CN104843734A - Method for separating superfine titanium silicalite molecular sieves in molecular sieve alkaline suspension - Google Patents
Method for separating superfine titanium silicalite molecular sieves in molecular sieve alkaline suspension Download PDFInfo
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- CN104843734A CN104843734A CN201510216500.3A CN201510216500A CN104843734A CN 104843734 A CN104843734 A CN 104843734A CN 201510216500 A CN201510216500 A CN 201510216500A CN 104843734 A CN104843734 A CN 104843734A
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Abstract
The invention relates to a method for separating superfine titanium silicalite molecular sieves in molecular sieve alkaline suspension. The method comprises the steps of (1) adding a dilute acid solution into crystallized molecular sieve alkaline suspension to adjust the molecular sieve alkaline suspension pH to be weakly acidic; (2) adding acid silica sol and flocculant solution successively; (3) adding a dilute alkaline solution to adjust the pH to be weakly alkaline; (4) adding a dilute acid solution to adjust the Ph to be neutral reversely, subjecting the mixture to still settlement and filtering to separate and recover superfine titanium silicalite molecular sieves. The separation method technological process is simple, the separation speed is fast, waste emission is little, and the separated nanometer titanium silicalite molecular sieve activity is easy to maintain.
Description
Technical field
The present invention relates to the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid, belong to chemical catalyst area.
Background technology
TS-1 type HTS is a kind of MFI structure transition metal hetero-atom molecular sieve containing framework titania atom, and what have a MFI structure high-silica zeolite uniqueness due to it selects shape effect, excellent stability and hydrophobic nature, and its titanium avtive spot of holding concurrently again is to H
2o
2there is unique adsorption activation performance, thus in multiple organic compound reaction, there is very high catalytic oxidation activity, selectivity of product is high, reaction conditions is gentle, and whole catalytic oxidation process non-pollution discharge, there is good prospects for commercial application, as its catalysis of phenol hydroxylation neighbour (to) industrial applications all such as dihydroxy-benzene and preparing cyclohexanone oxime by ammoximation of cyclohexanone.
The main drawback of TS-1 molecular sieve is that most avtive spot is all arranged in micropore (aperture only have an appointment 0.55 nanometer) structure, large organic molecule is comparatively difficult to spread wherein and catalyzed oxidation, the catalytic oxidation performance making it excellent is subject to a definite limitation, thus impel people to research and develop and prepare the less ultra-fine HTS of particle, to shorten the transmission distance of reactant molecule in duct.But the HTS particle of preparation is less, and its total surface can be higher, molecular sieve alkaline suspension liquid Middle molecule after completing crystallization sieve particle colloidal solsization is stronger, thus from complete be separated the molecular sieve alkaline suspension liquid after crystallization more difficult.Cause Separation and Recovery complete crystallization after molecular sieve alkaline suspension liquid in the complex process of ultra-fine HTS, equipment is huge, and energy consumption is high, and yield is low, and repeatability and poor stability, seriously constrain HTS application in the industry.
Summary of the invention
For a separation difficult problem for ultra-fine HTS in the molecular sieve alkaline suspension liquid after having solved crystallization, the invention provides the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid.Overcome the defect that prior art exists, not only technique is simple, with low cost, substantially increase the efficiency of the ultra-fine HTS of Separation and Recovery from the molecular sieve alkaline suspension liquid after completing crystallization, and stability, repeatability maintain the catalytic activity of the ultra-fine HTS of Separation and Recovery while being improved.
The present invention adopts and realizes with the following method:
A method for separating ultra-fine HTS in molecular sieve alkaline suspension liquid, comprises the following steps:
(1) to completing in the molecular sieve alkaline suspension liquid after crystallization, dilute acidic solution Molecular regulator sieve suspension pH value is added to slightly acidic; (2) then acidic silicasol and flocculant solution successively,
(3) then adding dilute alkali property solution adjust ph to weakly alkaline,
(4) add the anti-adjust pH of dilute acidic solution again to neutral, quiescent setting, filtering can the ultra-fine HTS of Separation and Recovery.
Further, a preferred embodiment of the present invention is: the TS-1 molecular sieve of described ultra-fine HTS to be grain-size be 50 ~ 300 nanometers.
Further, a preferred embodiment of the present invention is: in (1) described step, and adjustment Molecular regulator sieve suspension pH value is 3-4.
Further, a preferred embodiment of the present invention is: in (1) described step, dilute acidic solution for for dilute acidic solution be dust technology, dilute sulphuric acid or dilute hydrochloric acid.
Further, a preferred embodiment of the present invention is: add described acidic silicasol in suspension after, calculates, make the concentration of acidic silicasol in suspension be 100-1000ppm with silicon-dioxide quality densitometer.
Further, a preferred embodiment of the present invention is: add described flocculation agent in suspension after, makes the concentration of flocculation agent in suspension be 5-50ppm.
Further, a preferred embodiment of the present invention is: described flocculation agent is water miscible polyacrylamide, polyvinyl pyridine salt or polymine.
Further, a preferred embodiment of the present invention is: in (3) step, adjust ph is to 9-10.
Further, a preferred embodiment of the present invention is: the pH of described dilute alkaline solution is 10 ~ 14, described dilute alkaline solution ammoniacal liquor, saturated sodium carbonate solution or saturated sodium bicarbonate solution.
Further, a preferred embodiment of the present invention is: in (4) step, and anti-adjust pH is to 6-8.
Beneficial effect of the present invention:
Separation method technological process of the present invention is simple, and velocity of separation is fast, and discharging of waste liquid is few, is separated the nano-titanium si molecular sieves activity obtained and easily keeps.
Embodiment
Below in conjunction with specific embodiment, be clearly and completely described technical scheme of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The testing method of various parameter in embodiment:
Preparing molecular sieve suspension in this reference examples is process by the preparation TS-1 molecular sieve suspension described in " Zeolites, 1992, Vol.12:943 ~ 950 ".
Reference examples 1
1600 grams of alkaline molecular sieve suspension containing ultra-fine HTS, the method wherein preparing molecular sieve suspension is as follows: mixed with 178.5 grams of TPAOH by 382.5 grams of tetraethyl orthosilicates, and add 1046.6 grams of distilled water, mixing is even is afterwards hydrolyzed 1.0 hours at normal pressure and 60 DEG C, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 18.7 grams of tetrabutyl titanates and 85 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid.This is put into stainless steel sealed reactor by this, and at the temperature of 170 DEG C, thermostatic crystallization 3 days, obtains the suspension containing nano molecular sieve, and molecular sieve mean particle size is 50 nanometers, and its pH value is 13.5, and wherein molecular sieve content is 114.5 grams.Spraying dry in high temperature gas flow, by the ultra-fine HTS of cyclonic separator Separation and Recovery, after oven dry, calcining, reclaim ultra-fine HTS quality is 89 grams, molecular sieve yield is 78%.
Reference examples 2
1600 grams of alkaline molecular sieve prepare suspensions containing ultra-fine HTS, wherein prepare the method for molecular sieve suspension for change TPAOH quality into 119 grams, preparation method is identical with reference examples 1, gained molecular sieve mean particle size is 150 nanometers, its pH value is 12, and wherein molecular sieve content is 114.5 grams.Slowly add 180 grams of dust technology (10wt%) under stirring, stir 30min, regulate suspension pH value to 4.In suspension, add 20 grams of weak ammonias (2.5wt%) again, stir 30min, regulate suspension pH value to 7, have no obvious flocculating effect, after filtration, oven dry, calcining, reclaim ultra-fine HTS quality is 28 grams, molecular sieve yield is 24%.
Reference examples 3
1600 grams of alkaline molecular sieve reaction suspensions containing ultra-fine HTS, wherein prepare the method for molecular sieve suspension for change TPAOH quality into 83.3 grams, preparation method is identical with reference examples 1, gained molecular sieve mean particle size is 300 nanometers, its pH value is 10.5, and wherein molecular sieve content is 114.5 grams.Slowly add 70 grams of dust technology (10wt%) under stirring, stir 30min, regulate suspension pH value to 7.In suspension, adding 10 gram mass marks is again the polyacrylamide solution of 1 ‰, has no obvious flocculating effect, and after filtration, oven dry, calcining, reclaim ultra-fine HTS quality is 48 grams, molecular sieve yield is 42%.
Embodiment 1
Prepare molecular sieve suspension by the method for reference examples 1 gained, molecular sieve mean particle size is 50 nanometers, and wherein molecular sieve content is 114.5 grams.Slowly add 180 grams of dust technology (10wt%) under stirring, stir 30min, regulate suspension pH value to 4.3 grams of acidic silicasols (dioxide-containing silica 30wt%) are added again in suspension, the mass concentration of acidic silicasol in suspension is made to be 475ppm, in suspension, add 10 gram mass marks is again the polyacrylamide solution of 1 ‰, the mass concentration of polyacrylamide in suspension is made to be 5.3ppm, stir 30min, 20 grams of weak ammonias (2.5wt%) are added again in suspension, stir 30min, regulate suspension pH value to 10, add 10 grams of dust technology (10wt%) again, regulate suspension pH value to 7, there is obvious flocculating effect, filter and get final product the ultra-fine HTS of Separation and Recovery, dry, after calcining, reclaim ultra-fine HTS quality is 109 grams, molecular sieve yield is 95%.
Embodiment 2
Prepare molecular sieve suspension by the method for reference examples 1 gained, molecular sieve mean particle size is 50 nanometers, and wherein molecular sieve content is 114.5 grams.Slowly add 150 grams of dust technology (10wt%) under stirring, stir 30min, regulate suspension pH value to 4.6 grams of acidic silicasols (dioxide-containing silica 30wt%) are added again in suspension, the mass concentration of acidic silicasol in suspension is made to be 964ppm, in suspension, add 10 gram mass marks is again the polyacrylamide solution of 1 ‰, the mass concentration of polyacrylamide in suspension is made to be 5.3ppm, stir 30min, 20 grams of weak ammonias (2.5wt%) are added again in suspension, stir 30min, regulate suspension pH value to 10, add 10 grams of dust technology (10wt%) again, regulate suspension pH value to 7, there is obvious flocculating effect, filter and get final product the ultra-fine HTS of Separation and Recovery, reclaim ultra-fine HTS quality is 111 grams, molecular sieve yield is 97%.
Embodiment 3
Prepare molecular sieve suspension by the method for reference examples 1 gained, molecular sieve mean particle size is 50 nanometers, and wherein molecular sieve content is 114.5 grams.Slowly add 120 grams of dilute hydrochloric acid (10wt%) under stirring, stir 30min, regulate suspension pH value to 4.1 gram of acidic silicasol (dioxide-containing silica 30wt%) is added again in suspension, the mass concentration of acidic silicasol in suspension is made to be 164ppm, the polyvinyl pyridine salts solution that 20 gram mass marks are 1 ‰ is added again in suspension, the mass concentration of polyvinyl pyridine salt in suspension is made to be 10.8ppm, stir 30min, 20 grams of dilute sodium carbonate solution (2.5wt%) are added again in suspension, stir 30min, regulate suspension pH value to 10, add 10 grams of dust technology (10wt%) again, regulate suspension pH value to 7, there is obvious flocculating effect, filter and get final product the ultra-fine HTS of Separation and Recovery, dry, after calcining, reclaim ultra-fine HTS quality is 106 grams, molecular sieve yield is 93%.
Embodiment 4
Prepare molecular sieve suspension by the method for reference examples 2 gained, molecular sieve mean particle size is 150 nanometers, and wherein molecular sieve content is 114.5 grams.Slowly add 100 grams of dilute sulphuric acids (15wt%) under stirring, stir 30min, regulate suspension pH value to 4.3 grams of acidic silicasols (dioxide-containing silica 30wt%) are added again in suspension, the mass concentration of acidic silicasol in suspension is made to be 513ppm, in suspension, add 30 gram mass marks is again the polyethylenimine solution of 1 ‰, the mass concentration of polymine in suspension is made to be 16.8ppm, stir 30min, 20 grams of dilute sodium carbonate solution (1.5wt%) are added again in suspension, stir 30min, regulate suspension pH value to 10, add 10 grams of dust technology (10wt%) again, regulate suspension pH value to 7, there is obvious flocculating effect, filter and get final product the ultra-fine HTS of Separation and Recovery, reclaim ultra-fine HTS quality is 107 grams, molecular sieve yield is 93%.
Embodiment 5
Prepare molecular sieve suspension by the method for reference examples 3 gained, molecular sieve mean particle size is 300 nanometers, and wherein molecular sieve content is 114.5 grams.Slowly add 200 grams of dust technology (10wt%) under stirring, stir 30min, regulate suspension pH value to 3.In suspension, add 3 grams of acidic silicasols (dioxide-containing silica 30wt%) again makes the mass concentration of acidic silicasol in suspension be 494ppm, in suspension, add 46.8 gram mass marks is again the polyacrylamide solution of 2 ‰, stir 30min, 25 grams of weak ammonias (2.5wt%) are added again in suspension, the mass concentration of polyacrylamide in suspension is made to be 50ppm, stir 30min, regulate suspension pH value to 9, add 5 grams of dust technology (10wt%) again, regulate suspension pH value to 7, there is obvious flocculating effect, filter and get final product the ultra-fine HTS of Separation and Recovery, dry, after calcining, reclaim ultra-fine HTS quality is 111 grams, molecular sieve yield is 97%.
Embodiment 6
The present embodiment illustrates the effect of the ultra-fine HTS of method gained for the catalyzed reaction of acetone amine oximate of the inventive method and reference examples.
By the ultra-fine HTS of above-described embodiment and comparative example institute Separation and Recovery according to HTS: acetone: hydrogen peroxide: ammoniacal liquor: water: the weight ratio of the trimethyl carbinol=1:26:16:25:259:99 one with the there-necked flask of prolong in mix, be warming up to 80 DEG C, then under whipped state, react 3 hours at this temperature, reaction result the results are shown in Table 1.
The acetone conversion of table 1 different treatment method gained molecular sieve and acetoxime yield result
| Title | Acetone conversion (%) | Acetoxime yield (%) |
| Embodiment 1 | 99.8 | 99.6 |
| Embodiment 2 | 99.5 | 97.3 |
| Embodiment 3 | 99.7 | 99.1 |
| Embodiment 4 | 99.2 | 96.6 |
| Embodiment 5 | 99.0 | 95.2 |
| Reference examples 1 | 90.0 | 85.0 |
| Reference examples 2 | 93.0 | 90.0 |
| Reference examples 3 | 95.0 | 89.0 |
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the method for separating ultra-fine HTS in molecular sieve alkaline suspension liquid, is characterized in that, comprise the following steps:
(1) to completing in the molecular sieve alkaline suspension liquid after crystallization, dilute acidic solution Molecular regulator sieve suspension pH value is added to slightly acidic; (2) then acidic silicasol and flocculant solution successively,
(3) then adding dilute alkali property solution adjust ph to weakly alkaline,
(4) add the anti-adjust pH of dilute acidic solution again to neutral, quiescent setting, filtering can the ultra-fine HTS of Separation and Recovery.
2. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1, is characterized in that: the TS-1 molecular sieve of described ultra-fine HTS to be grain-size be 50 ~ 300 nanometers.
3. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1 and 2, is characterized in that: in (1) described step, and adjustment Molecular regulator sieve suspension pH value is 3-4.
4. a kind of method from completing separating ultra-fine HTS the molecular sieve alkaline suspension liquid after crystallization according to claim 3, it is characterized in that: in (1) described step, dilute acidic solution is dust technology, dilute sulphuric acid or dilute hydrochloric acid.
5. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1 and 2, it is characterized in that: add described acidic silicasol in suspension after, calculate with silicon-dioxide quality densitometer, make the concentration of acidic silicasol in suspension be 100-1000ppm.
6. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1 and 2, is characterized in that: add described flocculation agent in suspension after, makes the concentration of flocculation agent in suspension be 5-50ppm.
7. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 6, is characterized in that: described flocculation agent is water miscible polyacrylamide, polyvinyl pyridine salt or polymine.
8. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1 and 2, is characterized in that: in (3) step, adjust ph is to 9-10.
9. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1 and 2, it is characterized in that: the pH of described dilute alkaline solution is 10 ~ 14, described dilute alkaline solution ammoniacal liquor, saturated sodium carbonate solution or saturated sodium bicarbonate solution.
10. the method for separating ultra-fine HTS in a kind of molecular sieve alkaline suspension liquid according to claim 1 and 2, it is characterized in that: in (4) step, anti-adjust pH is to 6-8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110496424A (en) * | 2019-08-08 | 2019-11-26 | 中国汽车技术研究中心有限公司 | It is a kind of alkalinity synthetic solvent in superfine molecular sieves product solid-liquid fast separating process |
| CN111547737A (en) * | 2020-05-22 | 2020-08-18 | 萍乡市石化填料有限责任公司 | Method for separating ultrafine titanium silicalite molecular sieve from molecular sieve alkaline suspension |
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| US6194591B1 (en) * | 2000-04-27 | 2001-02-27 | Arco Chemical Technology, L.P. | Aqueous epoxidation process using modified titanium zeolite |
| CN101786638A (en) * | 2009-12-25 | 2010-07-28 | 湘潭大学 | Titanium silicate molecular sieve modification method |
| US20140356279A1 (en) * | 2011-10-31 | 2014-12-04 | Dalian University Of Technology | Method for modifying titanium silicon molecular sieves |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6194591B1 (en) * | 2000-04-27 | 2001-02-27 | Arco Chemical Technology, L.P. | Aqueous epoxidation process using modified titanium zeolite |
| CN101786638A (en) * | 2009-12-25 | 2010-07-28 | 湘潭大学 | Titanium silicate molecular sieve modification method |
| US20140356279A1 (en) * | 2011-10-31 | 2014-12-04 | Dalian University Of Technology | Method for modifying titanium silicon molecular sieves |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110496424A (en) * | 2019-08-08 | 2019-11-26 | 中国汽车技术研究中心有限公司 | It is a kind of alkalinity synthetic solvent in superfine molecular sieves product solid-liquid fast separating process |
| CN111547737A (en) * | 2020-05-22 | 2020-08-18 | 萍乡市石化填料有限责任公司 | Method for separating ultrafine titanium silicalite molecular sieve from molecular sieve alkaline suspension |
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