CN103626131A - Method for producing chlorine dioxide - Google Patents
Method for producing chlorine dioxide Download PDFInfo
- Publication number
- CN103626131A CN103626131A CN201310240568.6A CN201310240568A CN103626131A CN 103626131 A CN103626131 A CN 103626131A CN 201310240568 A CN201310240568 A CN 201310240568A CN 103626131 A CN103626131 A CN 103626131A
- Authority
- CN
- China
- Prior art keywords
- reactor
- reaction medium
- mineral acid
- alkaline metal
- metal chlorate
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/026—Preparation from chlorites or chlorates from chlorate ions in the presence of a peroxidic compound, e.g. hydrogen peroxide, ozone, peroxysulfates
Abstract
The invention relates to a method for producing chlorine dioxide, to be specific, relates to a method for producing the chlorine dioxide in at least two reaction chambers continuously under the non-crystallization condition.
Description
The application is dividing an application of application number is 200580032178.3, the applying date is on September 6th, 2005, denomination of invention is " producing the method for dioxide peroxide " application.
The present invention relates to a kind of method of producing continuously dioxide peroxide under non-crystallizable condition at least two reactors.
The dioxide peroxide using with aqueous solution form receives very large concern industrial, is mainly used in association with pulp bleaching, and also for water, purifies, grease bleaching, from trade effluent, removes phenols etc.Therefore be desirable to provide the method for energy High-efficient Production dioxide peroxide.
The different methods of existing many production dioxide peroxide.Maximum plant-scale production method is alkaline metal chlorate to be carried out to successive reaction with reductive agent such as hydrogen peroxide, methyl alcohol, chlorion or sulfurous gas in acidic medium form dioxide peroxide, and it is shifted out from reaction medium with gas form.Conventionally be mainly to provide acidity with sulfuric acid, and vitriol is to shift out with solid alkali metal vitriol or the form being dissolved in useless reaction medium as by product.
In class methods, the reaction medium in single reaction vessel maintains under subatmospheric boiling condition, and wherein an alkali metal salt of acid precipitates and shifts out with salt-cake form.These class methods are for example described in US patent 5770171,5091166 and 5091167.
In another kind of method, reaction medium maintains under non-crystallizable condition, is atmospheric pressure substantially conventionally.In most of the cases, the reaction medium that will give up is delivered to the second reactor further reaction from the first reactor and is produced dioxide peroxide.The early stage example of these class methods is to use respectively sulfurous gas and methyl alcohol as Mathieson and the Solvay method of reductive agent.Attempt by least part of job description that improves these methods with hydrogen peroxide as reductive agent in for example Japanese Unexamined Patent Publication application, JP No.1988-008203,1991-115102 and WO01/077012, but be only the very industrialization of limited extent.Disruptive technology comes from that EP612686 is disclosed uses hydrogen peroxide as the method for reductive agent at the first and second reactors simultaneously.The method is in registered trademark
lower commercialization and be easy to operation and can be in simple device come high yield to produce dioxide peroxide with high yield.
In non-crystallizable method, an alkali metal salt that the useless reaction medium shifting out from last reactor comprises acid, acid and unreacted and the alkaline metal chlorate that loses.It is believed that the method in the end under the alap condition of perchlorate concentration of a reactor (being normally the second reactor) operation so that loss amount minimize.On the other hand.If find, perchlorate concentration is too low, and the corrosion of processing unit (equipment of conventionally being manufactured by titanium at least partly) can increase.But, be surprised to find now using hydrogen peroxide can operate under the perchlorate concentration than previously higher in as the method for reductive agent, it is believed that the loss of oxymuriate is not significantly increased.
Therefore the present invention is directed to a kind of method of producing continuously dioxide peroxide under non-crystallizable condition at least two reactors; comprise the following steps: alkaline metal chlorate, mineral acid and hydrogen peroxide are sent into the first reactor, form the acid reaction medium maintaining in described the first reactor; Make alkaline metal chlorate, hydrogen peroxide and mineral acid in described reaction medium, react an alkali metal salt that forms dioxide peroxide and described mineral acid; From the described reaction medium of described the first reactor, shift out gas form dioxide peroxide; The useless reaction medium that comprises an alkali metal salt of mineral acid, alkaline metal chlorate and described mineral acid is shifted out and sends into the second reactor from described the first reactor; To sending into hydrogen peroxide in the reaction medium in described the second reactor and making alkaline metal chlorate's concentration of reaction medium wherein maintain about 9-75mmol/l, preferred about 14-56mmol/l, more preferably 20-47mmol/l; Make alkaline metal chlorate, hydrogen peroxide and mineral acid in described reaction medium, react an alkali metal salt that forms dioxide peroxide and described mineral acid; From the described reaction medium of described the second reactor, shift out gas form dioxide peroxide; With the useless reaction medium that comprises an alkali metal salt of mineral acid and described mineral acid is shifted out from described the second reactor.
The reaction of carrying out in reactor is complicated and is not to understand completely to each details.Primary product is an alkali metal salt of dioxide peroxide, oxygen and described mineral acid.In some cases, some oxymuriates change into muriate as final product rather than dioxide peroxide.Found can reduce by improving the concentration of oxymuriate in the second reactor the muriate obtaining as final product.Therefore, lower amount of chloride the useless reaction medium shifting out from the second reactor, has compensated the loss causing because perchlorate concentration is high to a great extent.
Preferably to reactor, blowing rare gas element increases and stirs and make dioxide peroxide be diluted to safe concentration.Also rare gas element can be guided in reactor on liquid level.Can use any available rare gas element as nitrogen or oxygen, but conventionally preferably use air from cost consideration.
The dioxide peroxide forming in reactor shifts out with any rare gas element that blows into container with gas form with oxygen.Preferably gas is delivered to a resorber, it is contacted to dissolve most of oxygen of dioxide peroxide while and insoluble gas with water and pass through through this.Then chlorine dioxide water can be collected in a storage tank and for any intended use as association with pulp bleaching.
The useless reaction medium preferably the second reactor being shifted out send into a stripper that has an inert gas feed blow out dioxide peroxide and other still stay wherein gaseous substance.Stripper gas is out delivered to resorber together with reactor gas out.Useless reaction medium after stripping claims again spent acid under many occasions, to can be used as the sulphur source of PH conditioning agent and/or pulping process processed.Also can as described in US patent 5487881 and 6322690, in battery, carry out electrochemistry increases acid treatment and optionally by its all or part of first reactor that loops back, becomes at least a portion of mineral acid charging.
Conventionally use sodium chlorate, Potcrate and composition thereof, but also can consider to use other an alkali metal salt.Alkaline metal chlorate normally with aqueous solution form, preferably with high density for example about 3mol/l to the aqueous solution form charging of saturation concentration.Except the oxymuriate from contained in the useless reaction medium of the first reactor, do not need to send into any oxymuriate in the second reactor in most cases.
Alkaline metal chlorate comprises a small amount of chloride impurity conventionally, but preferably this amount is low as far as possible, to reduce the formation volume of by product nitrogen.In the charging of preferred as alkali oxymuriate, amount of chloride is less than about 1mol%, more preferably less than about 0.5mol%, be most preferably less than about 0.05mol%, be especially most preferably less than about 0.02mol%.
Mineral acid is preferably the acid of halogen as sulfuric acid or phosphoric acid, most preferably the about 60-98wt% sulfuric acid of concentration for example.Also can consider to use mixtures of mineral acids.In most of the cases except the mineral acid from contained in the useless reaction medium of the first reactor, do not need to send into any mineral acid in the second reactor.
Preferably the impurity in alkaline metal chlorate substantially without muriate.But also there is a small amount of muriate in other incoming flow in as mineral acid.The muriate total amount that comprises impurity in alkaline metal chlorate of preferably sending into process is the muriatic about lmol% that is less than alkali metal chlorate feed, more preferably less than about 0.5mol%, be most preferably less than about 0.05mol%, be especially most preferably less than about 0.02mol%.
In the first and second reactors, all use hydrogen peroxide as reductive agent and aqueous solution form normally, the about 10-70wt% of preferred concentration, 25-60wt% most preferably from about.The amount of hydrogen peroxide that preferably will send into is about 0.5-2mol/mol alkali metal chlorate feed, is most preferably 0.5-lmol/mol alkali metal chlorate feed, 0.5-0.6mol/mol alkali metal chlorate feed especially most preferably from about.Preferably by the approximately 50-99.9% of hydrogen peroxide total amount, most preferably the approximately 85-99.5% of hydrogen peroxide total amount sends into the first reactor.Except being present in as impurity a small amount of muriate in oxymuriate, preferably only add hydrogen peroxide as reductive agent, although can separately add other reductive agent completely as methyl alcohol, formaldehyde, formic acid, sugar alcohol, sulfurous gas and muriate.In the situation that being added with other reductive agent, can reduce added amount of hydrogen peroxide.
Each reactant can be distinguished or with the charging of pre-mixed feed streams form.Especially, hydrogen peroxide and alkaline metal chlorate can be blended together to one incoming flow in advance, preferably mineral acid is sent into separately simultaneously.
The temperature of reaction medium preferably maintains about 30-100 ℃, 40-80 ℃ most preferably from about in reactor.The temperature of the first and second reactors can be basic identical, but also can differing temps operation.In the first and second reactors, the temperature of reaction medium is preferably lower than the boiling point under wirking pressure.According to envrionment temperature, feed stream temperature, rare gas element, be blown into speed and other processing condition, heating or cooling reactor maintain desired temperature as required.
The absolute pressure maintaining in reactor preferably about 50-120kPa, most preferably from about 80-110kPa, most preferably be normal atmosphere especially.Pressure in the first and second reactors conventionally but be not must be basic identical.
The acidity of reaction medium preferably maintains about 4-14N, 6-12N most preferably from about in the first and second reactors.In most cases, in the first and second reactors, acidity difference is very little, is preferably less than approximately 15%, is most preferably less than approximately 10%.
In the reaction medium of the first reactor, alkaline metal chlorate's concentration preferably maintains that about 0.05-is saturated, more preferably from about 0.075-2.5mol/l, 0.1-1mol/l most preferably from about.
In a preferred embodiment, the reaction medium of the first reactor preferably maintains the about 0.05-2.5mol/l of alkaline metal chlorate's concentration, the about 6-12N of acidity, the about 40-80 of temperature ℃ and the about 80-110kPa of absolute pressure, and the reaction medium of the second reactor preferably maintains the about 14-56mmol/l of alkaline metal chlorate's concentration, the about 6-12N of acidity, the about 40-80 of temperature ℃ and the about 80-110kPa of absolute pressure.
Can use with other non-crystallizable technique (as Mathieson, Solvay and
the reactor of same type and other processing unit.The processing unit that comprises the contact reacts medium of reactor is applicable to making or be with it to make lining by tolerating the wherein material of chemical.Preferred material is titanium or other metal or alloy that can form and keep protective oxide layer while contacting with reaction medium, although equipment also can be made as fluoroplastics or other polymeric material by other chemicals-resisting material.The equipment preferably contacting with reaction medium at least partly comprises that the second reactor is be made of titanium or be with titanium lining.
By the following example, further illustrate the present invention.
embodiment: in a generating unit that comprises the first reactor (main reactor) and the second reactor (secondary response device), produce continuously dioxide peroxide.Sodium chlorate (containing about 0.01wt% sodium chloride as impurity), sulfuric acid and hydrogen peroxide are sent into the first reactor.The reaction medium flowing out from the first reactor enters the second reactor that separately has hydrogen peroxide to send into.The reaction medium flowing out from the second reactor takes out as spent acid by stripper.The reaction medium that air is blowed by two reactors dilutes the dioxide peroxide that therefrom shifted out.Two reactors all maintain the temperature of under atmospheric pressure with 57 ℃.Under steady state conditions, collect the data under several different situations, the results are shown in following table.
Obviously, in the second reactor, density of sodium chlorate decline has caused sodium chloride concentration increase.Because this increasing amount is because oxymuriate is converted into muriate as the result of final product, this has also represented the loss due to the spent acid.The loss of the unreacted oxymuriate therefore, causing by increasing the perchlorate concentration of the second reactor is chlorinated at least partly thing formation volume minimizing institute and compensates.Consider the situation that processing unit corrosion phenomenon reduces, even if total losses may be higher in some cases, but still can receive in level.
Claims (10)
1. under non-crystallizable condition, at least two reactors, produce continuously the method for dioxide peroxide, comprise the following steps: alkaline metal chlorate, mineral acid and hydrogen peroxide are sent into the first reactor, form the acid reaction medium maintaining in described the first reactor; Make alkaline metal chlorate, hydrogen peroxide and mineral acid in described reaction medium, react an alkali metal salt that forms dioxide peroxide and described mineral acid; From the described reaction medium of described the first reactor, shift out gas form dioxide peroxide; The useless reaction medium that comprises an alkali metal salt of mineral acid, alkaline metal chlorate and described mineral acid is shifted out and sends into the second reactor from described the first reactor; In the reaction medium in described the second reactor, send into hydrogen peroxide and make alkaline metal chlorate's concentration of described reaction medium wherein maintain about 9-75mmol/l; Make alkaline metal chlorate, hydrogen peroxide and mineral acid in described reaction medium, react an alkali metal salt that forms dioxide peroxide and described mineral acid; From the described reaction medium of described the second reactor, shift out gas form dioxide peroxide, and the useless reaction medium that comprises an alkali metal salt of mineral acid and described mineral acid is shifted out from described the second reactor.
2. by the process of claim 1 wherein that alkaline metal chlorate's concentration is maintained at about 14-56mmol/l in the second reactor.
3. by the method for claim 2, wherein in the second reactor, alkaline metal chlorate's concentration is maintained at about 20-47mmol/l.
4. by the method for claim 1-3 any one, wherein rare gas element is blowed and passes through reaction vessel.
5. by the method for claim 1-4 any one, the muriate total amount of wherein sending into process is less than the approximately 1mol% of alkali metal chlorate feed.
6. by the method for claim 1-5 any one, wherein in the first and second reactors, the temperature of reaction medium maintains lower than the boiling point under wirking pressure.
7. by the method for claim 1-6 any one, wherein in the first and second reactors, the acidity of reaction medium maintains about 4-14N.
8. by the method for claim 1-7 any one, wherein mineral acid is sulfuric acid.
9. by the method for claim 1-8 any one, wherein the reaction medium of the first reactor maintains the about 0.05-2.5mol/l of alkaline metal chlorate's concentration, the about 6-12N of acidity, the about 40-80 of temperature ℃ and the about 80-110kPa of absolute pressure, and the reaction medium of the second reactor maintains the about 14-56mmol/l of alkaline metal chlorate's concentration, the about 6-12N of acidity, the about 40-80 of temperature ℃ and the about 80-110kPa of absolute pressure.
10. by the method for claim 1-9 any one, the equipment wherein contacting with reaction medium is be made of titanium or be with titanium lining at least partly.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04445100.3 | 2004-09-24 | ||
| EP04445100 | 2004-09-24 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800321783A Division CN101031505A (en) | 2004-09-24 | 2005-09-06 | A process for the production of chlorine dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103626131A true CN103626131A (en) | 2014-03-12 |
Family
ID=34932999
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800321783A Pending CN101031505A (en) | 2004-09-24 | 2005-09-06 | A process for the production of chlorine dioxide |
| CN201310240568.6A Pending CN103626131A (en) | 2004-09-24 | 2005-09-06 | Method for producing chlorine dioxide |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800321783A Pending CN101031505A (en) | 2004-09-24 | 2005-09-06 | A process for the production of chlorine dioxide |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP1791784A1 (en) |
| JP (2) | JP4913057B2 (en) |
| KR (1) | KR100916974B1 (en) |
| CN (2) | CN101031505A (en) |
| AU (1) | AU2005285645B2 (en) |
| BR (1) | BRPI0516016B1 (en) |
| CA (1) | CA2581318C (en) |
| MA (1) | MA28944B1 (en) |
| MX (1) | MX2007002706A (en) |
| MY (1) | MY145982A (en) |
| RU (1) | RU2355626C2 (en) |
| WO (1) | WO2006033609A1 (en) |
| ZA (1) | ZA200702595B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2589721C (en) * | 2004-12-06 | 2010-05-04 | Akzo Nobel N.V. | Chemical process and production unit |
| CA2589714C (en) * | 2004-12-06 | 2010-04-06 | Akzo Nobel N.V. | Process and apparatus for producing chlorine dioxide |
| MY146251A (en) | 2007-01-12 | 2012-07-31 | Akzo Nobel Nv | Process for the production of chlorine dioxide |
| TWI447065B (en) | 2007-07-13 | 2014-08-01 | Akzo Nobel Nv | Process for the production of chlorine dioxide |
| SA109300539B1 (en) | 2008-10-06 | 2012-04-07 | اكزو نوبل أن . في | Process For The Production Of Chlorine Dioxide |
| ES2553738T3 (en) | 2009-06-16 | 2015-12-11 | Akzo Nobel N.V. | Process for the production of chlorine dioxide |
| KR101765735B1 (en) | 2010-01-18 | 2017-08-07 | 아크조 노벨 케미칼즈 인터내셔널 비.브이. | Process for the production of chlorine dioxide |
| WO2012004233A1 (en) * | 2010-07-08 | 2012-01-12 | Akzo Nobel Chemicals International B.V. | Process for the production of chlorine dioxide |
| CN108439341A (en) * | 2018-05-18 | 2018-08-24 | 广西大学 | A kind of method and device producing chlorine dioxide with high purity gas |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4640527B1 (en) * | 1969-12-11 | 1971-11-30 | ||
| JPS5366892A (en) * | 1976-11-27 | 1978-06-14 | Osaka Soda Co Ltd | Production of chlorine dioxide |
| JPH0621004B2 (en) * | 1989-08-29 | 1994-03-23 | ダイソー株式会社 | Chlorine dioxide manufacturing method |
| JPH0621005B2 (en) * | 1989-09-29 | 1994-03-23 | ダイソー株式会社 | Chlorine dioxide manufacturing method |
| SE500043C2 (en) * | 1990-08-31 | 1994-03-28 | Eka Nobel Ab | Process for continuous production of chlorine dioxide |
| US5486344A (en) * | 1992-06-09 | 1996-01-23 | Eka Nobel Inc. | Method of producing chlorine dioxide |
| US5380517B1 (en) * | 1993-02-26 | 1999-01-19 | Eka Nobel Inc | Process for continuously producing chlorine dioxide |
| SE9502077L (en) * | 1995-06-07 | 1996-08-22 | Eka Chemicals Ab | Methods of producing chlorine dioxide |
| JPH1192104A (en) * | 1997-09-16 | 1999-04-06 | Chisso Corp | High-purity chlorine dioxide aqueous composition, its production and producing device |
| US6565828B2 (en) * | 2000-04-07 | 2003-05-20 | Bristol-Myers Squibb Company | Macrocyclic chelants for metallopharmaceuticals |
| FI108536B (en) * | 2000-04-12 | 2002-02-15 | Kemira Chemicals Oy | Process for producing chlorine dioxide by using several reducing agents together |
-
2005
- 2005-09-06 WO PCT/SE2005/001288 patent/WO2006033609A1/en active Application Filing
- 2005-09-06 ZA ZA200702595A patent/ZA200702595B/en unknown
- 2005-09-06 RU RU2007115409/15A patent/RU2355626C2/en active
- 2005-09-06 JP JP2007533425A patent/JP4913057B2/en active Active
- 2005-09-06 EP EP05778039A patent/EP1791784A1/en not_active Withdrawn
- 2005-09-06 AU AU2005285645A patent/AU2005285645B2/en not_active Ceased
- 2005-09-06 CN CNA2005800321783A patent/CN101031505A/en active Pending
- 2005-09-06 BR BRPI0516016A patent/BRPI0516016B1/en not_active IP Right Cessation
- 2005-09-06 CA CA2581318A patent/CA2581318C/en active Active
- 2005-09-06 KR KR1020077009258A patent/KR100916974B1/en active IP Right Grant
- 2005-09-06 MX MX2007002706A patent/MX2007002706A/en active IP Right Grant
- 2005-09-06 CN CN201310240568.6A patent/CN103626131A/en active Pending
- 2005-09-23 MY MYPI20054489A patent/MY145982A/en unknown
-
2007
- 2007-04-23 MA MA29844A patent/MA28944B1/en unknown
-
2011
- 2011-11-04 JP JP2011242676A patent/JP2012067007A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| RU2007115409A (en) | 2008-10-27 |
| MX2007002706A (en) | 2007-05-18 |
| RU2355626C2 (en) | 2009-05-20 |
| WO2006033609A1 (en) | 2006-03-30 |
| EP1791784A1 (en) | 2007-06-06 |
| AU2005285645A1 (en) | 2006-03-30 |
| CA2581318C (en) | 2011-03-15 |
| JP4913057B2 (en) | 2012-04-11 |
| JP2012067007A (en) | 2012-04-05 |
| ZA200702595B (en) | 2008-06-25 |
| CA2581318A1 (en) | 2006-03-30 |
| JP2008514535A (en) | 2008-05-08 |
| BRPI0516016A (en) | 2008-08-19 |
| MA28944B1 (en) | 2007-10-01 |
| KR100916974B1 (en) | 2009-09-14 |
| MY145982A (en) | 2012-05-31 |
| AU2005285645B2 (en) | 2010-12-16 |
| KR20070061894A (en) | 2007-06-14 |
| BRPI0516016B1 (en) | 2018-11-21 |
| CN101031505A (en) | 2007-09-05 |
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Application publication date: 20140312 |