CN101590420A - A kind of preparation method of zeolite supported zinc oxyhydroxide - Google Patents
A kind of preparation method of zeolite supported zinc oxyhydroxide Download PDFInfo
- Publication number
- CN101590420A CN101590420A CNA2009100724036A CN200910072403A CN101590420A CN 101590420 A CN101590420 A CN 101590420A CN A2009100724036 A CNA2009100724036 A CN A2009100724036A CN 200910072403 A CN200910072403 A CN 200910072403A CN 101590420 A CN101590420 A CN 101590420A
- Authority
- CN
- China
- Prior art keywords
- preparation
- zeolite
- solution
- zinc
- specific embodiment
- 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
Images
Abstract
A kind of preparation method of zeolite-loaded nano-hydroxy zinc oxide, it relates to a kind of preparation method of zeolite-loaded metal oxide.The existence that its solves existing zinc oxyhydroxide be difficult to moisture from, cause secondary pollution, the settling property difference of handling the back water outlet and be difficult to problem easily in real project using.Method: one, system mixed liquor A; Two, system suspension B; Three, system mixed liquor C; Four, with after mixed liquor C filtration, washing, the drying, promptly.The zeolite-loaded nano-hydroxy Zinc oxide particles crystalline form that the present invention obtains is complete, densification and particle diameter are evenly distributed, have and in water, be easy to disperse, good settling property is arranged, can there be the secondary pollution phenomenon, can make the utilization rate of ozone improve 10～15 percentage points, O3 catalytic oxidation has improved 40～50 percentage points than independent ozone oxidation to the clearance of organic pollution in the water.Preparation technology of the present invention is simple, and is with low cost, can be applied in the sewage treatment project on a large scale.
Description
Technical field
The present invention relates to the preparation method that a kind of zeolite carries metal oxide.
Background technology
Zinc oxyhydroxide is as the successful laboratory research that is applied to heterogeneous catalysis ozone oxidation field of catalyst, to improve processing aspect to organic pollution in the water, but be the suspension state after zinc oxyhydroxide is water-soluble, precipitation-free generates after leaving standstill 30min, be difficult to moisture from, therefore settling property is poor, is difficult to recycling, cause the secondary pollution of handling the back water outlet easily, so the utilization difficulty is bigger in engineering reality.
Summary of the invention
Goal of the invention be for the existence that solves existing zinc oxyhydroxide be difficult to moisture from, cause secondary pollution, the settling property difference of handling the back water outlet and be difficult to problem easily in real project using, and provide a kind of preparation method of zeolite-loaded nano-hydroxy zinc oxide.
The preparation method of zeolite supported zinc oxyhydroxide implements according to the following steps: one, earlier with zeolite with distilled water flushing 5～8 times, in concentration is the soluble zinc salt solution environmental of 0.2～2.0mol/L, soak 24～48h then, mixed liquor A; Two, be that the alkaline solution of 0.2～2.5mol/L is added drop-wise in the mixed liquor A with concentration, be stirred to while dripping no longer include precipitation in the solution and produce till, suspension B; Three, the pH value of adjusting suspension B is 12～14, staticly settles 10～30min then, is activation processing 12～24h under 30～60 ℃ of conditions in temperature then, gets mixed liquor C; Four, will get solid formation after the mixed liquor C filtration, the pH that then solid formation is washed with distilled water to cleaning solution is 7.0, is dry under 30～60 ℃ of conditions in temperature then, promptly gets zeolite supported zinc oxyhydroxide; Wherein the step 1 mesolite is analcime, chabasie, scolecite, heulandite, sodalite, modenite, foresite or artificial zeolite; The soluble Zn salting liquid is zinc nitrate solution, solution of zinc sulfate, liquor zinci chloridi, zinc carbonate solution or zinc acetate solution; Step 2 neutral and alkali solution is sodium hydroxide solution, potassium hydroxide solution, aqua calcis or magnesium hydroxide solution.
The zeolite-loaded nano-hydroxy Zinc oxide particles crystalline form that the present invention obtains is complete, even compact and particle diameter are evenly distributed, zeolite-loaded nano-hydroxy zinc oxide has the dispersion of being easy in water, specific area is big, settling property is good, catalyst combines with carrier closely, very easy and moisture from, the advantage that is evenly distributed, and the zeolite supported zinc oxyhydroxide that the present invention obtains can promote ozone to decompose the generation hydroxyl radical free radical, increase the generating rate and the quantity of free radical in the water body, can make the utilization rate of ozone improve 10～15 percentage points, O3 catalytic oxidation has improved 40～50 percentage points than independent ozone oxidation to the clearance of organic pollution in the water.The catalyst that zeolite supported zinc oxyhydroxide decompose to generate hydroxyl radical free radical as catalysis ozone is used for the Continuous Flow test, and to have a catalytic elimination organic pollution active strong, and the self stability height is easy to recycle, and does not produce advantages such as secondary pollution.Preparation technology of the present invention is simple, easily synthetic, with low cost, can be applied in the sewage treatment project on a large scale.
Description of drawings
Fig. 1 is a design sketch of removing organic pollution parachloronitrobenzene in the water, " ■ " expression adds the organic pollutant removal rate curve of the zeolite-loaded nano-hydroxy zinc oxide that ozone and the specific embodiment 25 obtain among the figure, " ◆ " expression adds the organic pollutant removal rate curve of ozone separately among the figure, and " ▲ " expression adds the zeolite-loaded nano-hydroxy zinc oxide that the specific embodiment 25 obtains separately and is adsorbed with organic pollutants clearance curve among the figure.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method of present embodiment zeolite supported zinc oxyhydroxide implements according to the following steps: one, earlier with zeolite distilled water flushing 5～8 times, in concentration is the soluble zinc salt solution environmental of 0.2～2.0mol/L, soak 24～48h then, mixed liquor A; Two, be that the alkaline solution of 0.2～2.5mol/L is added drop-wise in the mixed liquor A with concentration, be stirred to while dripping no longer include precipitation in the solution and produce till, suspension B; Three, the pH value of adjusting suspension B is 12～14, staticly settles 10～30min then, is activation processing 12～24h under 30～60 ℃ of conditions in temperature then, gets mixed liquor C; Four, will get solid formation after the mixed liquor C filtration, the pH that then solid formation is washed with distilled water to cleaning solution is 7.0, is dry under 30～60 ℃ of conditions in temperature then, promptly gets zeolite supported zinc oxyhydroxide; Wherein the step 1 mesolite is analcime, chabasie, scolecite, heulandite, sodalite, modenite, foresite or artificial zeolite; The soluble Zn salting liquid is zinc nitrate solution, solution of zinc sulfate, liquor zinci chloridi, zinc carbonate solution or zinc acetate solution; Step 2 neutral and alkali solution is sodium hydroxide solution, potassium hydroxide solution, aqua calcis or magnesium hydroxide solution.
The employed raw material of present embodiment are all buied in market.
The zeolite supported zinc oxyhydroxide that present embodiment obtains is the white granular solid.
The specific embodiment two: the quality that is not both the step 1 mesolite of the present embodiment and the specific embodiment one is 42.0～58.0g.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: the quality that is not both the step 1 mesolite of the present embodiment and the specific embodiment one is 45.0～55.0g.Other step and parameter are identical with the specific embodiment one.
The specific embodiment four: the quality that is not both the step 1 mesolite of the present embodiment and the specific embodiment one is 50.0g.Other step and parameter are identical with the specific embodiment one.
The specific embodiment five: the present embodiment and the specific embodiment one be not both that washing time is 6 times in the step 1.Other step and parameter are identical with the specific embodiment one.
The specific embodiment six: the concentration that is not both soluble Zn salting liquid in the step 1 of the present embodiment and the specific embodiment one is 0.4～1.8mol/L.Other step and parameter are identical with the specific embodiment one.
The specific embodiment seven: the concentration that is not both soluble Zn salting liquid in the step 1 of the present embodiment and the specific embodiment one is 1.2mol/L.Other step and parameter are identical with the specific embodiment one.
The specific embodiment eight: the concentration that is not both soluble Zn salting liquid in the step 1 of the present embodiment and the specific embodiment one is 1.5mol/L.Other step and parameter are identical with the specific embodiment one.
The specific embodiment nine: present embodiment and the specific embodiment one, six, seven or eight are not both that soak time is 30～40h in the step 1.Other step and parameter are identical with the specific embodiment one, six, seven or eight.
The specific embodiment ten: present embodiment and the specific embodiment one, six, seven or eight are not both that soak time is 36h in the step 1.Other step and parameter are identical with the specific embodiment one, six, seven or eight.
The specific embodiment 11: present embodiment and the specific embodiment nine or tens' the concentration that is not both step 2 neutral and alkali solution is 0.4～2.0mol/L.Other step and parameter are identical with the specific embodiment nine or ten.
The specific embodiment 12: present embodiment and the specific embodiment nine or tens' the concentration that is not both step 2 neutral and alkali solution is 0.8～1.2mol/L.Other step and parameter are identical with the specific embodiment nine or ten.
The specific embodiment 13: present embodiment and the specific embodiment nine or tens' the concentration that is not both step 2 neutral and alkali solution is 1.0mol/L.Other step and parameter are identical with the specific embodiment nine or ten.
The specific embodiment 14: present embodiment and the specific embodiment one, six, seven, eight, 11,12 or 13 be not both that stir speed (S.S.) is 100～300r/min in the step 2.Other step and parameter are identical with the specific embodiment one, six, seven, eight, 11,12 or 13.
The specific embodiment 15: present embodiment and the specific embodiment one, six, seven, eight, 11,12 or 13 be not both that stir speed (S.S.) is 200r/min in the step 2.Other step and parameter are identical with the specific embodiment one, six, seven, eight, 11,12 or 13.
The specific embodiment 16: present embodiment and the specific embodiment one, six, seven, eight, 11,12 or 13 be not both that stir speed (S.S.) is 150r/min in the step 2.Other step and parameter are identical with the specific embodiment one, six, seven, eight, 11,12 or 13.
The specific embodiment 17: the pH value that is not both adjusting suspension B in the step 3 of present embodiment and the specific embodiment 14,15 or 16 is 13.Other step and parameter are identical with the specific embodiment 14,15 or 16.
The specific embodiment 18: present embodiment and the specific embodiment one, six, seven, eight, 11,12,13 or 17 be not both that temperature is 35～55 ℃ in the step 3.Other step and parameter are identical with the specific embodiment one, six, seven, eight, 11,12,13 or 17.
The specific embodiment 19: present embodiment and the specific embodiment one, six, seven, eight, 11,12,13 or 17 be not both that temperature is 40 ℃ in the step 3.Other step and parameter are identical with the specific embodiment one, six, seven, eight, 11,12,13 or 17.
The specific embodiment 20: present embodiment and the specific embodiment one, six, seven, eight, 11,12,13 or 17 be not both that temperature is 50 ℃ in the step 3.Other step and parameter are identical with the specific embodiment one, six, seven, eight, 11,12,13 or 17.
The specific embodiment 21: present embodiment and the specific embodiment 18,19 or 20 be not both that the activation processing time is 15～20h in the step 3.Other step and parameter are identical with the specific embodiment 18,19 or 20.
The specific embodiment 22: present embodiment and the specific embodiment 18,19 or 20 be not both that the activation processing time is 18h in the step 3.Other step and parameter are identical with the specific embodiment 18,19 or 20.
The specific embodiment 23: the present embodiment and the specific embodiment one not to be both in the step 4 in temperature be dry under 40 ℃ of conditions.Other step and parameter are identical with the specific embodiment one.
The specific embodiment 24: the present embodiment and the specific embodiment one not to be both in the step 4 in temperature be dry under 50 ℃ of conditions.Other step and parameter are identical with the specific embodiment one.
The specific embodiment 25: the preparation method of present embodiment zeolite supported zinc oxyhydroxide implements according to the following steps: one, elder generation is with artificial zeolite distilled water flushing 7 times of 50.0g, in concentration is the zinc nitrate solution environment of 0.2mol/L, soak 24h then, mixed liquor A; Two, be that the sodium hydroxide solution of 0.25mol/L dropwise is added drop-wise in the mixed liquor A with concentration, while dripping with the mixing speed of 100r/min be stirred to no longer include precipitation in the solution and produce till, suspension B; Three, the pH value of adjusting suspension B is 13, staticly settles 20min then, is activation processing 24h under 40 ℃ of conditions in temperature then, gets mixed liquor C; Four, will get sediment after the mixed liquor C filtration, the pH that then sediment is washed with distilled water to cleaning solution is 7.0, is dry under 40 ℃ of conditions in temperature then, promptly gets zeolite supported zinc oxyhydroxide.
Respectively to the organic pollution in the water with same concentrations---parachloronitrobenzene (pCNB) divides three groups of tests to remove; Shown in first group carry out parachloronitrobenzene and remove test for adding zeolite supported zinc oxyhydroxide that present embodiment obtains separately; Second group is carried out parachloronitrobenzene and removes test for adding ozone (the ozonisation gas flow is 5mg/L, and concentration of liquid phase ozone is 1mg/L) separately; The 3rd group of zeolite supported zinc oxyhydroxide that is present embodiment obtains combines as catalyst (dosage of catalyst is 10g/L) and ozone (the ozonisation gas flow is 5mg/L, and concentration of liquid phase ozone is about 1mg/L) and carries out parachloronitrobenzene (pCNB) removal test; Experimental condition is: water inlet flow velocity and go out water flow velocity and be 6L/h, adopt the reactive mode of continuous water-inlet continuous water-outlet, the content of parachloronitrobenzene in the water outlet of 20min sampling and measuring.Three groups of parachloronitrobenzene clearances such as Fig. 1, as can be seen from Figure 1 the influence of object being removed as the adsorptivity of catalyst of the zeolite supported zinc oxyhydroxide that obtains of present embodiment is less only is 20%, though and under the same terms during independent ozone oxidation removal effect increase, but clearance is still very low only is 40%, but when the zeolite supported zinc oxyhydroxide that obtains when present embodiment joins in the water sample as catalyst and ozone simultaneously, the adding of zeolite supported zinc oxyhydroxide has significantly improved parachloronitrobenzene removal (reaction 20min) ability as can be seen, and by test data as can be seen zeolite supported zinc oxyhydroxide (catalyst) O3 catalytic oxidation that obtains of present embodiment to remove the effect of organic pollution strong, active high.
The zeolite supported zinc oxyhydroxide that present embodiment obtains leaves standstill 10min sedimentation fully after can adding in the entry fully as catalyst, and this has well solved the problem that existing catalyst (zinc oxyhydroxide) is difficult to reclaim.
The zeolite supported zinc oxyhydroxide particle crystalline form that present embodiment obtains is complete, even compact and particle diameter are evenly distributed, zeolite supported zinc oxyhydroxide has the dispersion of being easy in water, specific area is big, and settling property is good, catalyst combines closely with carrier, the advantage that is evenly distributed.
The specific embodiment 26: the preparation method of the zeolite-loaded nano-hydroxy zinc oxide of present embodiment implements according to the following steps: one, elder generation is with modenite distilled water flushing 8 times of 48.0g, in concentration is the zinc carbonate solution environmental of 1.0mol/L, soak 36h then, mixed liquor A; Two, be that the aqua calcis of 1.5mol/L dropwise is added drop-wise in the mixed liquor A with concentration, while dripping with the mixing speed of 200r/min be stirred to no longer include precipitation in the solution and produce till, suspension B; Three, the pH value of adjusting suspension B is 12, staticly settles 15min then, is activation processing 16h under 50 ℃ of conditions in temperature then, gets mixed liquor C; Four, will get sediment after the mixed liquor C filtration, the pH that then sediment is washed with distilled water to cleaning solution is 7.0, is dry under 50 ℃ of conditions in temperature then, promptly gets zeolite supported zinc oxyhydroxide.
The zeolite supported zinc oxyhydroxide particle crystalline form that present embodiment obtains is complete, even compact and particle diameter are evenly distributed, zeolite supported zinc oxyhydroxide has the dispersion of being easy in water, specific area is big, and settling property is good, catalyst combines closely with carrier, is evenly distributed.
Claims (8)
1, a kind of preparation method of zeolite supported zinc oxyhydroxide, the preparation method who it is characterized in that zeolite supported zinc oxyhydroxide implements according to the following steps: one, earlier with zeolite distilled water flushing 5～8 times, in concentration is the soluble zinc salt solution environmental of 0.2～2.0mol/L, soak 24～48h then, mixed liquor A; Two, be that the alkaline solution of 0.2～2.5mol/L is added drop-wise in the mixed liquor A with concentration, be stirred to while dripping no longer include precipitation in the solution and produce till, suspension B; Three, the pH value of adjusting suspension B is 12～14, staticly settles 10～30min then, is activation processing 12～24h under 30～60 ℃ of conditions in temperature then, gets mixed liquor C; Four, will get solid formation after the mixed liquor C filtration, the pH that then solid formation is washed with distilled water to cleaning solution is 7.0, is dry under 30～60 ℃ of conditions in temperature then, promptly gets zeolite supported zinc oxyhydroxide; Wherein the step 1 mesolite is analcime, chabasie, scolecite, heulandite, sodalite, modenite, foresite or artificial zeolite; The soluble Zn salting liquid is zinc nitrate solution, solution of zinc sulfate, liquor zinci chloridi, zinc carbonate solution or zinc acetate solution; Step 2 neutral and alkali solution is sodium hydroxide solution, potassium hydroxide solution, aqua calcis or magnesium hydroxide solution.
2, the preparation method of a kind of zeolite supported zinc oxyhydroxide according to claim 1, the concentration that it is characterized in that soluble Zn salting liquid in the step 1 is 0.4～1.8mol/L.
3, the preparation method of a kind of zeolite supported zinc oxyhydroxide according to claim 1 and 2 is characterized in that soak time is 30～40h in the step 1.
4, the preparation method of a kind of zeolite supported zinc oxyhydroxide according to claim 3, the concentration that it is characterized in that step 2 neutral and alkali solution is 0.4～2.0mol/L.
5,, it is characterized in that stir speed (S.S.) is 100～300r/min in the step 2 according to the preparation method of claim 1,2 or 4 described a kind of zeolite supported zinc oxyhydroxides.
6, the preparation method of a kind of zeolite supported zinc oxyhydroxide according to claim 5 is characterized in that the pH of adjusting suspension B in the step 3 is 13.
7,, it is characterized in that temperature is 35～55 ℃ in the step 3 according to the preparation method of claim 1,2,4 or 6 described a kind of zeolite supported zinc oxyhydroxides.
8, the preparation method of a kind of zeolite supported zinc oxyhydroxide according to claim 7 is characterized in that the activation processing time is 15～20h in the step 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100724036A CN101590420A (en) | 2009-06-30 | 2009-06-30 | A kind of preparation method of zeolite supported zinc oxyhydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100724036A CN101590420A (en) | 2009-06-30 | 2009-06-30 | A kind of preparation method of zeolite supported zinc oxyhydroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101590420A true CN101590420A (en) | 2009-12-02 |
Family
ID=41405416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100724036A Pending CN101590420A (en) | 2009-06-30 | 2009-06-30 | A kind of preparation method of zeolite supported zinc oxyhydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101590420A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059109A (en) * | 2010-11-29 | 2011-05-18 | 哈尔滨工业大学 | Preparation method of pumice-loaded zinc oxide hydroxide |
| CN102898681A (en) * | 2012-09-27 | 2013-01-30 | 河南科技大学 | Loaded type nano-zinc oxide composite material |
| CN102898682A (en) * | 2012-09-27 | 2013-01-30 | 河南科技大学 | Supported nano zinc oxide composite material |
| CN103143360A (en) * | 2013-03-22 | 2013-06-12 | 黑龙江省科学院自然与生态研究所 | Preparation method of multi-element polyhydroxy pumice ozone catalyst |
-
2009
- 2009-06-30 CN CNA2009100724036A patent/CN101590420A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059109A (en) * | 2010-11-29 | 2011-05-18 | 哈尔滨工业大学 | Preparation method of pumice-loaded zinc oxide hydroxide |
| CN102898681A (en) * | 2012-09-27 | 2013-01-30 | 河南科技大学 | Loaded type nano-zinc oxide composite material |
| CN102898682A (en) * | 2012-09-27 | 2013-01-30 | 河南科技大学 | Supported nano zinc oxide composite material |
| CN103143360A (en) * | 2013-03-22 | 2013-06-12 | 黑龙江省科学院自然与生态研究所 | Preparation method of multi-element polyhydroxy pumice ozone catalyst |
| CN103143360B (en) * | 2013-03-22 | 2014-09-24 | 黑龙江省科学院自然与生态研究所 | Preparation method of multi-element polyhydroxy pumice ozone catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105731624B (en) | A method of utilizing heterogeneous Fenton-like reaction catalytic oxidation treatment reverse osmosis concentrated water | |
| CN107088413A (en) | A kind of CuO/Cu2O photochemical catalysts and preparation method and application | |
| CN110639563B (en) | Bismuth oxychloride/silver ferrite ternary composite Z-type photocatalyst and preparation method and application thereof | |
| CN102553590B (en) | Abandoned shell/nanometer Cu2O composite photocatalyst material as well as preparation and application thereof | |
| CN110354887A (en) | A kind of catalyst capable of magnetic separating and its preparation method and application for photocatalytic degradation antibiotic | |
| CN108514870B (en) | Hydrotalcite-poly (m-phenylenediamine) composite material and preparation method and application thereof | |
| CN101590420A (en) | A kind of preparation method of zeolite supported zinc oxyhydroxide | |
| CN104667935A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| Gu et al. | Calcium oxide modification of activated sludge as a low-cost adsorbent: preparation and application in Cd (II) removal | |
| CN102730703B (en) | Method for inexpensive preparation of surface modified nano-silicon dioxide with rice husks | |
| CN102059109A (en) | Preparation method of pumice-loaded zinc oxide hydroxide | |
| CN101798092A (en) | Polyferro-silicate, preparation method thereof and applications thereof in water treatment | |
| CN102114420A (en) | Method for preparing zinc silicate catalyst | |
| CN115155592B (en) | Preparation method and application of iron cobaltate/coal gangue catalyst for efficiently activating persulfate | |
| CN109621993A (en) | Utilize silver orthophosphate/multi-walled carbon nanotube/bismuth tungstate composite photocatalyst material processing antibiotic method | |
| CN113893841A (en) | Barium titanate nano material for piezoelectric catalytic degradation of trace organic pollutants in water and preparation and application thereof | |
| CN101613148B (en) | Method for removing nitrate nitrogen, corresponding combination preparation, and preparation method and application thereof | |
| CN101792206B (en) | Copper polysilicate, preparation method thereof and application thereof in water treatment | |
| CN103933960B (en) | The preparation method of poly-zinc silicon salt dopping hydroxyl oxidize zinc catalyst and application thereof | |
| Yang et al. | Synergistic effect of novel Co-modified micro/nano geopolymers in a photo-PDS system | |
| CN110152736B (en) | Expanded perlite-bismuth oxyiodide composite photocatalyst for oily sewage treatment | |
| CN103933980B (en) | The preparation method of Polyferro-silicate doping hydroxyl oxidize iron catalyst and application thereof | |
| CN107583645A (en) | A kind of preparation method of silicon dioxide powder composite material for sewage disposal | |
| CN107583605A (en) | A kind of preparation method and applications of sorbing material | |
| CN104667933A (en) | Method for preparing wet oxidation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091202 |