined films method prepares ultra-pure sulfuric acid | |
| US20240083837A1 (en) | Processes for purifying organic amines | |
| JP4118605B2 (en) | Method for producing fused silica particles | |
| JP2005296839A (en) | Method and apparatus for making ultrapure water, and cleaning electronic components and members using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |