NO125883B - - Google Patents
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- Publication number
- NO125883B NO125883B NO0595/70A NO59570A NO125883B NO 125883 B NO125883 B NO 125883B NO 0595/70 A NO0595/70 A NO 0595/70A NO 59570 A NO59570 A NO 59570A NO 125883 B NO125883 B NO 125883B
- Authority
- NO
- Norway
- Prior art keywords
- manganese
- electrolyte
- oxide
- value
- lead
- Prior art date
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- 239000003792 electrolyte Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 14
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- 150000007514 bases Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- GZMKWMMWAHQTHD-UHFFFAOYSA-L [Mn++].OS([O-])(=O)=O.OS([O-])(=O)=O Chemical compound [Mn++].OS([O-])(=O)=O.OS([O-])(=O)=O GZMKWMMWAHQTHD-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000012173 estrus Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229940037395 electrolytes Drugs 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/21—Manganese oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
Fremgangsmåte til elektrolytisk fremstilling av brunsten. Process for electrolytic production of the rut.
Oppfinnelsen vedrdrer en fremgangsmåte til elektrolytisk fremstilling av brunsten fra elektrolytter som i det vesentlige består av svovelsure mangansulfatopplosninger, som som forurensning-er inneholder kobber, ved hjelp av blykatoder. The invention relates to a method for the electrolytic production of the rut from electrolytes which essentially consist of sulfuric acid manganese sulphate solutions, which contain copper as a contaminant, by means of lead cathodes.
Til elektrolytisk fremstilling av brunsten fra svovelsure mangansulfatopplosninger benytter man vanligvis blykatoder. Lead cathodes are usually used for the electrolytic production of the slag from sulfuric acid manganese sulphate solutions.
Bly og noen av dets legeringer har en god korrosjonsfasthet i et svovelsurt medium, også ved hoyere temperaturer. Denne resistens henger sammen med dannelsen av en sammenhengende beskyttende film av blysulfat på den metalliske overflate. Når bly anvendes som katodemateriale, så uteblir dannelsen av en blysulfatfilm på grunn av blysulfåtets katodiské reduksjon. Den hoye hydrogenoverspenning ved en med en tilstrekkelig stromtetthet belagt blykatode hindrer imidlertid katodematerialets opplosning. Lead and some of its alloys have good corrosion resistance in a sulfuric acid medium, also at higher temperatures. This resistance is related to the formation of a continuous protective film of lead sulfate on the metallic surface. When lead is used as cathode material, the formation of a lead sulphate film does not occur due to the lead sulphate's cathodic reduction. However, the high hydrogen overvoltage at a lead cathode coated with a sufficient current density prevents the cathode material from dissolving.
Erfaring viser imidlertid at stabiliteten ikke er sikret i hver elektrolytt og en opplosning av blyet kan opptre på tross av i og for seg tilstrekkelig katodebelastning» Opplosningsgraden er ikke så stor at katodene ville tape deres mekaniske fasthet i lopet av vanlige driftstider. Imidlertid kommer da så meget bly i elektro-lyttene og dermed i det produkt som utskiller 'seg anodisk at dette da har relativt hoye blyinnhold. Hoye blyinnhold i brunstenen gjor det imidlertid uegnet for mange anvendelsesformål. Experience shows, however, that stability is not guaranteed in every electrolyte and a dissolution of the lead can occur despite sufficient cathode loading in and of itself." The degree of dissolution is not so great that the cathodes would lose their mechanical strength over the course of normal operating times. However, so much lead then ends up in the electro-lytes and thus in the product that separates anodically that this then has a relatively high lead content. However, the high lead content in brownstone makes it unsuitable for many applications.
Overraskende ble det funnet at for opplosning av bly-katodene er det i og for seg ansvarlig et på disse katoder dannet belegg av kobber. Dette var desto mer forbausende, da hydrogenoverspenningen ved en kobberkatode ved samme stromtetthet ikke var vesentlig mindre enn på en. tilsvarende dimensjonert blyelektrode (sml. fig. 1, kurve I og II). Den ved hydrogenoverspenningen, hvis verdi oker med okende stromtetthet (med negativt fortegn), frem-bragte katodepolarisasjon utgjorde ved en stromtetthet på 1,2 A/cm i tilfelle blykatoden -960 mV", i tilfelle'kobberkatode ca. -800 mV. Bly opploser seg imidlertid forst når katodepotensialet er mindre negativt enn blykorrosjonspotensialet som i benyttede elektrolytt ligger ved -520 mV. Surprisingly, it was found that a coating of copper formed on these cathodes is in and of itself responsible for the dissolution of the lead cathodes. This was all the more astonishing, as the hydrogen overvoltage at a copper cathode at the same current density was not significantly less than at one. correspondingly dimensioned lead electrode (cf. Fig. 1, curves I and II). The cathode polarization produced by the hydrogen overvoltage, whose value increases with increasing current density (with a negative sign), amounted to -960 mV in the case of the lead cathode at a current density of 1.2 A/cm", in the case of the copper cathode approx. -800 mV. Lead however, only dissolves when the cathode potential is less negative than the lead corrosion potential, which in the electrolyte used is -520 mV.
Det viste seg imidlertid at ved overskridelse av en bestemt kobberkonsentrasjon i elektrolytten utskilles, kobber på katoden i svampform. Derved oker den virkelige katodeoverflate seg betraktelig i forhold til den geometriske overflate. På grunn av den dermed forbundne nedsettelse av den faktiske stromtetthet faller også hydrogenoverspenningen på katoden således at katodepotensialet på tross av den hoye formelle stromtetthet kan synke til verdier som ligger mer positivt enn blyets korrosjonspotensial (kurve ITI However, it turned out that when a certain copper concentration in the electrolyte is exceeded, copper is separated on the cathode in sponge form. Thereby, the real cathode surface increases considerably in relation to the geometric surface. Due to the associated reduction in the actual current density, the hydrogen overvoltage on the cathode also falls so that, despite the high formal current density, the cathode potential can drop to values that are more positive than the lead's corrosion potential (curve ITI
og IV). Dermed fremtvinges en opplosning av blyet på de steder av katoden som ikke helt er tett belagt med kobber. Opplosningsgraden er desto storre jo storre katodepotensialets avvikning er i positiv retning fra korrosjonspotensialet. and IV). Thus, a dissolution of the lead is forced in the places of the cathode which are not completely covered with copper. The degree of dissolution is the greater the greater the deviation of the cathode potential in the positive direction from the corrosion potential.
Videre ble det funnet at dannelsen av den svampaktige kobberutskillelse avhenger av et minsteinnhold av kobberioner i elektrolytten. Furthermore, it was found that the formation of the spongy copper precipitation depends on a minimum content of copper ions in the electrolyte.
Oppfinnelsen vedrorer nå en fremgangsmåte til fremstilling av brunsten ved hjelp av blykatoder fra elektrolytter, som i det vesentlige består av svovelsure mangansulfatopplosninger og hvis opprinnelig hoyere kobberinnhold er blitt redusert, idet frem-gangsmåten er karakterisert ved at man innstiller kobberinnholdet i elektrolytten til verdier som er mindre enn 0,0005 vektfo, fortrinnsvis mindre enn 0,0002 vekt$, idet man avgrener en del av elektrolytten fra elektrolysebadet, innstiller ved hjelp av teknisk mangan-(II)-oksyd alene eller av teknisk mangan-(II)-oksyd og en basisk forbindelse til en bestemt pH-verdi, deretter filtrerer og tilbakefSrer elektrolytten i elektrolysebadet idet man nøytrali-serer elektrolytten enten alene med teknisk mangan-(II)-oksyd til en pH-verdi fra 6,2 til 7,6, fortrinnsvis 7,8 til 7,2 eller i forste rekke med teknisk mangan-(II)-oksyd inntil en pH-verdi fra 5,0 til 5,5 og deretter noytraliserer med en basisk forbindelse inntil en pH-verdi fra 6,2 til 7,6, fortrinnsvis 6,8 til 7,2 eller at man noytraliserer elektrolytten med teknisk mangan-(II)-oksyd inntil en pH-verdi fra 5,° til 6,5, fortrinnsvis til 5,5» filtrerer og deretter forer gjennom en noytral kationutveksler, hvis kationeplasser fullstendig er besatt med manganioner for man tilbakefører elektrolytten i elektrolysebadet. The invention now relates to a method for producing the rut using lead cathodes from electrolytes, which essentially consist of sulfuric acid manganese sulfate solutions and whose originally higher copper content has been reduced, the method being characterized by setting the copper content in the electrolyte to values that are less than 0.0005 wt.fo, preferably less than 0.0002 wt.$, branching off a part of the electrolyte from the electrolytic bath, adjusting with the help of technical manganese (II) oxide alone or of technical manganese (II) oxide and a basic compound to a specific pH value, then filtering and returning the electrolyte to the electrolytic bath, neutralizing the electrolyte either alone with technical manganese (II) oxide to a pH value of from 6.2 to 7.6, preferably 7 .8 to 7.2 or primarily with technical manganese (II) oxide up to a pH value of 5.0 to 5.5 and then neutralizing with a basic compound up to a pH value of 6.2 to 7 ,6, preferably 6.8 to 7.2 or that one neutralizes the electrolyte with technical manganese (II) oxide until a pH value of 5.0 to 6.5, preferably to 5.5" filters and then passes through a neutral cation exchanger , whose cation sites are completely occupied by manganese ions before returning the electrolyte to the electrolysis bath.
Derved går man fortrinnsvis frem således at man avgrener en del av den svovelsure elektrolytt fra elektrolysebadet, for regenerering av manganinnholdet innstiller med teknisk mangan-(Il)-oksyd til en pH-verdi på 6,2-7,6, fortrinnsvis 6,8 til 7,2, deretter filtrerer og tilbakefører i elektrolysebadet. Thereby, one proceeds preferably in such a way that one branches off a part of the sulfuric acid electrolyte from the electrolysis bath, for regeneration of the manganese content adjusts with technical manganese (II) oxide to a pH value of 6.2-7.6, preferably 6.8 to 7.2, then filter and return to the electrolysis bath.
Det lonner seg i forste rekke å fornoytralisere den avgrenede elektrolytt med det tekniske mangan (II)-oksyd fortrinnsvis til en pH-verdi fra 5,0 til 5,5, deretter å innstille med en basisk forbindelse til en pH-verdi fra 6,2 til 7,6, fortrinnsvis 6,8 til 7,2, deretter å frafiltrere og å tilbakefore de regenererte elektrolytter i elektrolysebadet. It pays primarily to pre-neutralize the branched electrolyte with the technical manganese (II) oxide, preferably to a pH value of 5.0 to 5.5, then to adjust with a basic compound to a pH value of 6, 2 to 7.6, preferably 6.8 to 7.2, then filtering off and returning the regenerated electrolytes to the electrolytic bath.
Herved kan man som basisk forbindelse anvende kalsiumhydroksyd, kalsiumoksyd eller et alkahlihydroksyd. In this way, calcium hydroxide, calcium oxide or an alkali hydroxide can be used as a basic compound.
En ytterligere utforelsesform av oppfinnelsen består eksempelvis i at man innstiller en svovelsur mangansulfatopplosning med teknisk mangan (Il)-oksyd til en pH-verdi fra 5,0 til 6,5, fortrinnsvis på 5,5, filtrerer, deretter forer gjennom en noytral kationutveksler hvis kationplasser fullstendig er besatt med manganioner og deretter anvender den dannede opplosning som elektrolysebad eller til regenerering av et forbrukt elektrolyse— bad. A further embodiment of the invention consists, for example, in setting a sulphurous manganese sulphate solution with technical manganese (II) oxide to a pH value of from 5.0 to 6.5, preferably 5.5, filtering, then passing through a neutral cation exchanger whose cation sites are completely occupied with manganese ions and then use the resulting solution as an electrolysis bath or for the regeneration of a spent electrolysis bath.
Fordelen ved den nye fremgangsmåte ligger i at man The advantage of the new method is that one
får en brunsten som er praktisk talt fri for blyforurensninger og at blykatodens anvendelsesvarighet okes vesentlig. get a rut that is practically free of lead contamination and that the duration of use of the lead cathode is significantly increased.
Elektrolysebadets forstyrrende kobberinnhold som vanligvis har innhold av mangansulfat fra 4-0 til 300 g/l og av svovelsyre fra 0 til 120 g/l samt en pH-verdi fra 0 til 5» stammer fra rå-manganmalm. Innhold av kobber i slike bad kan utgjore 0,001 til 0,03 vekt$. The disturbing copper content of the electrolysis bath, which usually has a content of manganese sulphate from 4-0 to 300 g/l and of sulfuric acid from 0 to 120 g/l as well as a pH value from 0 to 5", originates from raw manganese ore. The content of copper in such baths can amount to 0.001 to 0.03 by weight.
Den nye fremgangsmåtens virkningsmåte skal forklares ved hjelp av folgende eksempler. The mode of action of the new method shall be explained with the help of the following examples.
Eksempel 1. Example 1.
En svovelsur mangansulfatopplosning med innhold av MnSO^ på 100 g/l og HgSO^ på 65 g/l og kobber på 100 mg/l samt en pH-verdi på rundt 0,5 fornoytraliseres med teknisk manganoksyd inntil en pH-verdi på 5,5 og deretter omsettes med samme manganoksyd langsomt til en pH-verdi på 6,8 og filtreres. Filtratet består da av en for oppfriskning av et bEd til elektrolyttisk brun-stenfremstilling egnet elektrolytt med et kobberinnhold på 0,0002 vekt$. Den herav med en blykatode utskilte brunsten har et blyinnhold på 0,10 vektfo. Blykatodens anvendelsesvarighet utgjor mer enn 2000 elektrolysetimer. A sulfuric acid manganese sulphate solution containing MnSO^ of 100 g/l and HgSO^ of 65 g/l and copper of 100 mg/l and a pH value of around 0.5 is pre-neutralized with technical manganese oxide until a pH value of 5, 5 and then reacted with the same manganese oxide slowly to a pH value of 6.8 and filtered. The filtrate then consists of an electrolyte suitable for refreshing a bed for electrolytic lignite production with a copper content of 0.0002 wt. The dross separated from this with a lead cathode has a lead content of 0.10% by weight. The duration of use of the lead cathode amounts to more than 2,000 electrolysis hours.
Eksempel 2. Example 2.
Man går frem som omtalt i eksempel 1, omsetter imidlertid den fornoytraliserte opplosning deretter med teknisk manganoksyd og kalsiumhydroksyd til en pH-verdi på 7,0 til 7,2 og filtreres deretter. Herved senkes filtratets kobberinnhold til en kon-sentrasjon på 0,00005$. Den herav med en blykatode utskilte brunsten har et blyinnhold på 0.,08 vekt$. Blykatodens levetid utgjor mer enn 3000 elektrolysetimer. One proceeds as described in example 1, however, the pre-neutralized solution is then reacted with technical manganese oxide and calcium hydroxide to a pH value of 7.0 to 7.2 and then filtered. This lowers the filtrate's copper content to a concentration of 0.00005$. The dross separated from this with a lead cathode has a lead content of 0.08% by weight. The lifetime of the lead cathode amounts to more than 3,000 electrolysis hours.
Eksempel 3»Example 3»
En svovelsur mangansulfatopplosning fremstilt som i eksempel 1, nøytraliseres med teknisk mangan-(II)-oksyd til en pH-verdi på 5,5 °g filtreres. Filtratet fores deretter gjennom en noytral kationutveksler, som har alle kationplasser besatt med mangan. Den utstrommende elektrolytt inneholder mindre enn 0,0001$ kobber. Den herav med en blykatode utskilte brunsten har et blyinnhold på eksempelvis 0,08 vekt%. A sulphurous manganese sulphate solution prepared as in example 1 is neutralized with technical manganese (II) oxide until a pH value of 5.5 °g is filtered. The filtrate is then fed through a neutral cation exchanger, which has all cation sites occupied with manganese. The flowing electrolyte contains less than 0.0001$ of copper. The rut separated from this with a lead cathode has a lead content of, for example, 0.08% by weight.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1908493A DE1908493C3 (en) | 1969-02-20 | 1969-02-20 | Process for the electrolytic extraction of manganese dioxide |
Publications (1)
Publication Number | Publication Date |
---|---|
NO125883B true NO125883B (en) | 1972-11-20 |
Family
ID=5725824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO0595/70A NO125883B (en) | 1969-02-20 | 1970-02-19 |
Country Status (8)
Country | Link |
---|---|
US (1) | US3634215A (en) |
BE (1) | BE746291A (en) |
CS (1) | CS167892B2 (en) |
DE (1) | DE1908493C3 (en) |
FR (1) | FR2041054B1 (en) |
GB (1) | GB1256991A (en) |
NL (1) | NL167735C (en) |
NO (1) | NO125883B (en) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1874827A (en) * | 1931-05-12 | 1932-08-30 | Burgess Battery Co | Production of manganese dioxide |
FR1448939A (en) * | 1965-06-28 | 1966-08-12 | E J Lavino & Co | Process for preparing a solution of manganese sulfate from ferromanganese and an ore essentially consisting of manganese dioxide |
-
1969
- 1969-02-20 DE DE1908493A patent/DE1908493C3/en not_active Expired
-
1970
- 1970-02-04 GB GB1256991D patent/GB1256991A/en not_active Expired
- 1970-02-12 NL NL7002017A patent/NL167735C/en not_active IP Right Cessation
- 1970-02-16 US US11514A patent/US3634215A/en not_active Expired - Lifetime
- 1970-02-17 CS CS1095A patent/CS167892B2/cs unknown
- 1970-02-19 NO NO0595/70A patent/NO125883B/no unknown
- 1970-02-20 BE BE746291D patent/BE746291A/en not_active IP Right Cessation
- 1970-02-20 FR FR707006153A patent/FR2041054B1/fr not_active Expired
Also Published As
Publication number | Publication date |
---|---|
NL167735C (en) | 1982-01-18 |
GB1256991A (en) | 1971-12-15 |
DE1908493A1 (en) | 1970-09-17 |
CS167892B2 (en) | 1976-05-28 |
NL167735B (en) | 1981-08-17 |
DE1908493C3 (en) | 1979-04-12 |
US3634215A (en) | 1972-01-11 |
BE746291A (en) | 1970-08-20 |
FR2041054B1 (en) | 1974-06-14 |
FR2041054A1 (en) | 1971-01-29 |
NL7002017A (en) | 1970-08-24 |
DE1908493B2 (en) | 1978-08-10 |
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