NO172888B - PROCEDURE FOR DRYING HYDROCARBONES - Google Patents
PROCEDURE FOR DRYING HYDROCARBONES Download PDFInfo
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- NO172888B NO172888B NO900687A NO900687A NO172888B NO 172888 B NO172888 B NO 172888B NO 900687 A NO900687 A NO 900687A NO 900687 A NO900687 A NO 900687A NO 172888 B NO172888 B NO 172888B
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- Prior art keywords
- water
- drying
- hydrochloric acid
- mixture
- desiccant
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000001035 drying Methods 0.000 title claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000002274 desiccant Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229940050176 methyl chloride Drugs 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 235000011148 calcium chloride Nutrition 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000007138 Deacon process reaction Methods 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-OUBTZVSYSA-N chloromethane Chemical group Cl[13CH3] NEHMKBQYUWJMIP-OUBTZVSYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Drying Of Solid Materials (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Compression Or Coding Systems Of Tv Signals (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Closed-Circuit Television Systems (AREA)
- Drying Of Gases (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en fremgangsmåte for tørking av en blanding inneholdende minst et hydrokarbon, saltsyre og vann. The present invention relates to a method for drying a mixture containing at least one hydrocarbon, hydrochloric acid and water.
Man har allerede beskrevet tørking av perkloretylen ved hjelp av en kalsiumkloridoppløsning<M>C. Abstracts", Vol. 99-177 849d og i fravær av saltsyre. Man har videre beskrevet tørking av kloroform CHCI3 og karbontetraklorid CCI4 efter rensing ved ekstrahering fra vann "C. Abstracts", Vol. 62-2227 e med kalsiumklorid CaCl2 men alltid i fravær av saltsyre. Det problem som interesserte foreliggende oppfinnere var å tørke hydrokarboner inneholdende saltsyre og vann uten å fjerne saltsyre. Man finner dette problem ved syntese av klormetaner ved utløpet av kloreringsreaktoren der klormetanene er blandet med saltsyre (hver gang man erstatter et hydrogen-atom med et kloratom får man som underprodukt et mol saltsyre) og vann som innføres under prosessen som urenhet i utgangsstoffene. Det er nødvendig å fjerne vann for å unngå dettes akkumulering i prosessen og også for å unngå å tette til rørledninger og slangeverk på grunn av is og hydrater. Saltsyre gjenvinnes og utnyttes senere ved omdanning til klor i en DEACON-prosess eller en oksykloreringsreaksjon. Hvis man fjerner vann fra denne blanding fra klormetaner ved kondensasjon risikerer man, på grunn av den store oppløselig-het av saltsyre i vann, å oppnå en saltsyreoppløsning i vann som derefter er vanskelig å separere. Det samme ugunstige forhold kan foreligge hvis man vil separere vann fra denne blanding ved hjelp av et tørkemiddel. Til stor overraskelse er det nu funnet at man selektivt kan tørke hydrokarboner inneholdende saltsyre og vann ved å fjerne kun vannet. The drying of perchlorethylene by means of a calcium chloride solution<M>C has already been described. Abstracts", Vol. 99-177 849d and in the absence of hydrochloric acid. One has further described the drying of chloroform CHCI3 and carbon tetrachloride CCI4 after purification by extraction from water "C. Abstracts", Vol. 62-2227 e with calcium chloride CaCl2 but always in the absence of hydrochloric acid. The problem that interested the present inventors was drying hydrocarbons containing hydrochloric acid and water without removing hydrochloric acid. This problem is found in the synthesis of chloromethanes at the outlet of the chlorination reactor where the chloromethanes are mixed with hydrochloric acid (every time you replace a hydrogen atom with a chlorine atom, you get a mole of hydrochloric acid as a by-product) and water, which is introduced during the process as an impurity in the starting materials. It is necessary to remove water to avoid its accumulation in the process and also to avoid clogging of pipelines and hose works due to ice and hydrates. Hydrochloric acid is recovered and later utilized by conversion to chlorine in a DEACON process or an oxychlorination reaction. Removing water from this mixture from chloromethanes by condensation risks, due to the high solubility of hydrochloric acid in water, to obtain a hydrochloric acid solution in water which is then difficult to separate. The same unfavorable situation can exist if one wants to separate water from this mixture by means of a desiccant. Much to his surprise, it has now been found that hydrocarbons containing hydrochloric acid and water can be selectively dried by removing only the water.
Foreliggende oppfinnelse angår således en fremgangsmåte for tørking av en blanding inneholdende minst et hydrokarbon, saltsyre og vann, og fremgangsmåten karakteriseres ved at man bringer blandingen i kontakt med et tørkemiddel valgt blant (i) vannfrie metalliske sulfater, klorider eller perklorater, eller (ii) fosforpentoksyd inntil tørkemidlet har fanget opp mesteparten av vannet. The present invention thus relates to a method for drying a mixture containing at least one hydrocarbon, hydrochloric acid and water, and the method is characterized by bringing the mixture into contact with a drying agent selected from (i) anhydrous metallic sulphates, chlorides or perchlorates, or (ii) phosphorus pentoxide until the desiccant has absorbed most of the water.
Selv om oppfinnelsen angår alle hydrokarboner anvendes den fortrinnsvis på benzen og alkyl- eller polyalkylderivater derav, det vil si benzen som er substituert med en eller flere hydrokarbonkjeder av lineær eller forgrenet type med hver opptil 8 karbonatomer. Man kan for eksempel nevne benzen, toluen, xylen, isopropylbenzen, styren og etylbenzen. Oppfinnelsen også hydrogenerte karboner. Although the invention relates to all hydrocarbons, it is preferably applied to benzene and alkyl or polyalkyl derivatives thereof, i.e. benzene which is substituted with one or more hydrocarbon chains of linear or branched type with up to 8 carbon atoms each. Examples include benzene, toluene, xylene, isopropylbenzene, styrene and ethylbenzene. The invention also hydrogenated carbons.
Halogenerte hydrokarboner kan inneholde fluor, klor eller brom eller to eller tre av disse elementer, være mettet eller umettet, ha en eller flere dobbeltbindinger eller en eller flere trippelbindinger, eller enhver kombinasjon av disse muligheter. Fortrinnsvis inneholder det halogenerte hydrokarbon mellom 1 og 4 karbonatomer. Oppfinnelsen er spesielt brukbar for klormetaner og for klorerte hydrokarboner med 2 karbonatomer. Blant klorerte hydrokarboner med 2 karbonatomer snakker man fortrinnsvis om 1,2-dikloretan, vinyl-klorid, 1,1,1-trikloretan, 1,1,2-trikloretan, trikloroetylen og perkloroetylen. Halogenert hydrokarbon kan være en blanding av flere halogenerte hydrokarboner. Den kan også være et oppløsningsmiddel. Mengden saltsyre kan være en hvilken som helst og mengden vann også. Imidlertid ligger vannmengden fortrinnsvis under 1 vekt-# og fortrinnsvis under 0,2 vekt-#. Halogenated hydrocarbons may contain fluorine, chlorine or bromine or two or three of these elements, be saturated or unsaturated, have one or more double bonds or one or more triple bonds, or any combination of these possibilities. Preferably, the halogenated hydrocarbon contains between 1 and 4 carbon atoms. The invention is particularly useful for chloromethanes and for chlorinated hydrocarbons with 2 carbon atoms. Among chlorinated hydrocarbons with 2 carbon atoms, we preferably talk about 1,2-dichloroethane, vinyl chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene and perchloroethylene. Halogenated hydrocarbon can be a mixture of several halogenated hydrocarbons. It can also be a solvent. The amount of hydrochloric acid can be any and the amount of water as well. However, the amount of water is preferably below 1 wt-# and preferably below 0.2 wt-#.
Man går ikke utenfor oppfinnelsens ramme hvis det gjelder større vannmengder men oppfinnelsen har da ikke den samme økonomiske interesse. For vesentlige mengder vann i størrel-sesorden noen $ eller derover er det mye enklere å benytte konvensjonell separering som destillasjon eller en ekstrahering og derefter å benytte oppfinnelsen. Blandingen kan være gassformig eller flytende eller partielt gassformig. Temperaturen og trykket kan være hvilke som helst. Man kan anvende oppfinnelsen for å tørke blandinger som befinner seg ved temperaturer og trykk der de er disponible uten at det er nødvendig å modifisere dem. Blandingen kan videre inneholde andre produkter, for eksempel fluor. One does not go outside the scope of the invention if larger quantities of water are concerned, but the invention then does not have the same financial interest. For significant amounts of water in the order of a few $ or more, it is much easier to use conventional separation such as distillation or an extraction and then to use the invention. The mixture may be gaseous or liquid or partially gaseous. The temperature and pressure can be any. One can use the invention to dry mixtures which are at temperatures and pressures where they are available without it being necessary to modify them. The mixture may also contain other products, for example fluorine.
Tørkemidlene foreligger i fast form og er lett separerbare fra blandingen. De kan ha form av pulver eller granulat i fast eller hvirvelsjikt. Tørkemidlet er et produkt hvis funksjon er å fange opp kun vann men ikke saltsyre, ikke eventuelt klor hvis dette er tilstede og slett ikke det halogenerte hydrokarbon. Tørkemidlet er et vannfritt salt som selvfølgelig ikke må reagere kjemisk med saltsyre. Metallsulfatet, klorider og perklorater kan med hell benyttes. Man kan for eksempel benytte kalsiumsulfat, natriumsulfat, kobbersulfat, sinkklorid, kalsiumklorid, bariumperklorat eller magnesiumperklorat. Man benytter med hell kalsiumklorid. Kvaliteten til tørkemidlet avhenger av den mengde vann som er i blandingen. The drying agents are in solid form and are easily separable from the mixture. They can be in the form of powder or granules in a fixed or fluidized bed. The desiccant is a product whose function is to capture only water but not hydrochloric acid, not any chlorine if this is present and not at all the halogenated hydrocarbon. The desiccant is an anhydrous salt which, of course, must not react chemically with hydrochloric acid. The metal sulphate, chlorides and perchlorates can be successfully used. For example, you can use calcium sulphate, sodium sulphate, copper sulphate, zinc chloride, calcium chloride, barium perchlorate or magnesium perchlorate. Calcium chloride is successfully used. The quality of the desiccant depends on the amount of water in the mixture.
Fordelaktig benytter man et kalsiumklorid hvis vannmengde ligger mellom 0 og 25 vekt-# og fortrinnsvis mellom 0 og 12$. A calcium chloride whose water content is between 0 and 25% by weight and preferably between 0 and 12% by weight is advantageously used.
For å oppnå en blanding som ikke inneholder mer enn noen ppm vann er det nødvendig å benytte et i det vesentlige vannfritt tørkemiddel. For for eksempel å oppnå en blanding som ikke inneholder mer enn 10 ppm vann er det for eksempel nødvendig å benytte et kalsiumklorid hvis vannmengde er under 5 vekt-5. In order to obtain a mixture that does not contain more than a few ppm of water, it is necessary to use an essentially water-free desiccant. In order to obtain, for example, a mixture which does not contain more than 10 ppm water, it is necessary, for example, to use a calcium chloride whose amount of water is below 5 wt-5.
Eva angår mengden tørkemiddel avhenger denne av den totale mengde vann som skal fanges opp. Når man for eksempel arbeider med et fast tørkemiddelsjikt som befinner seg nær innløpet av strømmen av blandingen som skal tørkes, mettes dette med vann og derefter blir hele sjiktet mettet. For å sikre god tørking er det tilstrekkelig at det er tilbake tilstrekkelig vannfritt tørkemiddel som ennu ikke er mettet med vann. Oppholdstiden for blandingen som skal tørkes sammen med tørkemidlet kan være en hvilken som helst. Fordelaktig er den under 10 minutter og den ligger helst mellom 1 og 5 minutter. Man går ikke utenfor oppfinnelsens ramme ved å benytte oppholdstider som er lengre men dette er ikke nødvendig for å oppnå oppfinnelsens resultat. Eva concerns the amount of desiccant, this depends on the total amount of water to be collected. For example, when working with a solid desiccant layer that is located near the inlet of the flow of the mixture to be dried, this is saturated with water and then the entire layer is saturated. To ensure good drying, it is sufficient that there is sufficient anhydrous desiccant remaining that is not yet saturated with water. The residence time of the mixture to be dried together with the desiccant can be any. Advantageously, it is under 10 minutes and preferably between 1 and 5 minutes. One does not go outside the framework of the invention by using residence times which are longer, but this is not necessary to achieve the result of the invention.
Lange oppholdstider tilsvarer et stort tørkemiddelvolum. Dette er en god sikkerhet for å oppnå en god tørking men dette vesentlige volum kan gi grunn til tap som ikke er kompatible med resten av prosessen. Fagmannen vet å velge de riktige størrelser for å oppnå et godt kompromiss. Long residence times correspond to a large desiccant volume. This is a good guarantee for achieving good drying, but this significant volume can cause losses that are not compatible with the rest of the process. The professional knows how to choose the right sizes to achieve a good compromise.
Oppfinnelsen kan anvendes ved syntese av klormetaner idet man på et hvilket som helst punkt under prosessen bringer en blanding inneholdende minst et klormetan, saltsyre og vann i kontakt med et tørkemiddel valgt blant (i) vannfrie metalliske sulfater, klorider eller perklorater eller (ii) fosforpentaklorid. The invention can be used in the synthesis of chloromethanes by contacting at any point during the process a mixture containing at least one chloromethane, hydrochloric acid and water with a drying agent selected from (i) anhydrous metallic sulfates, chlorides or perchlorates or (ii) phosphorus pentachloride .
Oppfinnelsen skal illustreres nærmere under henvisning til figur 1 som viser oppfinnelsen med eksempel i en syntese av klormetan som er beskrevet nærmere i NO-søknad ....... The invention shall be illustrated in more detail with reference to Figure 1, which shows the invention with an example in a synthesis of chloromethane, which is described in more detail in the NO application .......
I figuren er (20) er en kloreringsreaktor, (30) er HC1 separeringskolonnen, (40) er CH3CI kolonnen, (50) er innretningen for tørking ifølge oppfinnelsen og (60) er innretningen for separering av høyere klormetaner. Ved (1) innfører man CH3CI som kommer fra ikke vist hydroklorering, ved (2) kloreres denne og ved (3) resirkuleres klormetan. Utløpet (4) destilleres ved (30) og man gjenvinner HC1 ved (5) og derefter blir bunnen inneholdende klormetaner, vann og noe EC1 matet til kolonnen (40) via ledningen (6). (7) angir produksjonen av CH3CI, (8) angir tilbakeløpet og (9) resirkuleringen. Ved (60) separerer man de høyere klormetaner; (10, 11 henholdsvis 12) viser fremstilling av CH2CI2» CHCI3 henholdsvis CC14. (9, 13, 14 og 15) representerer CH3CI, CE2CI2, CECI3 og CCI4 som forenes til strømmen (3) og resirkuleres til reaktoren (20). In the figure, (20) is a chlorination reactor, (30) is the HC1 separation column, (40) is the CH3CI column, (50) is the device for drying according to the invention and (60) is the device for separating higher chloromethanes. In (1) CH3CI is introduced which comes from hydrochlorination not shown, in (2) this is chlorinated and in (3) chloromethane is recycled. The outlet (4) is distilled at (30) and HC1 is recovered at (5) and then the bottom containing chloromethanes, water and some EC1 is fed to the column (40) via line (6). (7) denotes the production of CH3CI, (8) denotes the reflux and (9) the recycle. At (60) the higher chloromethanes are separated; (10, 11 and 12 respectively) show the preparation of CH2CI2» CHCI3 and CC14 respectively. (9, 13, 14 and 15) represent CH3CI, CE2CI2, CECI3 and CCI4 which are combined into stream (3) and recycled to reactor (20).
Tørkemidlet er fortrinnsvis kalsiumklorid. Blandingen som skal tørkes trer ut over topp av kolonnen CH3CI ved en temperatur mellom 5 og 60° C og fortrinnsvis mellom 20 og 50°C. Trykket ligger fortrinnsvis mellom 1 og 12 bar absolutt og fortrinnsvis ligger det mellom 4 og 10 bar absolutt. The drying agent is preferably calcium chloride. The mixture to be dried emerges over the top of the CH 3 Cl column at a temperature between 5 and 60°C and preferably between 20 and 50°C. The pressure is preferably between 1 and 12 bar absolute and preferably between 4 and 10 bar absolute.
Mengden vann kan variere innen vide grenser, den er fortrinnsvis under 0,5 vekt-# og ligger aller helst mellom 50 og 500 ppm. Hva angår mengden HC1 er denne avhengig av effekti-viteten til separeringskolonnen HC1, den er generelt under 1000 ppm og ligger fortrinnsvis mellom 50 og 500 pm. The amount of water can vary within wide limits, it is preferably below 0.5% by weight and most preferably between 50 and 500 ppm. As regards the amount of HC1, this depends on the efficiency of the separation column HC1, it is generally below 1000 ppm and is preferably between 50 and 500 pm.
Blandingen over topp av CH3CI kolonnen og som skal tørkes kan også inneholde klor idet konsentrasjonen varierer i henhold til kloreringsreaktorens effektivitet og den eventuelle sluttreaksjon man kan gjennomføre i HC1 kolonnen. Denne konsentrasjon kan gå helt opp i 10.000 ppm. The mixture above the top of the CH3CI column and which is to be dried may also contain chlorine as the concentration varies according to the efficiency of the chlorination reactor and the possible final reaction that can be carried out in the HC1 column. This concentration can go all the way up to 10,000 ppm.
Separeringskolonnen for CH3CI kan være koblet med kolonnen for separering av CH2CI2 eller man kan også ha en enkelt kolonne som avgir CH3CI2 over topp og høyere klormetaner gjennom forskjellige sideavtrekk eller en hvilken som helst kombinasjon av dette, alt godt kjent for fagfolk på destina-sjonsområdet. Man går ikke utenfor oppfinnelsens ramme ved å anbringe tørkeren som anvendes i fremgangsmåten ifølge oppfinnelsen i toppen av denne kolonne i gassfasen som i det vesentlige består av metylklorid. De følgende eksempler skal illustrere oppfinnelsen. The separation column for CH3CI can be connected with the column for separation of CH2CI2 or one can also have a single column which emits CH3CI2 over the top and higher chloromethanes through various side extractions or any combination thereof, all well known to those skilled in the destination area. One does not go outside the scope of the invention by placing the dryer used in the method according to the invention at the top of this column in the gas phase which essentially consists of methyl chloride. The following examples shall illustrate the invention.
Eksempel 1 Example 1
En tørker består av en glasskolonne med høyde 0,5 m og diameter 0,40 m og den er fyllt med 30 kg CaClg korn med diameter 3 til 8 mm i en høyde av 37,5 cm. Mengden vann av dette CaCl2 er 2, 3%. Derefter fører, man gjennom dette sjikt, nedenfra og oppover, strømmen av gassformig CH3CI inneholdende HC1, vann og klor og dette gjør man i 408 timer. Resultatene er angitt i tabell 1. A dryer consists of a glass column with a height of 0.5 m and a diameter of 0.40 m and it is filled with 30 kg of CaClg grains with a diameter of 3 to 8 mm at a height of 37.5 cm. The amount of water in this CaCl2 is 2.3%. The flow of gaseous CH3CI containing HC1, water and chlorine is then passed through this layer, from below upwards, and this is done for 408 hours. The results are shown in Table 1.
Eksempel 2 Example 2
Man arbeider som i eksempel 1 men chargerer tørkeren (nedenfra og oppover i sjiktet) med: You work as in example 1, but charge the dryer (from the bottom up in the layer) with:
Man arb3ider derefter i 32 timer og observerer så en gjennomhull ing av sjiktet. Resultatene er angitt i tabell You then work for 32 hours and then observe a perforation of the layer. The results are shown in the table
II. II.
Eksempel 3 Example 3
Man arbeider som i eksempel 1 men chargerer tørkeren (nedenfra og oppover i sjiktet) med: You work as in example 1, but charge the dryer (from the bottom up in the layer) with:
Man arbeider på denne måte i 12 timer og tilsetter derefter 15 kg CaCl£ med 1$ vann øverst i sjiktet. Man arbeider så ti Isammen 50 timer. You work in this way for 12 hours and then add 15 kg of CaCl£ with 1$ of water at the top of the layer. You then work ten In total 50 hours.
Resultatene er angitt i tabell III. The results are shown in Table III.
Eksempel 4 Example 4
Man arbeider som i eksempel 1 men chargerer tørkeren (nedenfra og oppover i sjiktet) med: You work as in example 1, but charge the dryer (from the bottom up in the layer) with:
Resultatene er angitt i tabell IV. The results are shown in Table IV.
Eksempel 5 (Sammenligning) Example 5 (Comparison)
Man tørker klormetanet på molekylsiktet. Man disponerer i et glassrør med indre diameter 13 mm og høyde 700 mm, 50 g molekylsikt, nemlig 71 ml over 540 mm høyde. Klormetanene er i en flaske og strømmer ved hjelp av tyngdekraften gjennom sjiktet av molekylsikter med en variabel mengde regulert ved hjelp av en nåleventil og dette oppfanges i en egnet innretning under en vasker med konsentrert svovelsyre. The chloromethane is dried on the molecular sieve. One disposes in a glass tube with an inner diameter of 13 mm and a height of 700 mm, 50 g molecular sieve, namely 71 ml over a height of 540 mm. The chloromethanes are in a bottle and flow by gravity through the layer of molecular sieves with a variable amount regulated by means of a needle valve and this is collected in a suitable device under a washer with concentrated sulfuric acid.
En regulær mengde klormetan oppnås og man anbringer kolben under et konstant nitrogentrykk. Man benytter en kaliumsikt på 3 Å i form av 2 mm kuler. A regular amount of chloromethane is obtained and the flask is placed under a constant nitrogen pressure. A potassium sieve of 3 Å in the form of 2 mm balls is used.
Resultatene er angitt i tabell IV der TM betyr molekylsikt. The results are given in Table IV where TM means molecular sieve.
Romhastigheten uttrykkes i l/t og pr. liter molekylsikter. The space velocity is expressed in l/h and per liter molecular sieves.
Man fastslår at HC1 fastholdes som vann på molekylsiktene. It is determined that HC1 is retained as water on the molecular sieves.
Eksempel 6 Example 6
Man benytter en innretning som i fig. 1 der kolonnen 40 med diameter 800 mm omfatter 35 plater med hetter og som virker under et trykk på 90 bar absolutt trykk. Kolonnehodetempera-turen er 40° C, sumptemperaturen er 110°C. Tørkemidlet, CaCl2 i en mengde på over 95$ er anordnet i et fast sjikt i en beholder (50) med diameter 2800 mm og høyde 5800 mm. One uses a device as in fig. 1 where the column 40 with a diameter of 800 mm comprises 35 plates with caps and which operates under a pressure of 90 bar absolute pressure. The column head temperature is 40°C, the sump temperature is 110°C. The desiccant, CaCl2 in an amount of over 95$ is arranged in a solid layer in a container (50) with a diameter of 2800 mm and a height of 5800 mm.
Kondensatoren mates med CE3CI som er tørr ved utløp av tørkeren. The condenser is fed with CE3CI which is dry at the outlet of the dryer.
Strømmen (6) inneholder: The stream (6) contains:
10 til 20% CE3CI 10 to 20% CE3CI
50-100 ppm H20 50-100 ppm H20
100-500 ppm Cl2100-500 ppm Cl2
50-500 ppm HC1 50-500 ppm HCl
80 til 90 % CH2C12+CHC13+CC14. 80 to 90% CH2C12+CHC13+CC14.
Strømmen (8) som utgjør tilbakeløpet i kolonnen som skal destilleres inneholder CE3CI, HC1, Cl2 hvis mengde av H20 er under 20 ppm. The stream (8) which constitutes the reflux in the column to be distilled contains CE3CI, HC1, Cl2 whose quantity of H20 is below 20 ppm.
Strømmen (7) representerer CE3CI trukket av fra kolonnen og hvis sammensetning er identisk med strømmen (8). Stream (7) represents CE3CI withdrawn from the column and whose composition is identical to stream (8).
Strømmen (9) som utgjør delen av tilbakeført CE3CI har samme sammensetning som strømmene (7) og (8). The stream (9) which forms part of the recovered CE3CI has the same composition as the streams (7) and (8).
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO930481A NO175363C (en) | 1989-02-16 | 1993-02-11 | Process for the preparation of chloromethanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8902024A FR2643072B1 (en) | 1989-02-16 | 1989-02-16 | PROCESS FOR DRYING HYDROCARBONS, ITS APPLICATION TO THE PREPARATION OF CHLOROMETHANES |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO900687D0 NO900687D0 (en) | 1990-02-13 |
| NO900687L NO900687L (en) | 1990-08-17 |
| NO172888B true NO172888B (en) | 1993-06-14 |
| NO172888C NO172888C (en) | 1993-09-22 |
Family
ID=9378837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO900687A NO172888C (en) | 1989-02-16 | 1990-02-13 | PROCEDURE FOR DRYING HYDROCARBONES |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0383675B1 (en) |
| JP (1) | JPH07110820B2 (en) |
| KR (1) | KR920005051B1 (en) |
| CN (1) | CN1027502C (en) |
| AT (1) | ATE93505T1 (en) |
| CA (1) | CA2010121C (en) |
| DE (1) | DE69002839T2 (en) |
| DK (1) | DK0383675T3 (en) |
| ES (1) | ES2058829T3 (en) |
| FI (1) | FI101790B1 (en) |
| FR (1) | FR2643072B1 (en) |
| IE (1) | IE68770B1 (en) |
| NO (1) | NO172888C (en) |
| PT (1) | PT93163B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4475564B2 (en) * | 2004-02-03 | 2010-06-09 | 月島機械株式会社 | Concentration system, concentration method, heat treatment system and heat treatment method for water-containing waste liquid |
| EP2560938B1 (en) * | 2010-04-19 | 2017-11-15 | Blue Cube IP LLC | Process for separating chlorinated methanes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307260A (en) * | 1979-12-06 | 1981-12-22 | The Dow Chemical Company | Drying alkyl halides |
| US4614572A (en) | 1985-07-08 | 1986-09-30 | The Dow Chemical Company | Liquid phase chlorination of chlorinated methanes |
-
1989
- 1989-02-16 FR FR8902024A patent/FR2643072B1/en not_active Expired - Lifetime
-
1990
- 1990-02-13 DK DK90400391.0T patent/DK0383675T3/en active
- 1990-02-13 AT AT90400391T patent/ATE93505T1/en not_active IP Right Cessation
- 1990-02-13 DE DE90400391T patent/DE69002839T2/en not_active Expired - Fee Related
- 1990-02-13 EP EP90400391A patent/EP0383675B1/en not_active Expired - Lifetime
- 1990-02-13 NO NO900687A patent/NO172888C/en unknown
- 1990-02-13 ES ES90400391T patent/ES2058829T3/en not_active Expired - Lifetime
- 1990-02-14 IE IE53990A patent/IE68770B1/en not_active IP Right Cessation
- 1990-02-15 CA CA002010121A patent/CA2010121C/en not_active Expired - Fee Related
- 1990-02-15 PT PT93163A patent/PT93163B/en not_active IP Right Cessation
- 1990-02-15 FI FI900770A patent/FI101790B1/en not_active IP Right Cessation
- 1990-02-16 CN CN90101418A patent/CN1027502C/en not_active Expired - Fee Related
- 1990-02-16 KR KR1019900001917A patent/KR920005051B1/en not_active IP Right Cessation
- 1990-02-16 JP JP2036004A patent/JPH07110820B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FI101790B (en) | 1998-08-31 |
| FR2643072A1 (en) | 1990-08-17 |
| NO900687D0 (en) | 1990-02-13 |
| FI900770A0 (en) | 1990-02-15 |
| DK0383675T3 (en) | 1993-10-25 |
| ATE93505T1 (en) | 1993-09-15 |
| IE68770B1 (en) | 1996-07-10 |
| PT93163B (en) | 1996-01-31 |
| JPH07110820B2 (en) | 1995-11-29 |
| IE900539L (en) | 1990-08-16 |
| EP0383675A1 (en) | 1990-08-22 |
| CA2010121C (en) | 1997-08-19 |
| CA2010121A1 (en) | 1990-08-16 |
| DE69002839D1 (en) | 1993-09-30 |
| PT93163A (en) | 1990-08-31 |
| NO172888C (en) | 1993-09-22 |
| KR920005051B1 (en) | 1992-06-26 |
| FR2643072B1 (en) | 1991-07-26 |
| DE69002839T2 (en) | 1994-02-10 |
| ES2058829T3 (en) | 1994-11-01 |
| KR900012873A (en) | 1990-09-03 |
| JPH02255632A (en) | 1990-10-16 |
| CN1027502C (en) | 1995-01-25 |
| EP0383675B1 (en) | 1993-08-25 |
| NO900687L (en) | 1990-08-17 |
| CN1044949A (en) | 1990-08-29 |
| FI101790B1 (en) | 1998-08-31 |
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