CN1162324C - Prepn of Cr-P-Al molecular sieve with AFI structure - Google Patents
Prepn of Cr-P-Al molecular sieve with AFI structure Download PDFInfo
- Publication number
- CN1162324C CN1162324C CNB011184396A CN01118439A CN1162324C CN 1162324 C CN1162324 C CN 1162324C CN B011184396 A CNB011184396 A CN B011184396A CN 01118439 A CN01118439 A CN 01118439A CN 1162324 C CN1162324 C CN 1162324C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- aluminium
- accordance
- phosphorus
- boehmite
- 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.)
- Expired - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a preparation method of chrome-phosphorus-aluminum molecular sieve with an AFI structure. Reaction mixtures comprising ethyl chromate or tertiary butyl chromate, an aluminum source, a phosphorus source and an organic template agent are crystallized, filtered, washed, dried and calcined according to a synthetic method of a conventional molecular sieve. Compared with the molecular sieve produced by the prior art, the molecular sieve prepared by the method has the characteristics of less dosage and equivalent performance in a decomposition reaction of naphthenic or cycloalkenyl peroxide.
Description
Technical field
The invention relates to a kind of preparation method of Cr-P-Al molecular sieve, further say so about a kind of preparation method of Cr-P-Al molecular sieve of the AFI of having crystalline structure.
Background technology
USP4310440 at first discloses phosphate aluminium molecular sieve (AlPO
4) structure and preparation, the sial tetrahedron does not appear in this novel molecular sieve first in the framework of molecular sieve structure, but by AlO
2And PO
2Tetrahedron is formed, and framework of molecular sieve is electric neutrality, does not have exchangeable cation.Aluminium phosphate molecular sieve adopts hydrothermal crystallization method synthetic, is earlier equimolar active hydrated aluminum oxide and phosphoric acid to be mixed the generation phosphaljel in water, and then adds organic formwork agent, and the back crystallization under 125～200 ℃ of autogenous pressures that stirs obtains.AlPO wherein
4-5 phosphate aluminium molecular sieves have the AFI structure.
Subsequently, EP83109860 and USP4440871 disclose with silicon and have substituted part aluminium and phosphorus, synthetic aluminium silicophosphate molecular sieve (SAPO).EP0121232A2 discloses with titanium and has replaced part phosphorus and aluminium synthetic titanium phosphate aluminium molecular sieve (TAPO).CN85103240A discloses the titanium-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions that forms with part phosphorus in titanium and the silicon replacement aluminium phosphate molecular sieve skeleton and aluminium.
Silica removal and/or titanium are as outside the backbone element, and other heteroatoms also can replace phosphorus and the aluminium backbone element as the molecular sieve tetrahedral oxide.Magnesium-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions is disclosed as CN8510228A; CN85103238A discloses cobalt-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103257A discloses zinc-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103260A discloses manganese-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103247A discloses iron-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85104262A discloses boron-aluminium-phosphorus-titanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions; CN85103199A discloses by oxide compound that is selected from arsenic, beryllium, boron, gallium, germanium, lithium or vanadium and AlO
2 -, PO
2 +The tetrahedral oxide molecular sieve that forms; The disclosed a kind of aluminium phosphate molecular sieve composition of CN85103259A, be by the element that is selected from one of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium be selected from the tetrahedral oxide units skeleton structure that the element of one of cobalt, iron, magnesium, manganese, titanium and zinc and phosphorus and aluminium constitute; The disclosed combination of molecular sieve of CN85101026A is with iron and/or titanium and is selected from that a kind of in magnesium, manganese, cobalt, the zinc replaces part phosphorus, aluminium forms as the backbone element of tetrahedral oxide.
USP4759919 has disclosed chromium-aluminium-phosphorous oxides (CAPO) and the preparation method who forms with part phosphorus in the chromium replacement phosphate aluminium molecular sieve skeleton and aluminium.Wherein said CAPO-5 molecular sieve and AlPO
4-5 molecular sieves have identical AFI crystalline structure, and it is that the mixture of chromium source, aluminium source, phosphorus source and organic formwork agent 2 hours-30 days crystallization of reaction under 100-200 ℃ and autogenous pressure are formed.Prepare oxide compound, oxyhydroxide, muriate, bromide, iodide, nitrate, vitriol, acetate, phosphoric acid salt or basic chromic carbonate that the used chromium source of this molecular sieve is selected from chromium.
As a kind of novel chromium AFI molecular sieve that is substituted element, it is in the reaction process research of corresponding ketone and alcohol that the CAPO-5 molecular sieve is mainly used in cycloalkyl or cycloalkenyl group peroxide breakdown, for example selection decomposition reaction of catalysis cyclohexyl hydroperoxide or cyclohexenyl hydrogen peroxide.
In Applied Catalysis A:General.108 1994 L1-L6, reported with CAPO-5 to be the decomposition reaction of catalyzer, at cyclohexyl hydroperoxide is 2.9 mmoles (0.3364 grams), with 12 milliliters of hexanaphthenes is solvent, the molecular sieve injected volume is counted in the reaction system of 0.029 mmole (the molecular sieve amount is 0.3 gram) with chromium metal, the transformation efficiency of cyclohexyl hydroperoxide is 87%, the selectivity of pimelinketone and hexalin is respectively 86% and 13%, in this piece document, the used chromic salts of preparation molecular sieve, the aluminium source, phosphorus source and template are respectively alkali formula chromium acetate, boehmite, phosphoric acid and Tri-n-Propylamine are 0.05Cr by the proportioning of the reactant glue that they constituted
2O
3: 0.9Al
2O
3: P
2O
5: Pr
3N: 50H
2O.
At Studies in Surface Science and Catalysis.Vol.94, report among the p705 that the transformation efficiency of cyclohexenyl hydrogen peroxide is 73%, the selectivity of 2-tetrahydrobenzene-1-ketone and 2-tetrahydrobenzene-1-alcohol is respectively 71% and 29%.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of method of the CAPO-5 of preparation molecular sieve is provided, make the molecular sieve of this method preparation in the decomposition reaction of cycloalkyl or cycloalkenyl group superoxide, have better catalytic perfomance.
Method provided by the invention is to comprise molecular sieve synthetic method crystallization, filtration, washing, drying and the roasting of the reaction mixture of chromic acid ethyl ester or chromic acid tert-butyl, aluminium source, phosphorus source and organic formwork agent according to routine.
Specifically, preparation method provided by the invention is: chromic acid ethyl ester or chromic acid tert-butyl are mixed with the phosphorus source in the adding aluminium source, back, mix, and aging 1-10 hour, add organic formwork agent and water, obtain mole and consist of (0.005-0.1) Cr
2O
3: (0.8-1.2) Al
2O
3: P
2O
5: (1-3) template: (10-100) H
2The mixed solution of O, with mixed solution in closed reactor 150-180 ℃ after crystallization 1-10 days, with ordinary method filter, washing, dry, roasting.
In the preparation method of AFI structure Cr-P-Al molecular sieve provided by the invention, said chromic acid ethyl ester, its molecular formula is Cr (OCH
2CH
3)
3, can adopt following process synthetic: according to stoichiometry, sodium Metal 99.5 to be contacted the generation sodium ethylate with ethanol, the sodium ethylate that generates is generated the chromic acid ethyl ester with the chromic salts reaction again.
In the preparation method of AFI structure Cr-P-Al molecular sieve provided by the invention, said chromic acid tert-butyl, its molecular formula is Cr (OCCH
3CH
3CH
3)
3, can adopt following process synthetic: according to stoichiometry, sodium Metal 99.5 to be contacted the generation sodium tert-butoxide with the trimethyl carbinol, the sodium tert-butoxide that generates is generated chromic acid tert-butyl with the chromic salts reaction again.
When synthetic chromic acid ethyl ester or chromic acid tert-butyl, wherein said chromic salts is selected from one of chromium chloride, chromium nitrate or chromium acetate.
In the preparation method of AFI structure Cr-P-Al molecular sieve provided by the invention, said aluminium source is selected from one of aluminum isopropoxide, boehmite, pseudo-boehmite, aluminium colloidal sol, aluminum phosphate, gibbsite, sodium aluminate or aluminum chloride, wherein preferred boehmite, pseudo-boehmite or aluminium colloidal sol.Said aluminium source generally can be dissolved in the nitric acid in use to be accelerated into the glue process.
Said phosphorus source is selected from phosphoric acid, triethyl phosphoric acid or metaphosphate, wherein preferred ortho-phosphoric acid.
Said organic formwork agent is selected from one of di-n-propylamine, Tri-n-Propylamine or tetraethyl ammonium hydroxide or their mixture.
In the preparation method of AFI structure Cr-P-Al molecular sieve provided by the invention, the drying conditions of said routine be 100-130 ℃ 1-10 hour, roasting condition be 400-600 ℃ 1-10 hour.
The molecular sieve of the inventive method preparation, when being used for the decomposition reaction of catalysis cycloalkyl or cycloalkenyl group superoxide, when having the same conversion of reaching, injected volume is less than the characteristics of prior art greatly.For example, under the reactant ratio and reaction conditions of AppliedCatalysis A:General.108 1994 L1-L6 report, the Cr-P-Al molecular sieve of the inventive method preparation only need be thrown in 1/3rd of documents institute consumption, reaction times is the former 1/10th, just can reach the catalytic decomposition effect (example 8) suitable with document.
Description of drawings
Fig. 1 is Zeolite 16:323-802, the disclosed Standard X-Ray diffraction spectrogram with AFI crystalline structure molecular sieve of 1996 p353.
Embodiment
Below will the present invention is further illustrated with example, but content of the present invention is not subjected to the restriction of these examples.
In example, the X-ray diffraction analysis is carried out on the D5005D type x-ray diffractometer of German SIEMENS company, and condition is 40KV, 40mA, K alpha-ray Cu target.
Example 1
The preparation process of this example explanation chromic acid ethyl ester.
Restrain sodium Metal 99.5s with 23 and join several times in 200 ethanol that restrain, generate sodium ethylate 69 grams, restrain contact reactss, generate the chromic acid ethyl esters of 58.3 grams with the sodium ethylate of generation and through the chromium chloride 52.8 of 100 ℃ of dryings after 4 hours.
Example 2
The preparation process of this example explanation chromic acid tert-butyl.
Restrain sodium Metal 99.5s with 23 and join several times in 250 ethanol that restrain, generate sodium ethylate 96 grams, restrain contact reactss, generate the chromic acid tert-butyls of 271 grams with the sodium tert-butoxide of generation and through the chromium chloride 52.8 of 100 ℃ of dryings after 4 hours.
Example 3
76 grams, 56% boehmite is dissolved in 350 gram 1N HNO
3In the solution, pour 104 grams, 85% phosphoric acid into, add 8.4 gram chromic acid ethyl esters again, mix and stirred 4 hours, drip 98 gram Tri-n-Propylamine (Pr
3N), vigorous stirring obtains forming: 0.05Cr
2O
3: P
2O
5: 0.93Al
2O
3: 1.5Pr
3N: 50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filters, washing, 120 ℃ of dryings 2 hours, get white solid,, get sieve sample in 550 ℃ of roastings 10 hours, the X-ray diffraction wave spectrum of this sample has the feature of Fig. 1, illustrates that this molecular sieve has the crystalline structure of AFI.
Example 4
43 grams, 66% pseudo-boehmite is dissolved in 174 gram 1N HNO
3In the solution, pour in 69 grams, 85% phosphoric acid, add 2.8 gram chromic acid ethyl esters again, also stirred 4 hours the mixing back, and the 90 gram 24.0%TEAOH aqueous solution are added drop-wise in the said mixture.And then drip 60 gram di-n-propylamine (Pr
2NH), vigorous stirring obtains forming: 0.025Cr
2O
3: P
2O
5: 0.93Al
2O
3: 2.0Pr
2NH: 0.50TEAOH: 50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filter, washing, 110 ℃ of dryings 4 hours, white solid, in 550 ℃ of roastings 10 hours, sieve sample.This sample has X-ray diffraction wave spectrum feature shown in Figure 1.
Example 5
170 gram 25% aluminium colloidal sols (Haiyang Chemical Plant, Qingdao's product) and 4.22 gram chromic acid ethyl esters are poured in 104 grams, 85% phosphoric acid, add water 58 gram, mix and stirred 4 hours, again the 270 gram 24.0%TEAOH aqueous solution are added drop-wise in the said mixture, vigorous stirring obtains forming 0.025Cr
2O
3: P
2O
5: 0.93Al
2O
3: 1.0TEAOH: 50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filter, washing, 120 ℃ of dryings 3 hours, white solid, in 550 ℃ of roastings 10 hours, sieve sample.This sample has X-ray diffraction wave spectrum feature shown in Figure 1.
Example 6
76 grams, 56% boehmite is dissolved in 350 gram 1N HNO
3In the solution, pour 104 grams, 85% phosphoric acid into, add 12.2 gram chromic acid tert-butyls again, mix and stirred 4 hours, drip 98 gram Tri-n-Propylamine (Pr
3N), vigorous stirring obtains consisting of 0.05Cr
2O
3: P
2O
5: 0.93Al
2O
3: 1.5Pr
3N: 50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filters, washing, 120 ℃ of dryings 3 hours, get white solid,, get sieve sample in 550 ℃ of roastings 10 hours, the X-ray diffraction wave spectrum of this sample has the feature of Fig. 1, illustrates that this molecular sieve has the crystalline structure of AFI.
Example 7
The explanation of this example is according to the 0.05Cr that puts down in writing among Applied Catalysis A:General.108 1994 L1-L6
2O
3: P
2O
5: 0.9Al
2O
3: 1.0Pr
3N: 50H
2The O reactant ratio prepares the process of molecular sieve, and wherein alkali formula chromium acetate replaces with the chromic acid ethyl ester.
76 grams, 56% boehmite is dissolved in 350 gram 1N HNO
3In the solution, 8.4 gram chromic acid ethyl esters are poured in 104 grams, 85% phosphoric acid, mix and stir 4 hours, drip 65 gram Tri-n-Propylamine (Pr
3N), vigorous stirring obtains forming: 0.05Cr
2O
3: P
2O
5: 0.9Al
2O
3: 1.0Pr
3N: 50H
2Solution before the crystallization of O, this solution is in 170 ℃ of crystallization 2 days, filter, washing, 100 ℃ of dryings 4 hours, white solid, in 550 ℃ of roastings 10 hours, sieve sample, this sample has X-ray diffraction wave spectrum feature shown in Figure 1.
Example 8
The explanation of this example adopts the molecular sieve of the inventive method preparation to be used for the effect of cycloalkyl peroxide catalyzed decomposition reaction.
Molecular sieve with example 7 preparations is a catalyzer, raw material is 12 milliliters of industrial cyclohexane oxide solutions, consist of hexanaphthene 95.1029 heavy %, cyclohexyl hydroperoxide 3.4243 heavy %, hexalin 0.7975 heavy %, pimelinketone 0.3366 heavy %, acid 0.1547 heavy %, ester 0.1344 heavy %, this forms with the material system ratio of the described 2.9 mmole cyclohexyl hydroperoxides of document and 12 milliliters of cyclohexane solvent formations basic identical, and its difference is to contain in the used raw material of this example alcohol, ketone and acid, the ester impurity of minute quantity.
Be reflected in 100 ml flasks that have been equipped with condensation and magnetic stirring and carry out.The molecular sieve consumption is 0.1 gram.Reaction conditions is: 80 ℃, 0.5 hour.
The transformation efficiency of cyclohexyl hydroperoxide is obtained by iodometric titrationiodimetry titration: 3.0 gram reaction mixtures are 1: 2 chloroform with 35 ml volumes ratio: the acetum dilution, under lucifuge, add 2.5 milliliters of saturated solution of potassium iodide again and kept 30 minutes, add 50 ml deionized water then, with the Sulfothiorine titration of 0.1M.
Distribution of reaction products is by gas chromatographic analysis.Remaining cyclohexyl hydroperoxide concentration is the excessive triphenyl phosphine dichloroethane solution removal of 24 grams per liters in the reaction product.
Through the analysis to reaction product, reaction result is: the transformation efficiency of cyclohexyl hydroperoxide is 85%, and the selectivity of pimelinketone and hexalin is respectively 72% and 34%.From The above results as can be seen, adopt method provided by the invention, adopt the CAPO-5 molecular sieve of the reactant ratio preparation identical with document, in the decomposition reaction of cyclohexyl hydroperoxide, reaction times with 1/10th (30 minutes) and consumption only are under 1/3rd the situation of document consumption, can reach essentially identical reaction conversion ratio (85%), the selectivity sum of pimelinketone and hexalin is 106%, greater than 99% of document, here need to prove, in the cyclohexyl hydroperoxide decomposition course, produced atomic oxygen, atomic oxygen continues to generate more hexalin and pimelinketone, the pimelinketone that causes whole decomposition reaction to be calculated based on cyclohexyl hydroperoxide with hexanaphthene generation oxidizing reaction as solvent, the selectivity of alcohol is greater than 100%.
Claims (8)
1, a kind of preparation method of AFI structure Cr-P-Al molecular sieve, it is characterized in that this method is that chromic acid ethyl ester or chromic acid tert-butyl are mixed with the phosphorus source in the adding aluminium source, back, mixes aging 1-10 hour, add organic formwork agent and water, obtain mole and consist of (0.005-0.1) Cr
2O
3: (0.8-1.2) Al
2O
3: P
2O
5: (1-3) template: (10-100) H
2The mixed solution of O is with mixed solution in closed reactor 150-180 ℃ after crystallization 1-10 days, after filtration, washing, drying and roasting.
2,, it is characterized in that generating with the chromic salts reaction more said chromic acid ethyl ester contacts the generation sodium ethylate according to stoichiometry with sodium Metal 99.5 with ethanol after according to the method for claim 1; Said chromic acid tert-butyl generates with the chromic salts reaction after according to stoichiometry sodium Metal 99.5 being contacted the generation sodium tert-butoxide with the trimethyl carbinol again.
3, in accordance with the method for claim 2, it is characterized in that said chromic salts is selected from one of chromium chloride, chromium nitrate or chromium acetate.
4, in accordance with the method for claim 1, it is characterized in that said aluminium source is selected from one of aluminum isopropoxide, boehmite, pseudo-boehmite, aluminium colloidal sol, aluminum phosphate, gibbsite, sodium aluminate or aluminum chloride.
5, in accordance with the method for claim 4, it is characterized in that said aluminium source is selected from one of boehmite, pseudo-boehmite or aluminium colloidal sol.
6, in accordance with the method for claim 1, it is characterized in that said phosphorus source is selected from one of ortho-phosphoric acid, triethyl phosphoric acid or metaphosphate.
7, in accordance with the method for claim 6, it is characterized in that said phosphorus source is an ortho-phosphoric acid.
8, in accordance with the method for claim 1, it is characterized in that said organic formwork agent is selected from one of di-n-propylamine, Tri-n-Propylamine or tetraethyl ammonium hydroxide or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011184396A CN1162324C (en) | 2001-05-30 | 2001-05-30 | Prepn of Cr-P-Al molecular sieve with AFI structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011184396A CN1162324C (en) | 2001-05-30 | 2001-05-30 | Prepn of Cr-P-Al molecular sieve with AFI structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1388062A CN1388062A (en) | 2003-01-01 |
| CN1162324C true CN1162324C (en) | 2004-08-18 |
Family
ID=4663181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011184396A Expired - Lifetime CN1162324C (en) | 2001-05-30 | 2001-05-30 | Prepn of Cr-P-Al molecular sieve with AFI structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162324C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205975B (en) * | 2011-05-28 | 2015-02-04 | 山西昆明烟草有限责任公司 | Modified aluminium phosphate molecular sieve additive capable of reducing aldehyde and ketone compound contents in cigarette smoke as well as preparation and application thereof |
| CN103318906B (en) * | 2012-03-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | The preparation of the AFI structure aluminophosphate molecular sieve membrane that porous alumina carrier supports |
| KR20230067667A (en) * | 2020-09-14 | 2023-05-16 | 차이나 페트로리움 앤드 케미컬 코포레이션 | SCM-34 molecular sieve, manufacturing method thereof and use thereof |
-
2001
- 2001-05-30 CN CNB011184396A patent/CN1162324C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1388062A (en) | 2003-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9896343B2 (en) | Titanium silicalite molecular sieve and its synthesis | |
| DE60005969T2 (en) | METHOD FOR PRODUCING PHENOL AND ACETONE | |
| JPH0142889B2 (en) | ||
| CN1850606A (en) | Method for preparing AlPO4 or SAPO molecular sieve | |
| CN1226874A (en) | Preparation of Y zeolite | |
| US20220387980A1 (en) | Denitration catalyst and denitration method using the catalyst | |
| CN111495421A (en) | Method for directly preparing M-HZSM-5 molecular sieve | |
| CN1162324C (en) | Prepn of Cr-P-Al molecular sieve with AFI structure | |
| CN111017946B (en) | Preparation method of titanium-containing molecular sieve for olefin epoxidation process | |
| DE102006037314A1 (en) | Use of a catalyst based on zeolites in the reaction of oxygenates to lower olefins and processes for this purpose | |
| CN1830783A (en) | Synthesis method of silicon aluminium phosphate molecular sieve | |
| CN101239325B (en) | Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof | |
| US5192520A (en) | Synthesis of aluminosilicate zeolites of faujasite structure | |
| CN1152003C (en) | Catalytic decomposition process of cyclohexane oxide liquid | |
| CN1121979C (en) | Process for preparing ZSM-5 molecular sieve | |
| CN1100002C (en) | Zirconium-phosphorus-aluminium molecular sieve composition and its preparation method | |
| CN112573537B (en) | Preparation method of MRE molecular sieve | |
| JP7207154B2 (en) | Method for producing zeolite | |
| EP4421039A1 (en) | Scm-38 molecular sieve, preparation method therefor, and use thereof | |
| CN112742472A (en) | Preparation method of epoxidation catalyst with high activity and low byproduct | |
| CN1041616C (en) | Method No.2 for synthesizing beta zeolite | |
| CN1212892C (en) | Method of synthesizing titanium silicon molecular sieve | |
| CN113636571B (en) | SCM-33 molecular sieve and preparation method and application thereof | |
| CN101244393A (en) | Method for manufacturing AFI structure cerium-phosphor-aluminum molecular sieve | |
| CN1160298C (en) | Catalytic decomposition process of cyclohexane oxide liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040818 |
|
| CX01 | Expiry of patent term |