NO791556L - PROCEDURES FOR REDUCING IRON (III) CHLORIDE TO IRON (II) CHLORIDE - Google Patents
PROCEDURES FOR REDUCING IRON (III) CHLORIDE TO IRON (II) CHLORIDEInfo
- Publication number
- NO791556L NO791556L NO791556A NO791556A NO791556L NO 791556 L NO791556 L NO 791556L NO 791556 A NO791556 A NO 791556A NO 791556 A NO791556 A NO 791556A NO 791556 L NO791556 L NO 791556L
- Authority
- NO
- Norway
- Prior art keywords
- chloride
- iron
- iii
- reaction
- sulfur
- Prior art date
Links
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims description 87
- 229910021578 Iron(III) chloride Inorganic materials 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 44
- 229910021577 Iron(II) chloride Inorganic materials 0.000 title claims description 13
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 title claims description 13
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000004508 fractional distillation Methods 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 10
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4507—Compounds containing sulfur and halogen, with or without oxygen containing sulfur and halogen only
- C01B17/4538—Compounds containing sulfur and halogen, with or without oxygen containing sulfur and halogen only containing sulfur and chlorine only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
Description
"Fremgangsmåte til å redusere jern(III)-klorid til jern(II)- "Procedure for reducing iron(III) chloride to iron(II)-
klorid".chloride".
Denne oppfinnelse angår reduksjon av jern(III)-klorid til jern(II)-klorid. This invention relates to the reduction of iron (III) chloride to iron (II) chloride.
I henhold til en spesiell utførelsesform angår den foreliggende oppfinnelse en forbedret fremgangsmåte til å redusere jern(III)-klorid til jern(II)-klorid som en del av en prosess for utvinning av klorverdiene fra jernklorid. According to a particular embodiment, the present invention relates to an improved method for reducing iron (III) chloride to iron (II) chloride as part of a process for extracting the chlorine values from iron chloride.
I USA-patent 4 140 746 beskrives en fremgangsmåte til utvinning av klorverdiene fra jernklorid erholdt som biprodukt ved klorering av et titanholdig materiale, såsom ilmenitt. US patent 4,140,746 describes a method for extracting the chlorine values from iron chloride obtained as a by-product from the chlorination of a titanium-containing material, such as ilmenite.
I den britiske patentsøknad nr. 18652/78 beskrives en liknende prosess for utvinning av klorverdiene fra jernklorid erholdt som biprodukt ved klorering av et aluminiumholdig materiale, såsom bauksitt. In the British patent application no. 18652/78, a similar process is described for extracting the chlorine values from ferric chloride obtained as a by-product from the chlorination of an aluminium-containing material, such as bauxite.
Disse prosesser omfatter utvinning av klorverdiene fra jernklorid under anvendelse av tre trinn: These processes include the extraction of the chlorine values from ferric chloride using three steps:
(a) jern(III)-klorid underkastes en partiell avkloring(a) ferric chloride is subjected to partial dechlorination
i nærvær av ett eller flere egnede reduksjonsmidler under dannelse av jern(II)-klorid og en klorid-forbindelse; (b) jern(II)-klorid underkastes en oksydasjonsreaksjon med oksygen eller luft under dannelse av jern(III)-klorid og jern(III)-oksyd; (c) det resulterende jern(III)-klorid resirkuleres til trinnet for partiell avkloring (a). in the presence of one or more suitable reducing agents to form ferric chloride and a chloride compound; (b) ferric chloride is subjected to an oxidation reaction with oxygen or air to form ferric chloride and ferric oxide; (c) the resulting ferric chloride is recycled to the partial dechlorination step (a).
I henhold til disse prosesser blir således klorverdiene utvunnet fra .jernklorid-utgangsmaterialet under det partielle avkloringstrinn (a) i hvilket jern(III)-klorid reduseres til jern(II)-klorid, under anvendelse av et egnet reduksjonsmiddel. Thus, according to these processes, the chlorine values are recovered from the ferric chloride feedstock during the partial dechlorination step (a) in which ferric chloride is reduced to ferric chloride, using a suitable reducing agent.
Et egnet reduksjonsmiddel i forbindelse med disse oppfinnelser ble definert som et middel som oppfyller de to følgende kriterier: for det første at det er effektivt ved avkloring av jern(III)-klorid til jern(II)-klorid; for det annet at det ved reaksjon med jern(III)-klorid produserer en klorid-forbindelse som, direkte eller etter ytterligere prosessbehandling, enten er egnet for resirkulering til kloreringsprosessen (om dette er aktuelt eller ønskelig) eller har annen industriell anvendelse. A suitable reducing agent in connection with these inventions was defined as an agent which meets the following two criteria: firstly, that it is effective in dechlorinating ferric chloride to ferric chloride; secondly, that by reaction with iron(III) chloride it produces a chloride compound which, directly or after further process treatment, is either suitable for recycling to the chlorination process (if this is applicable or desirable) or has other industrial applications.
Av de forskjellige reduksjonsmidler som er beskrevet som egnet i USA-patent 4 140 746 og britisk patentsøknad nr.. 18652/78, er anvendelse av flytende svovel ved reaksjon med fast jern(III)-klorid spesielt eksemplifisert. Denne reaksjon er oppsummert i ligning (1) nedenfor: Of the various reducing agents described as suitable in US Patent 4,140,746 and British Patent Application No. 18652/78, the use of liquid sulfur in reaction with solid ferric chloride is particularly exemplified. This reaction is summarized in equation (1) below:
(hvor s representerer fast fase, £ representerer (where s represents solid phase, £ represents
væske og g representerer gass)liquid and g represents gas)
Skjønt den réaksjonsmetoden som er oppsummert i ligning (1) er effektiv, så medfører den ikke desto mindre visse problemer. Væske-faststoff-reaksjonen mellom svovel, Although the reaction method summarized in equation (1) is effective, it nevertheless entails certain problems. The liquid-solid reaction between sulfur,
og jern(III)-klorid krever således komplisert utstyr, og be-hovet for å kondensere det gassformige jern(III)-klorid fra oksydasjonstrinnet (b), slik at man kan tilføre fast jern(III)-klorid til den i ligning (1) angitte reaksjon, øker omkost-ningene. and iron(III) chloride thus require complicated equipment, and the need to condense the gaseous iron(III) chloride from the oxidation step (b), so that solid iron(III) chloride can be added to it in equation ( 1) stated reaction, the costs increase.
Gjenvinningen av elementært klor fra svovelmonoklorid som dannes i henhold til den i ligning (1) viste reaksjon, The recovery of elemental chlorine from sulfur monochloride which is formed according to the reaction shown in equation (1),
som er ønskelig med mindre svovelmonokloridet kan resirkuleres direkte til den prosess ved hvilken jernkloridet erholdtes som biprodukt fra først av, omfatter fortrinnsvis to destilla-sjonstrinn.med høye tilbakeløpsforhold i det første trinn. which is desirable unless the sulfur monochloride can be recycled directly to the process by which the ferric chloride was obtained as a by-product from the start, preferably comprises two distillation stages with high reflux ratios in the first stage.
Vi har nå funnet en fremgangsmåte ved hvilken disse We have now found a method by which these
problemer elimineres.problems are eliminated.
Den foreliggende oppfinnelse tilveiebringer såledesThe present invention thus provides
en fremgangsmåte til å redusere jern(III)-klorid til jern(II)-klorid, og fremgangsmåten erkarakterisert" ved at jérn(III)-klorid reduseres i nærvær av svovelmonoklorid.. Reaksjonen a method for reducing iron(III) chloride to iron(II) chloride, and the method is characterized by the fact that iron(III) chloride is reduced in the presence of sulfur monochloride. The reaction
i henhold til oppfinnelsen eksemplifiseres i ligning (2) nedenfor: according to the invention is exemplified in equation (2) below:
Gjennomførbarheten av fremgangsmåten i henhold til ligning (2) er i strid med indikasjonene i litteraturen, idet svovelmonoklorid konvensjonelt anses som et produkt av jern(III)-klorid-reduksjon, som illustrert ved ligning (1), og ikke som en tilført reaktant. Reduksjonen av jern(III)-klorid med svovel til svovelmonoklorid og jern(II)-klorid er en velkjent reaksjon, og det er derfor overraskende å gå ut over dannelsen av svovelmonoklorid ved reduksjonen av jern(III)-klorid, The feasibility of the method according to equation (2) is contrary to the indications in the literature, as sulfur monochloride is conventionally considered a product of iron(III) chloride reduction, as illustrated by equation (1), and not as an added reactant. The reduction of iron(III) chloride with sulfur to sulfur monochloride and iron(II) chloride is a well-known reaction, and it is therefore surprising to go beyond the formation of sulfur monochloride in the reduction of iron(III) chloride,
særlig i betraktning av at svoveldiklorid (SC^) antas å være ustabilt ved temperaturer, ved hvilke svovelmonoklorid (S,^^) i som koker ved 138°C, er gassformig. Vi har imidlertid funnet på basis av praktiske undersøkelser at svoveldiklorid er tilstrekkelig stabilt overfor jern(III)-klorid ved forhøyede temperaturer, og at ligning (2) faktisk er en brukbar fremgangsmåte. especially considering that sulfur dichloride (SC^) is believed to be unstable at temperatures at which sulfur monochloride (S,^^) i which boils at 138°C, is gaseous. However, we have found on the basis of practical investigations that sulfur dichloride is sufficiently stable towards iron (III) chloride at elevated temperatures, and that equation (2) is actually a usable procedure.
Fremgangsmåten til reduksjon av jern(III)-klorid i henhold til den foreliggende oppfinnelse er spesielt tilpasset til å være det partielle avkloringstrinn i en fremgangsmåte for utvinning av klorverdiene fra jernklorid. The method for reducing iron (III) chloride according to the present invention is particularly adapted to be the partial dechlorination step in a method for extracting the chlorine values from iron chloride.
Det jern(III)-klorid som inngår i den fremgangsmåteThe iron (III) chloride that is included in the method
som er oppsummert ved ligning (2), erholdes således fortrinnsvis fra en prosess som beskrevet i USA-patent 4 140 746 og britisk patentsøknad nr. 18652/78. Den foreliggende oppfinnelse er imidlertid ikke begrenset til jern (III)-klorid avledet fra noen spesiell kilde. which is summarized by equation (2), is thus preferably obtained from a process as described in US Patent 4,140,746 and British Patent Application No. 18652/78. However, the present invention is not limited to iron (III) chloride derived from any particular source.
Svovelmonokloridet som tilføres fremgangsmåten ifølge oppfinnelsen er fortrinnsvis hovedsakelig bare S2CI2/eller det er et svovelklorid hvor hovedandelen er S2CI2. I henhold til oppfinnelsen kan imidlertid noe svoveldiklorid eller svovel foreligge i utgangsmaterialet sammen med S2Cl2«The sulfur monochloride added to the method according to the invention is preferably mainly only S2CI2/or it is a sulfur chloride in which the main proportion is S2CI2. According to the invention, however, some sulfur dichloride or sulfur may be present in the starting material together with S2Cl2«
Dette sistnevnte kan således anvendes i kombinasjon med SC1„ eller S. I sistnevnte tilfelle omdannes svovel til S2CI2ved reaksjon med jern(III)-klorid og/eller SC12før reduksjonen av jern(III)-klorid i henholdtil ligning (2). The latter can thus be used in combination with SC1„ or S. In the latter case, sulfur is converted to S2CI2 by reaction with iron (III) chloride and/or SC12 before the reduction of iron (III) chloride according to equation (2).
Reaksjonen mellom svovelmonoklorid og jern(III)-The reaction between sulfur monochloride and iron(III)-
klorid utføres fortrinnsvis i et virvelsjikt av (produkt-) jern(II)-klorid. Sjikttemperaturen holdes fortrinnsvis mellom kokepunktet for svovelmonoklorid (138°C) dg 500°C, helst mellom 200 og 400°C og aller helst mellom 240 og 280°C. chloride is preferably carried out in a fluidized bed of (product) iron(II) chloride. The layer temperature is preferably kept between the boiling point of sulfur monochloride (138°C) and 500°C, preferably between 200 and 400°C and most preferably between 240 and 280°C.
Alternativt kan det anvendes en reaktor med omrørt. sjikt eller en roterovnsreaktor. Alternatively, a stirred reactor can be used. bed or a rotary kiln reactor.
Reaksjonen utføres fortrinnsvis kontinuerlig. The reaction is preferably carried out continuously.
Svovelmonokloridet tilføres fortrinnsvis til reaktoren som en gass, men kan også tilføres som en væske; i hvilket tilfelle det straks forgasses ved kontakt med det varme reaksjonssjikt. The sulfur monochloride is preferably supplied to the reactor as a gas, but can also be supplied as a liquid; in which case it is immediately gasified on contact with the hot reaction bed.
Jern(III)-kloridet tilføres fortrinnsvis som en gassThe iron(III) chloride is preferably supplied as a gas
til reaktoren, men det kan også tilføres som et fast stoff.to the reactor, but it can also be supplied as a solid.
Man foretrekker å anvende mer svovelmonoklorid ennIt is preferred to use more sulfur monochloride than
det som støkiometrisk er påkrevet ifølge ligning (2), slik at inneholdet av jern(III)-klorid i avgassen nedsettes. Eksempelvis vil et overskudd på ca. 100% i relasjon til what is stoichiometrically required according to equation (2), so that the content of iron(III) chloride in the exhaust gas is reduced. For example, a profit of approx. 100% in relation to
ligning (2). normalt være påkrevet, innenfor det mest fore-trukne temperaturområde, for å oppnå et jern(III)-klorid-innhold i avgassen innenfor industrielt akseptable grenser. Avgassen fra reduksjonsreaktoren vil således inneholde en blanding av svoveldiklorid og svovelmonoklorid, sammen med noe ureagert jern(III)-klorid. equation (2). normally be required, within the most preferred temperature range, to achieve an iron (III) chloride content in the exhaust gas within industrially acceptable limits. The exhaust gas from the reduction reactor will thus contain a mixture of sulfur dichloride and sulfur monochloride, together with some unreacted iron(III) chloride.
Avgassen blir fortrinnsvis kondensert til en væske, sentrifugert for fjerning av faste partikler (jern(III)- og jern(II)-klorid). Med mindre svovelklorid-produktet kan resirkuleres direkte til en sulfokloreringsprosess, foretrekker man å sende det til en fraksjoneringskolonne, fra hvilken det oventil uttas klor og nedentil uttas et produkt som tilnærmet består av svovelmonoklorid og som resirkuleres til reduksjonsreaksjonen. Destillasjonskolonnen drives fortrinnsvis ved et trykk-på ca. 10 atmosfærer og en temperatur The exhaust gas is preferably condensed into a liquid, centrifuged to remove solid particles (iron(III) and iron(II) chloride). Unless the sulfur chloride product can be recycled directly to a sulfochlorination process, it is preferred to send it to a fractionation column, from which chlorine is withdrawn at the top and a product consisting approximately of sulfur monochloride is withdrawn at the bottom and is recycled to the reduction reaction. The distillation column is preferably operated at a pressure of approx. 10 atmospheres and a temperature
tt
oventil mellom 20 og 60°C og en bunntemperatur mellom 160upper air between 20 and 60°C and a bottom temperature between 160
og 220°C, slik at rent elementært klor produseres som topp-produkt, og et svovelklorid i hvilket atomforholdet mellom-svovel og klor er tilnærmet lik 1 produseres som bunnprodukt. Alternativt kan destillasjonskolonnen drives ved atmosfære-trykk, med en temperatur oventil på ca. -4 0°C og en temperatur ved bunnen mellom 100 og 140°C. and 220°C, so that pure elemental chlorine is produced as top product, and a sulfur chloride in which the atomic ratio between sulfur and chlorine is approximately equal to 1 is produced as bottom product. Alternatively, the distillation column can be operated at atmospheric pressure, with an overhead temperature of approx. -4 0°C and a temperature at the bottom between 100 and 140°C.
En annen mulighet er å omsette S2Cl2~produktet med karbondisulfid for fremstilling av karbontetraklorid, som kan resirkuleres til karbokloreringsreaksjonen eller selges for andre industrielle prosesser; eller S2Cl2-produktet kan omsettes med karbonmonoksyd for fremstilling av fosgen for resirkulering til karbokloreringsreaksjonen eller for salg til andre industrielle prosesser. Another possibility is to react the S2Cl2~ product with carbon disulfide to produce carbon tetrachloride, which can be recycled to the carbochlorination reaction or sold for other industrial processes; or the S2Cl2 product can be reacted with carbon monoxide to produce phosgene for recycling to the carbochlorination reaction or for sale to other industrial processes.
Jern(II)-klorid-sjiktoverløpet fra reduksjonsreaktoren omdannes fortrinnsvis til jern(III)-klorid og jern(III)-oksyd ved omsetning med en regulert mengde oksygen eller luft, som beskrevet for trinn (b).i den prosess som er beskrevet i USA-patent 4 140 746 og britisk patentsøknad nr. 18652/78 vedrørende utvinning av klorverdier fra jernklorid avledet fra forskjellige kilder. Det resulterende jern(III)-klorid resirkuleres fortrinnsvis til den reduksjonsreaksjon som er foreliggende oppfinnelses gjenstand. The iron (II) chloride bed overflow from the reduction reactor is preferably converted to iron (III) chloride and iron (III) oxide by reaction with a controlled amount of oxygen or air, as described for step (b) in the process described in US Patent 4,140,746 and British Patent Application No. 18652/78 relating to the recovery of chlorine values from ferric chloride derived from various sources. The resulting iron (III) chloride is preferably recycled to the reduction reaction which is the subject of the present invention.
De følgende eksempler vil ytterligere belyse oppfinnelsen. The following examples will further illustrate the invention.
EKSEMPEL 1EXAMPLE 1
Et 100 mm diameter sjikt av jern(II)-klorid-pulverA 100 mm diameter layer of iron(II) chloride powder
ble fluidisert med 260°C med den følgende gassblanding:was fluidized at 260°C with the following gas mixture:
2,8 l/min. jern(III)-klorid-gass2.8 l/min. iron(III) chloride gas
2,4 l/min. nitrogen og2.4 l/min. nitrogen and
7,0 l/min. svovelklorid-gass7.0 l/min. sulfur chloride gas
(S/Cl-molforhold 0,93:1,00)(S/Cl molar ratio 0.93:1.00)
Jern(III)-klorid- og svovelklorid-gassene ble førtThe iron(III) chloride and sulfur chloride gases were passed
inn ved bunnplaten i fluidiseringsreaktoren gjennom separate åpninger og ble således ikke blandet før de kom inn i sjiktet... into the bottom plate of the fluidization reactor through separate openings and were thus not mixed before entering the bed...
Avgassen fra reaktoren ble oppsamlet og forholdsregler bleThe exhaust gas from the reactor was collected and precautions were taken
tatt for å sikre at eventuelt fritt klor ble absorbert i taken to ensure that any free chlorine was absorbed i
svovelklorid-blandingen. Analyse av avgassen gav de følgende the sulfur chloride mixture. Analysis of the exhaust gave the following
... mol-f raks joner: ... mole-f rak ions:
Atomforholdet mellom svovel og klor i svovelklorid-avgassen vil således ses å ha falt til 0,66:1,00 under avkloring av det tilførte jern(III)-klorid. Jern(II)-klorid-reaksjonsproduktet ble funnet i virvelsjiktet. The atomic ratio between sulfur and chlorine in the sulfur chloride exhaust gas will thus be seen to have fallen to 0.66:1.00 during dechlorination of the supplied iron (III) chloride. The ferric chloride reaction product was found in the fluidized bed.
EKSEMPEL 2EXAMPLE 2
Fremgangsmåten i eksempel 1 ble gjentatt under The procedure in example 1 was repeated below
anvendelse av en fluidiseringsgassblanding som følger:using a fluidizing gas mixture as follows:
2,5 l/min. jern(III)-klorid2.5 l/min. ferric chloride
3,7 l/min. nitrogen3.7 l/min. nitrogen
4,2 l/min. svovelmonoklorid med svovel/klor-atomforhold på 1,00:1,00 4.2 l/min. sulfur monochloride with a sulfur to chlorine atomic ratio of 1.00:1.00
Analyse av avgassen gav de følgende mol-forhold:Analysis of the exhaust gave the following mole ratios:
S/Cl-atomforholdet i avgassen falt til 0,64:1,00 The S/Cl atomic ratio in the exhaust dropped to 0.64:1.00
i avgassen.in the exhaust gas.
EKSEMPEL 3EXAMPLE 3
Destillasjonen av et klorrikt svovelklorid produsertThe distillation of a chlorine-rich sulfur chloride produced
i henhold til ligning (2) (skjønt med et lavere S2Cl2-innhold enn normalt) ble utført i en 80 mm diameter Inconel-kolonne. according to equation (2) (albeit with a lower S2Cl2 content than normal) was carried out in an 80 mm diameter Inconel column.
De anvendte tilførselshastigheter var under kolonnens kapasitet, da flaskehalsen var varmebelastningen på kondensatoren. Prøver ble tatt for analyse etter 3 timers forløp, og resultatene The feed rates used were below the capacity of the column, as the bottleneck was the heat load on the condenser. Samples were taken for analysis after 3 hours, and the results
er gitt nedenfor; De teoretiske varmemengder (dvs. varme-tilførselen ved bunnen og varmebelastningen på kondensatoren) are given below; The theoretical heat quantities (i.e. the heat supply at the bottom and the heat load on the condenser)
var opptil 50% høyere i praksis ved de angitte tilførsels-hastigheter. was up to 50% higher in practice at the indicated feed rates.
EKSEMPEL 4 EXAMPLE 4
Fremgangsmåten ble utført som beskrevet i eksempel 3 med unntakelse av at det ble anvendt et trykk på 10 atmosfærer, hvilket resulterte i at klor ble produsert som topp-produkt ved 3 0°C og bunnproduktet ved 210°C. The procedure was carried out as described in example 3 with the exception that a pressure of 10 atmospheres was used, which resulted in chlorine being produced as top product at 30°C and the bottom product at 210°C.
Claims (17)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1998878 | 1978-05-16 | ||
GB1998778 | 1978-05-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
NO791556L true NO791556L (en) | 1979-11-19 |
Family
ID=26254349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO791556A NO791556L (en) | 1978-05-16 | 1979-05-09 | PROCEDURES FOR REDUCING IRON (III) CHLORIDE TO IRON (II) CHLORIDE |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS54150391A (en) |
CA (1) | CA1110038A (en) |
DE (1) | DE2918879A1 (en) |
FR (1) | FR2426021A1 (en) |
IT (1) | IT1116854B (en) |
NO (1) | NO791556L (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2852339A (en) * | 1955-01-21 | 1958-09-16 | Texas Gulf Sulphur Co | Process of chlorinating iron sulfide to produce ferrous chloride and sulfur |
FR1522065A (en) * | 1967-05-08 | 1968-04-19 | Du Pont | Process for the production of metal halides |
GB1304345A (en) * | 1969-02-06 | 1973-01-24 | ||
GB1584359A (en) * | 1976-11-17 | 1981-02-11 | Mineral Process Licensing Corp | Recovery of chlorine values from iron chloride by-produced in chlorination of ilmenite and the like |
-
1979
- 1979-05-09 NO NO791556A patent/NO791556L/en unknown
- 1979-05-10 JP JP5641779A patent/JPS54150391A/en active Pending
- 1979-05-10 CA CA327,369A patent/CA1110038A/en not_active Expired
- 1979-05-10 IT IT49000/79A patent/IT1116854B/en active
- 1979-05-10 DE DE19792918879 patent/DE2918879A1/en not_active Withdrawn
- 1979-05-16 FR FR7912410A patent/FR2426021A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
IT7949000A0 (en) | 1979-05-10 |
DE2918879A1 (en) | 1979-11-22 |
IT1116854B (en) | 1986-02-10 |
JPS54150391A (en) | 1979-11-26 |
FR2426021A1 (en) | 1979-12-14 |
CA1110038A (en) | 1981-10-06 |
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