CN1037705C - Microfiltration - Google Patents
Microfiltration Download PDFInfo
- Publication number
- CN1037705C CN1037705C CN 92104547 CN92104547A CN1037705C CN 1037705 C CN1037705 C CN 1037705C CN 92104547 CN92104547 CN 92104547 CN 92104547 A CN92104547 A CN 92104547A CN 1037705 C CN1037705 C CN 1037705C
- Authority
- CN
- China
- Prior art keywords
- solution
- filter
- silicic acid
- strainer
- filtration
- 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 - Fee Related
Links
- 238000001471 micro-filtration Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims description 22
- 235000021110 pickles Nutrition 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 3
- 238000005554 pickling Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- 239000012530 fluid Substances 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009183 running Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001035 Soft ferrite Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicon Compounds (AREA)
Abstract
Proposed is a method for the desilification of aqueous inorganic solutions, in particular pickling solutions, and a method of producing iron oxide with a reduced silicic acid content. The aqueous inorganic solution to be processed is fed to a cross-flow filter and passed through the filter at a temperature of 60-90 DEG C. In order to produce oxide, the filtrate is then converted to the appropriate oxide by spray roasting.
Description
The present invention relates to a kind of in other words, is the ferritic method that a kind of production contains low amount silicic acid to aqueous solution of inorganic matter, particularly to the method for pickle solution removal silicate, and this method is particularly suitable for producing wustite.
In waste pickle liquor recovery technology field, the application of spray-drying process (Spr ü hr sttechnologie) is well known.Method can obtain titanium dioxide two iron (Fe whereby
2O
3), its primary purposes is as the preformed material in the electronic industry (production wustite).The characteristic electron of ferrite ceramics (electromagnetic property) at first depends on the silicate content in the material.The soft ferrite that is used for electronic industry at present limits silicic acid (SiO
2) maximum level in ferrite is 0.01%, and only several years ago this limit also rest on 0.02%.The development in ferrite field is expected to further reduce this ultimate value.Therewith correspondingly, puron oxysome (SiO
2Maximum level be 0.01%) price estimate also to have dropped to 4900 Austrian Schilling per ton ( S), and contain about 0.05%, SiO
2Ferrite, only be 700 to 950 Austrian Schilling per ton ( S) as the sort of ferritic price produced with legacy equipment.
Disclose a kind of equipment and method that contains silicate water that be used to handle among the JP-PS59-90688, wherein, the former current that contain silicate are through two filtration grades.Comprise a microporous membrane or ultra-filtration membrane in first filtration grade, comprise a reverse osmosis membrane in second filtration grade.This method can collect that maximum particle size is 1 micron a particle in the water, thereby the traditionally shaped silicic acid of can not emanating out, because silicic acid is to exist with the granularity less than 0.02 micron.It does not provide such enlightenment yet in addition, promptly this method also can be used to contain a large amount of additional substancess pickle solution go the silicate process.
Thereby in the past few years, people have imagined some and have been applicable to that pickle solution goes the method for silicate and enforcement or test in industrial equipments.These methods, the method described in AT-PS 380675 are by making part be included in iron(ic) chloride (accounting for 1%～2%) in the pickle solution with the form of ironic hydroxide precipitation and make the colloidal silicic acid that is attached together with it coprecipitation thereupon.But the weak point of these class methods is, if need in a large number to consider the mud of eliminating, then requires to adopt higher isolation technique.Need to consume more chemical reagent for example ammonia and flocculation agent for this reason.Thereby adopt the equipment of this method expensive, less economical.Estimate that the required total cost of this kind equipment accounts for 20～30% of spray drying device cost.
Therefore, the object of the present invention is to provide a kind of method of under the condition that does not consume chemical reagent and manpower, from inorganic aqueous solution arbitrarily, separating contained silicic acid in cheap mode.Another object of the present invention provides more than one and states the production ferritic simple method of method for the basis, and silicon content is no more than the desired ultimate value of electronic industry in the ferrite of being produced.The feature of this method is that also it can be used for the process of existing recovery waste pickle liquor, and its process preferably can obtain ferrite.
For realizing first goal of the invention, main points of the present invention are, make liquid that desire handles via a crossing current filter and at 60 ℃ to 90 ℃, preferably flow through under 70 ℃ to 80 ℃.
Silicic acid in the aqueous solution mainly is the influence of controlled temperature by the operational condition of crossing current filter, is converted into the micelle structure.(these polymer architectures exist with hydrated form and remain on suspended state when static electrifications.Its diameter is percentum or a few tenths of micron.Silicic acid can enter the micro-filtration stage because of its micelle structure reaches above-mentioned granularity.
Micro-filtration is defined as the particle of separable 0.02 to 10 micron granularity.The film of this class strainer is made of a variety of materials at present, wherein be useful on the derivatived cellulose in biochemical field, and be suitable for the cross flow filter technology, as be used for the material of the inventive method, these materials mainly are the plastic films of being made by polypropylene, polyethylene or polysulfones.But also can adopt hollow fiber, multicellular glass or porous ceramic film material.
It is well-known that the principle of cross flow filter itself contains liquid suspension or the emulsive material as purification.In the static filtering process, the tectum that filter cake forms on the filter cellular surface constantly increases and flow of filtrate is reduced, and in the cross flow filter process, the tectal increase of filter residue will be subjected to being inhibited with the poising action of the vertical shear force gradient that transversely forms of filtering direction.So just can under high flow of filtrate, filter for a long time.In addition, also can be by periodic counterflush, that is, make filtration procedure moment reverse, wash away in force and discharge thereby will filter tectum on the cellular surface, recover original filtration capacity thus.But this can't look to making silicic acid contained in the aqueous solution to become the structure that it is separated by horizontal filter immediately.But with this understanding, can form above-mentioned micelle structure, so just can silicic acid almost entirely be separated with 0.2 micron polypropylene fenestra with hundreds of angstroms dia.
It is desirable especially that method of the present invention is used for the removal process effect of waste pickle liquor, and its advantage is that this ferrite that is obtained by pickle solution is removed silicic acid significantly, thereby is highly suitable for the purposes of electronic industry.For this purpose, technical scheme of the present invention is, at 60 ℃ to 90 ℃, preferably under 70 ℃ to 80 ℃ temperature, make a kind of inorganic aqueous solution, particularly a kind of waste pickle liquor stream that contains dissolved iron and silicic acid through the cross flow filter device, and is converted into the corresponding oxide compound that contains 0.01% silicic acid at most with penetrating fluid thereupon by spraying drying.
In above-mentioned two kinds of methods, preferably make the concentrated solution crossing current filter of flowing through circularly, so that in the purity that improves penetrating fluid, further improve the separating power of strainer.
In this following explanation, will describe the preferred embodiment for preparing ferritic method by waste pickle liquor in detail by accompanying drawing.
Fig. 1 is the synoptic diagram of waste pickle liquor recovery system, comprises the silicate process in the recovery;
Fig. 2 is the synoptic diagram of silicate equipment, comprising two filtering units that are connected in series.
Pending solution is anti-in spray-drying after flowing through preconcentrator 2 and first runnings container 3 Answer and carry out spray-drying in the device 1, wherein, first runnings container 3 consists of the kerve of preconcentrator. The solid reaction product that produces in this process, namely metal oxide is arranged by eduction gear 11 Go out, and gaseous reaction product preferably is transported in the preconcentrator 2 again by electronics filter mouth. Preconcentrator 12 can be Lurji type or Venturi type, and it is through a conduit and two drops Separator 4 joins, and further is communicated with absorption tower 5,6, gets again in the absorption tower To pickle. Waste gas is the process liquid drop separator 7 rear atmosphere that finally enter from absorption tower 5,6.
But, the liquid through pre-concentration also can cause crossing current by first runnings container 3 through pump 31 In the filter 8. Here, the effect of pump 31 is to make concentrate repeatedly come and go the filter 8 of flowing through.
As shown in Figure 2, can be with two (or a plurality of) filter elements (8a and 8b) head Tail phase ground connection is chained together.
Embodiment:
In pickle solution recovery system shown in Figure 1, the waste pickle liquor with following composition (and the theoretic oxide compound that produces after spraying drying is formed) is handled.
1.ICP-analyzing the theoretic oxide compound that obtains thus forms
Fe：?87 g/l Fe
2O
3 99.16％
Cr：?0.03 Cr
2O
3 352ppm
Ni：?0.02 NiO 204
Al：?0.05 Al
2O
3 760
SiO：0.036 SiO
2 289
Mn：?0.27 MnO 2800
Ca：?0.08 CaO 900
Zn：?0.06 ZnO 598
Mg：0.16 MgO 2315
Pb：0.00 PbO 00
Cu：0.025 CuO 221
Total maximum in theory CL value of HCl:197g/l (accounting for 20%) is
0.15％GEB。
The crossing current filter directly links to each other with the concentrated solution circulation.Transport capacity in the concentrated solution circulation is 2,800l/h, and the transport capacity in filter is 2,000l/h.After having moved 13 and 17 hours, iron ion value and silicon oxide value in the concentrated solution are as shown in the table:
A) represent Fe (2+) unit: g/l
B) represent Fe (3+) unit: g/l
C) represent SiO
2Unit: mg/l
Concentrated solution
a) b) c)
13 hours 108.2 22.3 25
17 hours 111.3 23.3 27.6
Penetrating fluid
a) b) c)
110.2 17.5 42
13 106.6 20.8 22.5(124-148
Hour ppm/ oxide compound)
17 117.3 23.9 22.9(114-137
Hour ppm/ oxide compound)
To handle pickle solution in the experiment below, its concentrated solution value is: Fe (2+) 79.9g/l, Fe (+3) 5.6g/l, SiO
238mg/l (this value is corresponding to the maximum value in theory of 337ppm/ oxide compound).In one hour, and after using four hours cross flow filter processes, its value is:
Concentrated solution
a) b) c)
1 hour 113.0 24.6 27.0
4 hours 117.5 27.2 37.5
Penetrating fluid
a) b) c)
1 hour 117.5 25.8 15.5 (76-92ppm
/ oxide compound)
4 hours 118.3 27.6 22.8 (109-135
The ppm/ oxide compound)
Close the crossing current filter subsequently, its value is after flowing 4 hours:
Concentrated solution
a) b) c)
4 hours 113.8 32.4 56.2 (! )
Penetrating fluid
a) b) c)
4 hours 39 (350ppm/ oxide compound)
At silicon oxide shown in the last table is that total oxide compound of discharging in according to the solution of being dissolved into oxide compound is estimated.Therefore to the analytical results of spraying drying oxide compound also may be in this case:
Fe： Fe
2O
3：99.02％
Mn：3093ppm MnO：0.399％
SiO
2: 100 SiO
2: 0.010% maximum value
V：141 V
2O
5：0.025
Ti：95 TiO
2：0.016
Cr：338 Cr
2O
3：0.050
Cu：174 CuO：0.021
Ni：166 NiO：0.021
Co：23 CoO：0.029
Pb：26 PbO：0.003
Zn：246 ZnO：0.031
Al：749 Al
2O
3：0.139
Ca：766 CaO：0.018
Mg：692 MgO：0.128
P：30 P
2O
5：0.007
Claims (3)
1. one kind from inorganic aqueous solution, particularly remove the method for silicate in the pickle solution, comprising concentrating in advance and this solution of follow-up filtration, it is characterized in that pending solution is introduced the cross flow membrane strainer, being provided with in this strainer and can filtering diameter is percentum to the particulate film of a few tenths of micron, and makes the described solution described strainer of flowing through under 60 ℃ to 90 ℃ temperature.
2. method according to claim 1 is characterized in that described temperature is in 70 ℃ to 80 ℃ scopes.
3. method according to claim 1 is characterized in that the cross flow membrane strainer is sent in the concentrated solution circulation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA981/91 | 1991-05-13 | ||
| AT0098191A AT395408B (en) | 1991-05-13 | 1991-05-13 | MICROFILTRATION |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1068602A CN1068602A (en) | 1993-02-03 |
| CN1037705C true CN1037705C (en) | 1998-03-11 |
Family
ID=3504218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92104547 Expired - Fee Related CN1037705C (en) | 1991-05-13 | 1992-05-13 | Microfiltration |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0584146A1 (en) |
| JP (1) | JP2810234B2 (en) |
| KR (1) | KR0138070B1 (en) |
| CN (1) | CN1037705C (en) |
| AT (1) | AT395408B (en) |
| TW (1) | TW222610B (en) |
| WO (1) | WO1992020834A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829592C1 (en) * | 1998-07-02 | 1999-12-09 | Umweltanalytisches Zentrum Gro | Mineral acids containing metals from pickling plants are processed and recovered |
| AT411575B (en) * | 2002-07-25 | 2004-03-25 | Kcs Austria Engineering Gmbh | Regeneration of steelworks spray-roasting pickling solutions, comprises filtering settled solution using transverse-flow microfilter |
| FR2916205A1 (en) * | 2007-05-16 | 2008-11-21 | Siemens Vai Metals Tech Sas | INSTALLATION AND PROCESS FOR TREATING SILICON STEEL BAND REMOVAL SOLUTIONS |
| AT13601U1 (en) * | 2012-09-06 | 2014-04-15 | Astec Engineering Gmbh | Purification and desiccation of spent acid baths using combined microfiltration techniques |
| CN110272159A (en) * | 2019-06-17 | 2019-09-24 | 苏州乔发环保科技股份有限公司 | The recycling processing method and device of inorganic salts in a kind of industrial wastewater |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5990688A (en) * | 1982-11-15 | 1984-05-25 | Arubatsuku Service Kk | Device and method for treating silica-containing water |
| FR2670508B1 (en) * | 1990-12-13 | 1994-08-12 | Siderurgie Fse Inst Rech | PROCESS FOR SEPARATING THE SILICON COMPOUNDS CONTAINED IN A HYDROCHLORIC STRIPPING BATH OF PARTS, PARTICULARLY STEEL SHEETS. |
-
1991
- 1991-05-13 AT AT0098191A patent/AT395408B/en not_active IP Right Cessation
-
1992
- 1992-05-13 CN CN 92104547 patent/CN1037705C/en not_active Expired - Fee Related
- 1992-05-13 KR KR1019930703423A patent/KR0138070B1/en not_active IP Right Cessation
- 1992-05-13 WO PCT/AT1992/000069 patent/WO1992020834A1/en not_active Application Discontinuation
- 1992-05-13 JP JP4509113A patent/JP2810234B2/en not_active Expired - Fee Related
- 1992-05-13 EP EP19920909956 patent/EP0584146A1/en not_active Withdrawn
- 1992-05-15 TW TW81103811A patent/TW222610B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| TW222610B (en) | 1994-04-21 |
| EP0584146A1 (en) | 1994-03-02 |
| AT395408B (en) | 1992-12-28 |
| CN1068602A (en) | 1993-02-03 |
| KR0138070B1 (en) | 1998-04-27 |
| JPH06507206A (en) | 1994-08-11 |
| ATA98191A (en) | 1992-05-15 |
| WO1992020834A1 (en) | 1992-11-26 |
| JP2810234B2 (en) | 1998-10-15 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
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