NO120284B - - Google Patents
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- Publication number
- NO120284B NO120284B NO16969467A NO16969467A NO120284B NO 120284 B NO120284 B NO 120284B NO 16969467 A NO16969467 A NO 16969467A NO 16969467 A NO16969467 A NO 16969467A NO 120284 B NO120284 B NO 120284B
- Authority
- NO
- Norway
- Prior art keywords
- metal
- alkali metal
- halide
- molten
- reaction
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 150000004820 halides Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000011833 salt mixture Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims 1
- 150000005309 metal halides Chemical class 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/26—Fuel gas
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Fremgangsmåte for fremstilling av titan, zirkonium, Process for the production of titanium, zirconium,
vanadium, hafnium, tantal eller niob. vanadium, hafnium, tantalum or niobium.
Denne oppfinnelse går ut på en fremgangsmåte for fremstilling av titan, zirkonium, vanadium, hafnium, tantal eller niob. This invention concerns a method for the production of titanium, zirconium, vanadium, hafnium, tantalum or niobium.
Fremstilling av disse metaller har lenge Production of these metals has long
frembudt mange vanskeligheter. De mest lo-vende metoder har vært basert på reduksjon av et halogenid av metallet ved hjelp av et av alkalimetallene. Det er blitt foreslått mange metoder for utførelse av denne grunnleggende reaksjon, og noen er blitt anvendt i halvtek-nisk målestokk, men ingen av metodene har vist seg å være uten utførelsesvanskeligheter eller fare. Reduksjonsreaksjonen er av ekso-termisk art, hvorfor reaksjonsdeltakerne må føres sammen under nøyaktig regulerte for-hold, hvis tilfredsstillende resultater skal opp-nås. Blant de vanskeligheter som møtes i den tidligere teknikk for fremstilling av metaller som f. eks. titan er den at reaksjonsdeltaker-nes fordampning må nedsettes til et minimum. Reaksjoner i dampfase fører til at det på munnstykker og andre deler av utstyret av-settes produkter som gjør det vanskelig å styre reaksjonen og å fjerne reaksjonsproduk-tene. Omrøring av reaksjonsdeltakerne kom-pliseres ved at det dannes faste produkter som hindrer mekaniske røreres virksomhet. presented many difficulties. The most promising methods have been based on the reduction of a halide of the metal using one of the alkali metals. Many methods have been proposed for carrying out this basic reaction, and some have been used on a semi-technical scale, but none of the methods has proven to be without difficulties in execution or danger. The reduction reaction is of an exothermic nature, which is why the reaction participants must be brought together under precisely regulated conditions, if satisfactory results are to be achieved. Among the difficulties encountered in the prior art for the production of metals such as e.g. titanium is that the evaporation of the reaction participants must be reduced to a minimum. Reactions in the vapor phase lead to products being deposited on nozzles and other parts of the equipment which make it difficult to control the reaction and to remove the reaction products. Stirring of the reaction participants is complicated by the formation of solid products which hinder the operation of mechanical stirrers.
Formålet med den foreliggende oppfinnelse er å skaffe en hensiktsmessig fremgangsmåte til fremstilling av disse metaller, samt å- fremstille dem, særlig titan, med en høy grad av renhet. The purpose of the present invention is to provide a suitable method for the production of these metals, as well as to produce them, particularly titanium, with a high degree of purity.
Fremgangsmåten ifølge oppfinnelsens mål The method according to the object of the invention
er av den art hvor man i to trinn reduserer et halogenid av det metall som skal frem-stilles. I det første trinn reduseres halogenidet til et subhalogenid ved hjelp av et smeltet is of the kind where a halide of the metal to be produced is reduced in two stages. In the first step, the halide is reduced to a subhalide by means of a fused
reduserende metall. I det annet trinn blir sub-halogenidene redusert til metall ved videre tilsetning av smeltet reduserende metall i en mengde som er tilstrekkelig til å skaffe den støkiometrisk nødvendige mengde reduserende metall til å reagere med halogenidet. Under reduksjonen opprettholdes det en ikke forurensende atmosfære. reducing metal. In the second step, the sub-halides are reduced to metal by further addition of molten reducing metal in an amount sufficient to provide the stoichiometrically necessary amount of reducing metal to react with the halide. During the reduction, a non-polluting atmosphere is maintained.
I henhold til oppfinnelsen er fremgangsmåten karakterisert ved at man i en reaksjonsbeholder hvori befinner seg et smeltet bad av alkaliemetallet først på i og for seg kjent måte sprøyter inn vedkommende halogenid i en mengde som er i overskudd til den som kreves for fullstendig reaksjon med alkalimetallet, slik at det dannes delvis reduserte sub-halogenider av metallet, hvoretter man i reaksjonsbeholderen med det smeltede According to the invention, the method is characterized by the fact that in a reaction container in which there is a molten bath of the alkali metal, the halide in question is first injected in a manner known per se in an amount that is in excess of that required for complete reaction with the alkali metal, so that partially reduced sub-halides of the metal are formed, after which in the reaction vessel with the molten
bad av sub-halogenider sprøyter inn ekstra bath of sub-halides inject extra
smeltet alkalimetall i en mengde som er nød-vendig for fullstendig reaksjon med det delvis reduserte sub-halogenid, hvoretter man utvinner det reduserte metall fra saltblandingen. molten alkali metal in an amount necessary for complete reaction with the partially reduced sub-halide, after which the reduced metal is recovered from the salt mixture.
I henhold til et videre trekk ved oppfinnelsen blir det ekstra alkalimetall innført i badet under dettes overflate. According to a further feature of the invention, the additional alkali metal is introduced into the bath below its surface.
Den vedføyede tegning viser skjematisk et apparat i hvilket fremgangsmåten i henhold til oppfinnelsen kan utføres. The attached drawing schematically shows an apparatus in which the method according to the invention can be carried out.
Et av metall bestående reaksjonskammer 1 er oventil forsynt med en tilførselsledning 2 A reaction chamber 1 made of metal is provided at the top with a supply line 2
som ender i et munnstykke 3. I den nedre del av kammeret finnes det en tilførselsledning 4 for smeltet metall som ender med et munnstykke 5. Alternativt kan ledningen 4 strekke seg nedover fra toppen av kammeret, og eventuelt kunne dykkes ned i reaksjonsdeltakerne, which ends in a nozzle 3. In the lower part of the chamber there is a supply line 4 for molten metal which ends in a nozzle 5. Alternatively, the line 4 can extend downwards from the top of the chamber, and possibly be immersed in the reaction participants,
hvis det ønskes. De smeltede klorider kan tap- if desired. The molten chlorides can lose
pes ut gjennom ledningen 6. pesed out through the line 6.
Som et eksempel på utførelse av frem- As an example of the execution of the
gangsmåten i henhold til oppfinnelsen skal det nå beskrives redusering av titantetraklorid ved hjelp av natrium. Reaktoren 1 spyles ren for luft og fylles med en ikke forurensende gass, f. eks. argon. Deretter innføres det en viss mengde smeltet natrium gjennom lednin- the procedure according to the invention, the reduction of titanium tetrachloride by means of sodium will now be described. Reactor 1 is purged of air and filled with a non-polluting gas, e.g. argon. A certain amount of molten sodium is then introduced through the lead
gen 4 og munnstykket 5. Gjennom ledningen 2 og munnstykket 3 ledes det med stor hastig- gene 4 and the nozzle 5. Through the wire 2 and the nozzle 3 it is conducted at high speed
het inn omtrent den dobbelt støkiometriske mengde titantetraklorid, så det dannes en blanding av titansubklorider og natriumklorid. heat in approximately twice the stoichiometric amount of titanium tetrachloride, so a mixture of titanium subchlorides and sodium chloride is formed.
Det antas at titansubkloridet er enten prak- It is believed that the titanium subchloride is either prac-
tisk talt bare TiCb eller titansubklorider som er oppløst i alkalikloridet, eller klomplekser av disse subklorider og av alkalikloridet. I et hvert tilfelle blir badets fluiditet ikke nedsatt, technically only TiCb or titanium subchlorides which are dissolved in the alkali chloride, or clumps of these subchlorides and of the alkali chloride. In each case, the fluidity of the bath is not reduced,
og blandingens smeltepunkt ligger lavere enn rent natriumklorids smeltepunkt. and the melting point of the mixture is lower than the melting point of pure sodium chloride.
Etter at innsprøytingen av titantetraklo- After the injection of titanium tetrachloro-
ridet er avsluttet innføres det resterende na- the ride is finished, the remaining na-
trium i en mengde som er tilstrekkelig til full- trium in an amount sufficient to fully
stendig reaksjon med den i reaktoren 1 til- continuous reaction with it in reactor 1 to
stedeværende mengde klorid, for eksempel gjennom et i badet neddykket munnstykke 5. amount of chloride present, for example through a nozzle immersed in the bath 5.
Den største del av det resulterende natrium- The major part of the resulting sodium
klorid kan deretter tappes ut av reaktoren. chloride can then be drained from the reactor.
Eventuelt tilbakeblivende natriumklorid kan Any remaining sodium chloride can
fjernes fra det i reaktoren dannede titanme- is removed from the titanium metal formed in the reactor
tall ved vanlige metoder, f. eks. ved utlutning eller destillasjon i vakuum. numbers by usual methods, e.g. by leaching or distillation in vacuum.
Det er blitt funnet at innsprøytingshas- It has been found that injection has-
tigheten av halogenidet av det tungtsmelten- ity of the halide of the low-melting
de metall kan ligge mellom 0,03 og 60 m/sek, de metal can lie between 0.03 and 60 m/sec,
og at innsprøytingshastigheten av det smelte- and that the injection rate of the molten
de alkalimetall i det annet trinn av reduksjo- the alkali metals in the second step of the reduction
nen kan ligge mellom 0,003 og 45 m/sek. Det foretrekkes forholdsvis store hastigheter, da disse befordrer omrøring av reaksjonsdeltakerne. nen can lie between 0.003 and 45 m/sec. Relatively high speeds are preferred, as these promote stirring of the reaction participants.
De følgende eksempler er typiske utførel- The following examples are typical implementations
sesformer for oppfinnelsen. embodiments of the invention.
Eksempel 1. Example 1.
Ca. 44 kg smeltet natriummetall ble an- About. 44 kg of molten sodium metal was
brakt i en reaktor hvis atmosfære bestod av praktisk talt rent argon. Metallbadet blev opphetet til ca. 400° C. Deretter blev det i metallbadet ledet nnn 189 kg titantetraklorid brought into a reactor whose atmosphere consisted of practically pure argon. The metal bath was heated to approx. 400° C. Next, 189 kg of titanium tetrachloride were introduced into the metal bath
— ca. det dobbelte av den mengde som be- - about. twice the amount that be-
høves for støkiometrisk reaksjon med natri- be prepared for stoichiometric reaction with sodium
ummetallet for dannelse av titan — med en hastighet av 1—7 m/sek gjennom et munn- re-metalled to form titanium — at a speed of 1-7 m/sec through a mouth-
stykke i reaktorens lokk. I denne periode steg reaksjonsbadets temperatur langsomt og opp- piece in the reactor lid. During this period, the temperature of the reaction bath rose slowly and up-
hetet reaktorens vegger til ca. 850° C. Etter at tilførselen av titantetraklorid var ferdig, the reactor walls were heated to approx. 850° C. After the supply of titanium tetrachloride was finished,
blev det i blandingen innført 47,7 kg flytende natrium, nemlig den mengde som behøvdes for støkiometrisk reaksjon med titanforbindel- 47.7 kg of liquid sodium were introduced into the mixture, namely the amount required for stoichiometric reaction with titanium compounds
sene. Denne mengden blev innført gjennom en ledning hvis utløp befant seg under badets overflate. Natriumet ble tilført med en hastig- tendon. This quantity was introduced through a line whose outlet was below the surface of the bath. The sodium was added at a rapid
het av ca. 2 m/sek, og reaktorens vegger blev holdt på en temperatur mellom ca. 850° og 950° C. Deretter blev reaktorens innhold holdt på en temperatur mellom ca. 900° og 950° heated by approx. 2 m/sec, and the walls of the reactor were kept at a temperature between approx. 850° and 950° C. The reactor's contents were then kept at a temperature between approx. 900° and 950°
C i to timer, for at reaksjonene skulle C for two hours, for the reactions to take place
bli fullstendige. En hel del av det smeltede natriumklorid ble tappet ut, så det i reakto- become complete. A whole portion of the molten sodium chloride was drained off, so that in the reactor
ren blev tilbake en masse bestående av titan- pure remained a mass consisting of titanium
svamp og noe natriumklorid. Resten av na- sponge and some sodium chloride. The rest of the na-
triumkloridet blev fjernet ved utlutning. Ti- the trium chloride was removed by leaching. Ten-
tanmetallet viste seg å være meget rent, idet det inneholdt mindre enn 0,15 % surstoff, the tan metal turned out to be very pure, containing less than 0.15% oxygen,
0,03 % kvelstoff og 0.10 % klor. 0.03% nitrogen and 0.10% chlorine.
Eksempel 2. Example 2.
3,15 kg metallisk natrium og 7,94 kg na- 3.15 kg metallic sodium and 7.94 kg na-
triumklorid blev i et med argon fyllt kammer opphetet ved 850° C. I det smeltede bad blev det ledet inn titantetraklorid i en mengde av 12,61 kg med en hastighet av ca. 20 m/sek gjennom et munnstykke i kammerets lokk. trium chloride was heated in a chamber filled with argon at 850° C. Titanium tetrachloride was introduced into the molten bath in an amount of 12.61 kg at a rate of approx. 20 m/sec through a nozzle in the lid of the chamber.
Etter at tilføringen av titantetrakloridet var After the addition of the titanium tetrachloride was
fullført blev 2,88 kg smeltet natriummetall sprøytet inn i blandingen av de smeltede klo- completed, 2.88 kg of molten sodium metal was injected into the mixture of the molten claws
rider gjennom en annen ledning over badets overflate, og dette med en hastighet av 37,5 m/sek. Når natriumkloridet var blitt skilt fra titanmetallet viste det seg at metallet var av god kvalitet og var meget rent. rides through another wire over the bath's surface, and this at a speed of 37.5 m/sec. When the sodium chloride had been separated from the titanium metal, it turned out that the metal was of good quality and was very clean.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK469466A DK115861B (en) | 1966-09-12 | 1966-09-12 | Process for the production of gas mixtures with a high calorific value. |
Publications (1)
Publication Number | Publication Date |
---|---|
NO120284B true NO120284B (en) | 1970-09-28 |
Family
ID=8135855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO16969467A NO120284B (en) | 1966-09-12 | 1967-09-11 |
Country Status (7)
Country | Link |
---|---|
BE (1) | BE703755A (en) |
DK (1) | DK115861B (en) |
ES (1) | ES344923A1 (en) |
GB (1) | GB1198671A (en) |
NL (1) | NL6712449A (en) |
NO (1) | NO120284B (en) |
SE (1) | SE321536B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7908283A (en) * | 1979-11-13 | 1981-06-01 | Veg Gasinstituut Nv | PROCESS FOR THE PRODUCTION OF SYNTHETIC NATURAL GAS FROM HYDROCARBONS. |
-
1966
- 1966-09-12 DK DK469466A patent/DK115861B/en unknown
-
1967
- 1967-09-11 NO NO16969467A patent/NO120284B/no unknown
- 1967-09-11 ES ES344923A patent/ES344923A1/en not_active Expired
- 1967-09-12 SE SE12558/67A patent/SE321536B/xx unknown
- 1967-09-12 NL NL6712449A patent/NL6712449A/xx unknown
- 1967-09-12 GB GB4153467A patent/GB1198671A/en not_active Expired
- 1967-09-12 BE BE703755D patent/BE703755A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
NL6712449A (en) | 1968-03-13 |
DK115861B (en) | 1969-11-17 |
SE321536B (en) | 1970-03-09 |
BE703755A (en) | 1968-02-01 |
GB1198671A (en) | 1970-07-15 |
ES344923A1 (en) | 1969-01-01 |
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