CN1297981A - Method of eliminating catalyst powder from catalytic cracked oil pulp - Google Patents
Method of eliminating catalyst powder from catalytic cracked oil pulp Download PDFInfo
- Publication number
- CN1297981A CN1297981A CN 99125287 CN99125287A CN1297981A CN 1297981 A CN1297981 A CN 1297981A CN 99125287 CN99125287 CN 99125287 CN 99125287 A CN99125287 A CN 99125287A CN 1297981 A CN1297981 A CN 1297981A
- Authority
- CN
- China
- Prior art keywords
- oil
- solid content
- liquid
- slurry oil
- heavy
- 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.)
- Granted
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Catalytic cracked oil pulp is first mixed with flocculant in 0.05-2.0 wt% homogeneously to flocculate and precipitate at 80-100 deg.c for 16-48 hr and to separate out upper supernatant and lower flocculated liquid, the lower flocculated liquid is centrifugally separated at 80-100 deg.c for 5-20 hr to obtain clear centrifugal liquid, and the supernatant liquor and the clear centrifugal liquid are clarified oil products. The method can reduce the solid content in oil pulp to below 50 ppm and has a clarified oil product yield over 98 wt%, and is simple and practical.
Description
The invention belongs to a kind ofly with suspended solids isolating method from liquid, more particularly, is a kind of method that removes catalyst fines in the catalytically cracked oil with flocculation agent deposition and centrifugal force.
Usually the catalyst fines that contains 500～1000ppm in the catalytically cracked oil (hereinafter to be referred as FCC), the existence of these powder have limited effective utilization of FCC slurry oil, make most slurry oils can only act as a fuel oil blend component.According to the hydrocarbon composition of slurry oil, slurry oil more valuable use should be as the raw material of producing carbon black, acicular petroleum coke and hydrocracking.Solid content is produced acicular petroleum coke and is required the raw material solid content less than 100ppm less than 500ppm in the production carbon black requirement raw material, and hydrocracking then requires the raw material solid content less than 20ppm, to prevent the hydrogenation catalyst inactivation.
The method that removes catalyst fines in the FCC slurry oil has five kinds substantially: natural sedimentation, flocculation sedimentation, electrostatic separation method, filtering separation method and centrifugal separation.Natural sedimentation only depends on gravity settling, and efficient is low, the cycle is long, is difficult in industrial large-scale application; The electrostatic separation method is difficult to make that solid content is lower than 100ppm in the slurry oil; And the filtering separation rule has very high requirement to equipment.
USP4,407,707 disclose a kind of method that removes solid particulate in the hydrocarbon ils, and this method is to add sulfonic acid or sulfonate earlier in hydrocarbon ils, isolates solid particulate through washing then.In the method, solid particulate is not to settle from oil, settles but transfer in the water again.Although it is effective that water washes out solid particulate, owing to difficulty in process has hindered its application.
The spy open clear 60-245696 disclosed method be with the FCC slurry oil after gravity settling or centrifugation, take out supernatant liquid, a kind of or its mixture that adds ethylene glycol, propylene glycol, glycol ether, glycerol equal solvent, stirring and emulsifying under 1500 rev/mins rotating speed, left standstill under 70～80 ℃ 48 hours, the clarified oil solid content that obtains at last is lower than 20ppm.
USP4,686,048 discloses the method for catalyst fines in a kind of FCC of removing slurry oil, earlier be lower than 100 ℃ hydrocarbon ils and make thinner dilution slurry oil with boiling point, again after filtration, the catalyst fines of oil-contg about 2% is isolated in washing, go out thinner in the slurry oil by fractionation by distillation, the slurry oil that obtains is made carbon black raw material.
USP4,919, the 792 disclosed methods that remove catalyst fines in the FCC slurry oil, be to add sinking agents such as coal, coke, FCC catalyzer, moving bed catalytic cracking (TCC) catalyzer, aluminum oxide or silicon oxide in the high temperature slurry oil of extracting out at the bottom of the FCC separation column, this agent can promote the catalyst fines rapid subsidence, remove.Sedimentation can be carried out in slurry settler or whizzer.
USP5,593,572 disclose the method for spent catalyst powder in a kind of FCC of removing slurry oil, add the aliphatic polymer of the heteroatoms punctuate of capacity in slurry oil, carry out flocculating settling and separate.
WO 97/04042 discloses a kind of method of isolating water-insoluble solid from hydrocarbon ils, and as flocculation agent, the adding effective dose is carried out settlement separate with alkylphenol oxyethyl group thing, and solid content is reduced to below the 500ppm in the slurry oil, and this slurry oil can be used as carbon black raw material.
Except that the spy opens clear 60-245696, solid content is reduced to below the 50ppm in the above-mentioned patent.Although the special method of opening clear 60-245696 can be reduced to solid content in the slurry oil below the 50ppm, its complex technical process is difficult in industrial application.
The objective of the invention is provides the method that a kind of process is simple, remove catalyst fines in the catalytically cracked oil on the basis of existing technology, and this method can be reduced to solid content in the slurry oil below the 50ppm.
Method provided by the invention is: after the flocculation agent that adds effective dose in catalytically cracked oil mixes, 80～100 ℃ of following flocculating settlings 16～48 hours, isolate supernatant liquid, lower floor's flocculation liquid goes out centrifugal clear liquid through centrifugation.
Described flocculation agent is selected from one or more the mixture among amine, fats, silicone oil, sulfonic acid class, the Sulfonates.The effective dose of flocculation agent is meant and can makes the effective settled flocculation agent consumption of catalyst fines in the FCC slurry oil, is generally 0.05～2.0 heavy % of slurry oil, is preferably 0.1～1.0 heavy % of slurry oil.
Described centrifugation temperature is identical with the flocculating settling temperature, and promptly 80～100 ℃, the rotating speed of whizzer is 1500～6000 rev/mins, and the centrifugation time is 5～20 minutes.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction.
Accompanying drawing illustrates the flow process that removes the method for catalyst fines in the catalytically cracked oil provided by the invention, and the shape and size of equipment and pipeline are not subjected to the restriction of accompanying drawing, but determines as the case may be.
Each numbering is described as follows in the accompanying drawing:
1,2,6,8,12 be pump, 3 is static mixer, and 4,5 are the flocculating settling jar, and 7 is whizzer, and 9 is tundish, and 10,11,13 is pipeline.
FCC slurry oil and flocculant are respectively in pump 1,2 suction static mixers 3, enter flocculating setting tank 4,5 after mixing and carry out flocculating setting, the sedimentation clear liquid on settling tank upper strata 90% is extracted out through pump 8, goes out device as the part of clarified oil product through pipeline 10; The flocculation liquid of settling tank lower floor 10% is after pump 6 is extracted out, and the centrifugal clear liquid after centrifuge 7 is isolated the dead catalyst slag enters pans 9. If the solid content of this clear liquid is below 50ppm, then the part as the clarified oil product goes out device through pipeline 10; If the solid content of this clear liquid more than 50ppm, then uses with FCC slurry oil mixing circulation through pipeline 11, pump 12, pipeline 13 successively.
The method of catalyst fines can not only be down to solid content in the slurry oil below the 50ppm in the FCC of the removing slurry oil provided by the invention, and the clarified oil yield behind the Removal of catalyst powder reaches more than the 98 heavy %, and the method technological process is simple, in industrial easy enforcement.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
The used FCC slurry oil raw material properties of embodiment and Comparative Examples is as shown in table 1, is 680ppm comprising catalyst fines at interior solid content; Testing used flocculation agent tetraethylene pentamine, fatty dimeracid, mahogany acid and dimethyl silicone oil is produced by Shanghai Organic Chemical Plant, Mudanjiang Chemical Factory of Daily Use, Jinzhou general petrochemicals factory and Beijing chemical industry two factories respectively; Testing used whizzer is the discontinuous whizzer, is produced by Beijing Medical Centrifugal Machine Factory, and its model is LD4-2.The testing method of FCC slurry oil or clarified oil (comprising sedimentation clear liquid and centrifugal clear liquid) solid content is as follows: accurately take by weighing about oil sample 50 grams and (be accurate to 0.0001 gram), the toluene that adds 5 times is heated to 50 ℃, vacuumizing filtration, with gained filter residue ashing branch, ash content is 775 ± 15 ℃ of following constant weights, weighing is accurate to 0.0001 gram, and ash content and the ratio of the weight of oil sample are the solid content of oil sample.
350 gram FCC slurry oil raw materials are joined in 1000 ml beakers, add tetraethylene pentamine and fatty dimeracid totally 1.05 grams, after mixing, pour in 400 milliliters of graduated cylinders, sedimentation is 24 hours in 100 ℃ baking oven.Take out 90% supernatant liquid 315 grams, its solid content is 29ppm; Lower floor's 10% flocculation liquid, 36.05 grams are poured in 100 milliliters of centrifuge tubes, with 2000 rev/mins speed centrifugations 5 minutes, obtained 30 gram supernatant liquids, its solid content is 45ppm.
Operational condition and test-results are as shown in table 2, and as can be seen from Table 2, the solid content of clarified oil is 30ppm, and yield is 98.3 heavy %.
Comparative Examples 1
Compare with embodiment 1, this Comparative Examples is only passed through flocculating settling, and its clear liquid is no longer through centrifugation.The condition of flocculating settling and embodiment's 1 is identical.
Operational condition and test-results are as shown in table 2, and as can be seen from Table 2, although the clarified oil solid content is 45ppm, its yield only is 90 heavy %.
350 gram FCC slurry oil raw materials are joined in 1000 ml beakers, add mahogany acid 3.5 grams, after mixing, pour in 400 milliliters of graduated cylinders, sedimentation is 30 hours in 100 ℃ baking oven.Press scale and take out 90% supernatant liquid 315 grams, its solid content is 48ppm; Lower floor's 10% flocculation liquid, 38.5 grams are poured in 100 milliliters of centrifuge tubes, with 2000 rev/mins speed centrifugations 10 minutes, obtained 32 gram supernatant liquids, its solid content is 45ppm.
Operational condition and test-results are as shown in table 3, and as can be seen from Table 3, the solid content of clarified oil is 48ppm, and yield is 98.2 heavy %.
Comparative Examples 2
Compare with embodiment 2, this Comparative Examples is only passed through centrifugation, does not carry out flocculating settling before centrifugation.The condition of centrifugation and embodiment's 2 is identical.
Operational condition and test-results are as shown in table 3, as can be seen from Table 3, although the clarified oil solid content below 50ppm, its yield only is 90 heavy %, if and to handle 100,000 tons of FCC slurry oils in industrial every year, would then need many powerful continuous centrifugal machines.
350 gram FCC slurry oil raw materials are joined in 1000 ml beakers, add mahogany acid, tetraethylene pentamine and fatty dimeracid totally 5.25 grams, after mixing, pour in 400 milliliters of graduated cylinders, sedimentation is 24 hours in 100 ℃ baking oven.By supernatant liquid 315 grams that take out 90%, its solid content＜1ppm; Lower floor's 10% flocculation liquid, 40.25 grams are poured in 100 milliliters of centrifuge tubes, with 2000 rev/mins speed centrifugations 5 minutes, obtained 35 gram supernatant liquids, its solid content is 40ppm.
Operational condition and test-results are as shown in table 4, and as can be seen from Table 4, the solid content of clarified oil is 5ppm, and yield is 98.5 heavy %.
Embodiment 4
350 gram FCC slurry oil raw materials are joined in 1000 ml beakers, add dimethyl and tetraethylene pentamine totally 5.25 grams, after mixing, pour in 400 milliliters of graduated cylinders, sedimentation is 20 hours in 100 ℃ baking oven.By supernatant liquid 315 grams that take out 90%, its solid content is 40ppm; Lower floor's 10% flocculation liquid, 40.25 grams are poured in 100 milliliters of centrifuge tubes, with 3000 rev/mins speed centrifugations 5 minutes, obtained 35.5 gram supernatant liquids, its solid content is 45ppm.
Operational condition and test-results are as shown in table 4, and as can be seen from Table 4, the solid content of clarified oil is 42ppm, and yield is 98.7 heavy %.
Table 1
| Viscosity (100 ℃), millimeter 2/ second | ????7～8 |
| Condensation point, ℃ | ????＞26 |
| Carbon residue, heavy % | ????1.7～2.0 |
| Ash content, heavy % | ????0.09 |
| Solid content, ppm | ????680 |
Table 2
| | Embodiment | 1 | Comparative Examples 1 |
| Flocculation agent | Tetraethylene pentamine+fatty dimeracid | Tetraethylene pentamine+fatty dimeracid | |
| Classification | Amine+lipid acid | Amine+lipid acid | |
| Consumption, heavy % | ????0.3 | ????0.3 | |
| Operational condition | |||
| Flocculating settling | |||
| Temperature, ℃ | ????100 | ????100 | |
| Time, hour | ????24 | ????24 | |
| Centrifugation | |||
| Temperature, ℃ | ????100 | ||
| Rotating speed, rev/min | ????2000 | ||
| Time, minute | ????5 | ||
| Sedimentation clear liquid solid content, ppm | ????29 | ????45 | |
| The centrifugal clear liquid solid content, ppm | ????45 | ||
| Clarified oil | |||
| Total recovery, heavy % | ????98.3 | ????90 | |
| Solid content, ppm | ????30 | ????45 |
Table 3
| | Embodiment | 2 | Comparative Examples 2 |
| Flocculation agent | Mahogany acid | ||
| Classification | Sulfonic acid | ||
| Consumption, heavy % | ????1.0 | ||
| Operational condition | |||
| Flocculating settling | |||
| Temperature, ℃ | ????100 | ||
| Time, hour | ????30 | ||
| Centrifugation | |||
| Temperature, ℃ | ????100 | ????100 | |
| Rotating speed, rev/min | ????2000 | ????2000 | |
| Time, minute | ????10 | ????10 | |
| Sedimentation clear liquid solid content, ppm | ????48 | ||
| The centrifugal clear liquid solid content, ppm | ????45 | ????48 | |
| Clarified oil | |||
| Total recovery, heavy % | ????98.2 | ????90 | |
| Solid content, ppm | ????48 | ????47 |
Table 4
| | Embodiment | 3 | Embodiment 4 |
| Flocculation agent | Tetraethylene pentamine+fatty dimeracid+mahogany acid | Tetraethylene pentamine+dimethyl silicone oil | |
| Classification | Amine+lipid acid+sulfonic acid | Amine+silicone oil | |
| Consumption, heavy % | ????1.5 | ????1.5 | |
| Operational condition | |||
| Flocculating settling | |||
| Temperature, ℃ | ????100 | ????100 | |
| Time, hour | ????24 | ????20 | |
| Centrifugation | |||
| Temperature, ℃ | ????100 | ????100 | |
| Rotating speed, rev/min | ????2000 | ????3000 | |
| Time, minute | ????5 | ????5 | |
| Sedimentation clear liquid solid content, ppm | ????＜1 | ????40 | |
| The centrifugal clear liquid solid content, ppm | ????40 | ????45 | |
| Clarified oil | |||
| Total recovery, heavy % | ????98.5 | ????98.7 | |
| Solid content, ppm | ????5 | ????42 |
Claims (6)
1, a kind of method that removes catalyst fines in the catalytically cracked oil, after the flocculation agent that it is characterized in that in slurry oil adding effective dose mixes, 80～100 ℃ of following flocculating settlings 16～48 hours, isolate supernatant liquid, lower floor's flocculation liquid goes out centrifugal clear liquid through centrifugation.
2,, it is characterized in that described flocculation agent is selected from one or more the mixture among amine, fats, silicone oil, sulfonic acid class, the Sulfonates according to the method for claim 1.
3, according to the method for claim 1, the effective dose that it is characterized in that described flocculation agent is 0.05～2.0 heavy % that accounts for slurry oil.
4, according to the method for claim 1 or 3, the effective dose that it is characterized in that described flocculation agent is 0.1～1.0 heavy % that accounts for slurry oil.
5,, it is characterized in that described centrifugation temperature is identical with the flocculating settling temperature, promptly 80～100 ℃ according to the method for claim 1.
6, according to the method for claim 1, it is characterized in that the described centrifugation time is 5～20 minutes, the rotating speed of whizzer is 1500～6000 rev/mins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB99125287XA CN1136294C (en) | 1999-12-01 | 1999-12-01 | Method of eliminating catalyst powder from catalytic cracked oil pulp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB99125287XA CN1136294C (en) | 1999-12-01 | 1999-12-01 | Method of eliminating catalyst powder from catalytic cracked oil pulp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1297981A true CN1297981A (en) | 2001-06-06 |
| CN1136294C CN1136294C (en) | 2004-01-28 |
Family
ID=5283841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB99125287XA Expired - Lifetime CN1136294C (en) | 1999-12-01 | 1999-12-01 | Method of eliminating catalyst powder from catalytic cracked oil pulp |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1136294C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262150A (en) * | 2011-04-28 | 2011-11-30 | 山东东明石化集团有限公司 | Method for detecting solid content of oil slurry |
| CN102585895A (en) * | 2012-03-14 | 2012-07-18 | 李志英 | Separation method for solid particles in catalytic slurry oil |
| CN102649913A (en) * | 2012-04-19 | 2012-08-29 | 中国石油大学(华东) | Method for removing catalyst from catalytic cracking oil slurry |
| CN101619233B (en) * | 2009-07-28 | 2012-12-19 | 江汉大学 | Method for filtering and removing catalyst powder in catalytic cracking oil slurry through ultrasonic irradiation |
| CN103484148A (en) * | 2013-09-29 | 2014-01-01 | 中国石油大学(华东) | Purifying equipment and purifying method for purifying catalytic cracking slurry oil |
| CN104130222A (en) * | 2014-07-28 | 2014-11-05 | 宏业生化股份有限公司 | Furfuryl alcohol reaction solution catalyst separation technology |
| EP2867341A1 (en) * | 2012-06-27 | 2015-05-06 | Alfa Laval Corporate AB | A method and system for separating catalyst fines from an oil stream |
| CN110093176A (en) * | 2018-01-30 | 2019-08-06 | 深圳市科拉达精细化工有限公司 | A kind of method of purified treatment coal tar |
| CN111001193A (en) * | 2020-01-02 | 2020-04-14 | 深圳市科拉达精细化工有限公司 | Method and system for accelerating aggregation of catalyst particles in oil slurry |
| CN111001194A (en) * | 2020-01-02 | 2020-04-14 | 深圳市科拉达精细化工有限公司 | High-temperature continuous ashing-free treatment method and system for catalytic cracking slurry oil |
-
1999
- 1999-12-01 CN CNB99125287XA patent/CN1136294C/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619233B (en) * | 2009-07-28 | 2012-12-19 | 江汉大学 | Method for filtering and removing catalyst powder in catalytic cracking oil slurry through ultrasonic irradiation |
| CN102262150B (en) * | 2011-04-28 | 2015-04-22 | 山东东明石化集团有限公司 | Method for detecting solid content of oil slurry |
| CN102262150A (en) * | 2011-04-28 | 2011-11-30 | 山东东明石化集团有限公司 | Method for detecting solid content of oil slurry |
| CN102585895A (en) * | 2012-03-14 | 2012-07-18 | 李志英 | Separation method for solid particles in catalytic slurry oil |
| CN102585895B (en) * | 2012-03-14 | 2014-06-18 | 李志英 | Separation method for solid particles in catalytic slurry oil |
| CN102649913A (en) * | 2012-04-19 | 2012-08-29 | 中国石油大学(华东) | Method for removing catalyst from catalytic cracking oil slurry |
| CN102649913B (en) * | 2012-04-19 | 2014-06-04 | 中国石油大学(华东) | Method for removing catalyst from catalytic cracking oil slurry |
| EP2867341A1 (en) * | 2012-06-27 | 2015-05-06 | Alfa Laval Corporate AB | A method and system for separating catalyst fines from an oil stream |
| CN103484148A (en) * | 2013-09-29 | 2014-01-01 | 中国石油大学(华东) | Purifying equipment and purifying method for purifying catalytic cracking slurry oil |
| CN103484148B (en) * | 2013-09-29 | 2015-05-27 | 中国石油大学(华东) | Purifying equipment and purifying method for purifying catalytic cracking slurry oil |
| CN104130222A (en) * | 2014-07-28 | 2014-11-05 | 宏业生化股份有限公司 | Furfuryl alcohol reaction solution catalyst separation technology |
| CN104130222B (en) * | 2014-07-28 | 2016-06-15 | 宏业生化股份有限公司 | Furfuryl alcohol reactant liquor catalyst separation technique |
| CN110093176A (en) * | 2018-01-30 | 2019-08-06 | 深圳市科拉达精细化工有限公司 | A kind of method of purified treatment coal tar |
| CN111001193A (en) * | 2020-01-02 | 2020-04-14 | 深圳市科拉达精细化工有限公司 | Method and system for accelerating aggregation of catalyst particles in oil slurry |
| CN111001194A (en) * | 2020-01-02 | 2020-04-14 | 深圳市科拉达精细化工有限公司 | High-temperature continuous ashing-free treatment method and system for catalytic cracking slurry oil |
| CN111001194B (en) * | 2020-01-02 | 2023-09-26 | 深圳市科拉达精细化工有限公司 | High-temperature continuous ashing-free treatment method and system for catalytic cracking slurry oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1136294C (en) | 2004-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100395313C (en) | Method for removing powder of catalyst from catalytic cracking oil slurry | |
| CN1136294C (en) | Method of eliminating catalyst powder from catalytic cracked oil pulp | |
| CN106753742B (en) | Regeneration method of waste lubricating oil | |
| CN108587678B (en) | Catalytic cracking slurry oil settling agent and method for removing catalyst particles in slurry oil | |
| CN102604732A (en) | Static mixed rotational flow separation and extraction process of regenerative base oil N-methyl pyrrolidone | |
| CN101670199A (en) | Capturing settling agent and method for removing catalyst solid powder in oil slurry | |
| CN102666799A (en) | Process for de-acidifying hydrocarbons | |
| MX2014011361A (en) | Process for removing nitrogen from fuel streams with caprolactamium ionic liquids. | |
| CN103987816A (en) | Extraction of polycyclic aromatic compounds from petroleum feedstocks by using ionic liquids | |
| EP0032420A2 (en) | Reclamation of coking wastes | |
| CN101993704A (en) | Method for removing quinoline insoluble substances in coal tar pitch | |
| CN104046382A (en) | Method for removing catalyst from catalytic cracking oil slurry | |
| CN112079540A (en) | Method for treating oil sludge | |
| CN111991905A (en) | Method and device for solid-liquid separation of slurry discharged from slurry bed | |
| CN101633849B (en) | Method for removing catalyst powder from catalytic cracking slurry oil | |
| CN108977222B (en) | Separation system and separation method for direct coal liquefaction oil residue | |
| CN102533318B (en) | Method for removing catalyst powder from catalytic cracking slurry | |
| EP1108775B1 (en) | Method for seperating solids from hydrocarbon sluries | |
| US5076915A (en) | Apparatus for removing suspended solids from a liquid | |
| CN203333614U (en) | Regenerating device for waste emulsified liquid generated in steel rolling process | |
| CN111054103A (en) | Settler for accelerating sedimentation of oil slurry catalyst particles | |
| CN107903940A (en) | A kind of catalytic cracked oil pulp removal method of catalyst and system | |
| CN111621326A (en) | Device and method for purifying waste mineral oil | |
| US4357244A (en) | Method for removing suspended solids from a liquid | |
| CN86105200A (en) | From fuel, particularly divide the method for dried up and solids in the shale oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040128 |