GB2095220A - Concentrating antimony and tin - Google Patents
Concentrating antimony and tin Download PDFInfo
- Publication number
- GB2095220A GB2095220A GB8206455A GB8206455A GB2095220A GB 2095220 A GB2095220 A GB 2095220A GB 8206455 A GB8206455 A GB 8206455A GB 8206455 A GB8206455 A GB 8206455A GB 2095220 A GB2095220 A GB 2095220A
- Authority
- GB
- United Kingdom
- Prior art keywords
- antimony
- reactor
- tin
- oxide
- sulphide
- 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
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 21
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 150000003568 thioethers Chemical class 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000006227 byproduct Substances 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229960004424 carbon dioxide Drugs 0.000 claims description 2
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 239000011343 solid material Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/04—Blast roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process for the concentration of antimony and tin in the oxide state from the respective ores or by- products, characterised in that, in a single stage, one obtains, by means of air and/or oxygen and carbonaceous material (such as poor-quality coal), a volatilization of the sulphides and/or oxides, followed by oxidation in the gaseous phase of the sulphides to oxides. Antimony and/or tin in metallic form are obtained in the absence of the air and/or oxygen. An apparatus for carrying out the process is a reactor having a frustoconical outline, consisting of a metal casing (2) internally lined by a refractory lining (3), the reactor being rotated about its axis (1), which is arranged vertically, and is equipped with a bottom drain hole (5) so that the solid material charged therein adheres, due to the effect of the several forces in play, to the inner walls of the reactor and the liquid substances which are produced are allowed to flow down through the drain hole. <IMAGE>
Description
SPECIFICATION
Concentrating non-ferrous metals such as antimony and tin
This invention relates to a process for enriching, with oxides of antimony and/or tin, by volatilizing at an appropriate temperature, materials which contain them in amounts which can vary at random in the form of oxides and sulphides. The materials used can be either primary raw material (ores) or secondary materials (such as mineral residues and slags).
The most important methods used nowadays for the concentration of non-ferrous metals such as antimony and tin will now be described. These methods, in the case of antimony, fall into three classes, namely methods involving precipitation (wet methods), methods involving roasting with volatilization, and methods involving roasting without volatilization.
Roasting with volatilization is used whenever the starting material contains less than 40% of antimony and other revoverable metals in a blank phase such as copper and precious metals. The other processes, namely precipitation and roasting without volatilization, are used whenever the starting material contains at least 40% of antimony and not too many impurities. However, the precipitation method, even through it requires only a single step, is generally used only for very rich concentrates and for small quantities because it is very expensive.
Conventional roasting processes are characterised by the problems caused by the uncommon physico-chemical properties of antimony trisulphate and trioxide, namely a high vapour pressure and a low boiling point, a low melting point, and instability even in environments which are only slightly oxidizing.
Thus, these processes, since they take place in more than one stage, require slag recycling and recycling of the blanks, and result in large volumes of dust, with attendant reduction in yield and the necessity of treating a number of intermediates.
One behaviour common to antimony and tin when subjected to volatilization is that the highest yields are obtained by the volatilization of their sulphides. It is thus necessary that, in processing, irrespective of the procedure used, oxidizing conditions be avoided.
According to the present invention, there is provided a process for treating a particulate material containing sulphide and/or oxide of antimony and/or tin, which process comprises heating the material in the presence of an articulate carabonaceous material and in the presence of air and/or oxygen so as to cause volatilization of the sulphide and/or the oxide and so as subsequently to cause oxidation in the vapour phase of the sulphide to oxide.
The process according to the present invention is an alternative to the conventional procedures, and is carried out in a single stage with control of the environment, with volatilization of the sulphides, and with roasting (or post-combustion)
in the vapour phase of the sulphide, to produce
concentrates which are desirably rich in antimony
and/or tin.
The process permits savings in fuel to be
achieved, so that even poor-grade coal can be used used in comminuted form, without it being necessary to use natural gas or coke.
Thus the invention provides a process for the
concentration of oxides. At the start, volatilization
is effected of the suiphides and the oxides
contained in the starting materials, by exploiting
the reaction heat of the carbonaceous material
and the combustion aid (air and/or oxygen),
whereafter there occurs, in the vapour phase, the
roasting of the sulphides and the oxides with air and/or oxygen.
The temperatures preferably exceeds by at leas
500C the boiling point of the sulphide and/or the
oxide which is contained in the starting materials,
so as to bring about volatilization. As a rule, one
starts from a temperature of 1 5000C and above.
The non-volatile fraction of the charge, which
will be found in the slag, may have such
concentrations of its various components that the
slag may even so melt at a low temperature such
as below 12000 C. Thus, appropriate additions of
CaO, SiO2 and other oxides to the starting
materials may be made whenever such conditions
are not fully met.
As an alternative procedure, antimony or tin in
the metal state can be produced. If so, there is a
reaction of the oxides and/or sulphides to reduce
them to a metallic state by means of carbon and
carbon monoxide and a consequential
volatilization of the metals concerned.
Preferably, the process of the invention is carrier
out in a rotating frustoconical reactor such that
solid phase adheres to the wall of the reactor and
such that liquid phase flows out of the reactor
through a drain hole in the bottom of the reactor.
Thus, the process can be carried out in an
apparatus as claimed in any claim of our patent
application filed on the same day as the present
application for an invention entitled "Apparatus
For Recovering Metallic Materials".
One apparatus suitable for carrying out the
process is characterised in that it is frustoconical,
comprising one or more conical frustrums possibly
replaced by their enveloping curved surface
(external or internal) and comprising a metal casing lined with a refractory material and rotated about its vertically arranged geometrical axis and equipped with a bottom drain hole, so that the solid charge material, due to the effect of the several forces in play, adheres to the inner reactor walls and the liquid substances which are formed can flow down towards the drain hole, the inside diameter of the larger base being from 1 to 10 metres, the inside diameter of the lesser base being from 0.2 to 1 metre, the diameter of the drain hole being from 5 to 100% of the diameter of the lesser base, the angle of the generating lines of the cone with the vertical being from 10 to 600, and the rotational speed of the reactor being from 10 to 80 rpm. Preferably, the generating lines of the surfaces do not have a mutual inclination greater than 300.
Reference will now be made, by way of example, to Figures 1 and 2 of the accompanying drawings, showing reactors suitable for use in the invention.
The reactor is frustoconical, and consists of one or more conical frustums, possibly replaced by their external or internal enveloping surfaces. It is arranged so that its geometrical axis 1 is vertical.
In use, the reactor is rotated about its axis 1. The reactor consists of a metal casing 2, internally lined with refractory bricks 3. The angular rotational speed and the angle 4 between the generating lines of the inner surfaces of the wails of the frustoconical bodies (or their enveloping surfaces) and the vertical is such that the solid phase of the material heated in the reactor remains, from a dynamic standpoint, in equilibrium under the concurrent actions of the weight, the inertiai rotational forces, and the frictional forces on the inner wall, whereas the liquid phase runs down towards the reactor base, which has a drain hole 5.
The inside diameter of the larger base of the reactor is from 1 to 10 metres, preferably from 2 to 6 metres, whereas the inside diameter of the lesser base is from 0.2 to 1 metre.
The diameter of the drain hole is from 5% to 30% of the larger inside diameter, until reaching even 100% of the inside diameter of the lesser base depending upon the potential output of the installation.
The angle of the generating line of the cone to the vertical is from 100 to 600, angles greater than 200 being preferred. In the case of a reactor consisting of more than one conical frustum or of an enveloped curved surface, the generating lines and their tangents preferably do not have mutual inclination greater than 300. In use, the rotational speed of the reactor is usually from 10 to 80 rpm.
From two to four pipes or nozzles 6 and 7, with their ends opening into the inside of the inclined reactor, the nozzles being capable of being moved along a vertical axis, are used for charging both the feed material and the fuel. Alternatively, one or more pipes 8 (usually up to a maximum of four pipes) which are substantially parallel to the generating lines of the inner surface, may be used.
Through perforations 9 formed along the entire pipe length and possibly evenly spaced apart from each other, preheated air and/or oxygen is continuously blown into the reactor. This jet of combustion aid has a radial centrifugal component and a tangential component relative to the path at the point where the jet impinges on the reactor wall and along a direction concordant with the motion so as not to disturb the dynamic conditions of the charge which is held in the reactor, either in the liquid phase or in the solid phase.
Lastly, there is a central pipe 10 for introducing a combustion-aid, which is also used to burn the carbon monoxide formed.
The charge can be a primary raw material and/or a secondary raw material which contain sulphides and oxides of antimony and/or tin with a particle size of from 0.01 mm and 5 mm.
The charge can be fed into the top section of the reactor, possibly already admixed with the fuel, the latter also having a fine particle size, or it can be fed discretely into the reactor by means of the pipes 6 and 7, whereas the carbon-containing material is introduced by means of one of the pipes which is not otherwise used, so as to provide the desired thermal conditions for the process.
As the combustion aid, air, possibly preheated at 6000C and enriched with oxygen or pure oxygen, possibly preheated to 2000 C, is preferably used.
The reaction velocity is very high due to the very large inter-phase contact surfaces, which is direct consequence both of the fine particle size of the charge and fuel, and the rotary motion of the reactor.
An example will now be given to illustrate the invention.
EXAMPLE Starting from a sulphide material, a concentrate having a 50% to 60% antimony grade, one obtains an 80% grade oxide with yields of 95% and over and an output of 10 kg per minute by employing a frustoconical sheet metal reactor internally lined by refractory bricks. The diameter of the larger base of the reactor was 1 600 mm, the diameter of the lesser base of the reactor was 400 mm, the height of the conical frustum of the reactor was 1000 mm, and the angle of the generating line of the cone relative to the vertical was approximately 300. The rotational speed of the cone was 30-35 rpm, the rate of flow of air was 4 normal cubic metres per minute, the feed rate of coal was 3 kg per minute, and rate of feed of the charge, admixed with 0.05 kg of coal per one kg of charge, was 1 5 kg per minute.
Claims (10)
1. A process for treating a particulate material containing sulphide and/or oxide of antimony and/or tin, which process comprises heating the material in the presence of a particulate carbonaceous material and in the presence of air and/or oxygen so as to cause volatilization of the sulphide and/or the oxide and so as subsequently to cause oxidation in the vapour phase of the sulphide to oxide.
2. A process according to claim 1, wherein the material is heated to a temperature which is at least 500C greater than the boiling point of the sulphide and/or the oxide.
3. A process according to claim 1 or 2, wherein the material containing sulphide and/or oxide of antimony and/or tin, and/or the carbonaceous material, have a particle size of from 0.01 to 5 mm.
4. A process according to any of claims 1 to 4.
wherein the air and/or oxygen is preheated to a temperature of from 200 to 6000C.
5. A process for producing antimony and, or tin in metallic form from a material containing sulphide and/or oxide of antimony and/or tin, which process comprises heating the material in the presence of a carbonaceous material and/or carbon monoxide so as to cause reduction of the sulphide and/or oxide to metal and so as subsequently to cause volatilization of the metal.
6. A process for concentrating oxides of antimony or tin from the respective ore or secondary by-product containing sulphides and oxides, characterised in that, in a single step, one obtains with air and/or oxygen and carbonaceous compounds, even coal of a poor grade, a volatilization of the sulphides and the oxides, followed by a roasting in the vapour phase by air and/or oxygen of the sulphides to oxides, at an appropriate temperature, the charge materials having an appropriate particle size.
7. A process for the production of antimony and/or tin in the metallic state from primary or secondary raw material, characterised in that one obtains, in a single step, a reduction reaction of the oxide and/or sullphide contained in the charge, to the metallic state by carbon or carbon monoxide and a consequential volatilization of the metal.
8. A process according to any of claims 1 to 7, the process being carried out in a rotating frustoconical reactor such that solid phase adheres td the wall of the reactor and such that liquid phase flows out of the reactor through a drain hole in the bottom of the reactor.
9. A process according to claim 8, the process being carried out in an apparatus as claimed in any claim of our patent application filed on the same
day as the present application for an invention
entitled "Apparatus For Recovering Metallic
Material".
10. A process according to claim 1, 5 or 6,
substantially as hereinbefore described with
reference to Figure 1 or Figure 2 of the drawing.
11 . The product of a process according to any
of claims 1 to 10.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20342/81A IT1137504B (en) | 1981-03-13 | 1981-03-13 | PROCEDURE FOR THE CONCENTRATION OF NON-FERROUS METALS AS ANTIMONY AND WATERPROOF BY VOLATILIZATION FROM THEIR MINERAL OR SECONDARY PRODUCTS AND EQUIPMENT TO CONDUCT THAT PROCEDURE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2095220A true GB2095220A (en) | 1982-09-29 |
| GB2095220B GB2095220B (en) | 1985-02-06 |
Family
ID=11165874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8206455A Expired GB2095220B (en) | 1981-03-13 | 1982-03-04 | Concentrating antimony and tin |
Country Status (11)
| Country | Link |
|---|---|
| BE (1) | BE892473A (en) |
| DE (1) | DE3207024C2 (en) |
| DK (1) | DK101282A (en) |
| FR (1) | FR2501721A1 (en) |
| GB (1) | GB2095220B (en) |
| GR (1) | GR75515B (en) |
| IT (1) | IT1137504B (en) |
| LU (1) | LU83998A1 (en) |
| NL (1) | NL8201027A (en) |
| SE (1) | SE8201566L (en) |
| YU (1) | YU54382A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105695742B (en) * | 2016-02-24 | 2017-11-10 | 锡矿山闪星锑业有限责任公司 | A kind of smelting process of antimony oxygen low-temperature reduction antimony |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE475115C (en) * | 1924-05-31 | 1929-04-17 | Friedrich Johannsen Dr Ing | Extraction of volatile metals from sulfidic ores, hut products and residues of all kinds |
| DE525687C (en) * | 1925-08-08 | 1931-05-28 | Fried Krupp Grusonwerk Akt Ges | Extraction of tin-containing fly dust from tin-containing ores and hut products with the formation of tin sulfide |
| DE1269631B (en) * | 1954-09-14 | 1968-06-06 | Stora Kopparbergs Bergslags Ab | Process for obtaining molten pig iron |
| DE2019019A1 (en) * | 1970-04-21 | 1971-11-11 | Kloeckner Humboldt Deutz Ag | Process for the separation and enrichment of tin from tin-containing slags, concentrates and the like |
-
1981
- 1981-03-13 IT IT20342/81A patent/IT1137504B/en active
-
1982
- 1982-02-23 GR GR67408A patent/GR75515B/el unknown
- 1982-02-26 DE DE3207024A patent/DE3207024C2/en not_active Expired
- 1982-03-04 GB GB8206455A patent/GB2095220B/en not_active Expired
- 1982-03-09 DK DK101282A patent/DK101282A/en not_active Application Discontinuation
- 1982-03-10 LU LU83998A patent/LU83998A1/en unknown
- 1982-03-11 FR FR8204136A patent/FR2501721A1/en not_active Withdrawn
- 1982-03-12 BE BE0/207553A patent/BE892473A/en not_active IP Right Cessation
- 1982-03-12 SE SE8201566A patent/SE8201566L/en not_active Application Discontinuation
- 1982-03-12 YU YU00543/82A patent/YU54382A/en unknown
- 1982-03-12 NL NL8201027A patent/NL8201027A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| SE8201566L (en) | 1982-09-14 |
| IT1137504B (en) | 1986-09-10 |
| LU83998A1 (en) | 1983-02-22 |
| BE892473A (en) | 1982-09-13 |
| GR75515B (en) | 1984-07-25 |
| GB2095220B (en) | 1985-02-06 |
| DE3207024A1 (en) | 1982-09-16 |
| YU54382A (en) | 1985-03-20 |
| NL8201027A (en) | 1982-10-01 |
| DK101282A (en) | 1982-09-14 |
| IT8120342A0 (en) | 1981-03-13 |
| FR2501721A1 (en) | 1982-09-17 |
| DE3207024C2 (en) | 1985-02-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |