CS254480B1 - Separation method of water from water solutions of morpholine - Google Patents
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- CS254480B1 CS254480B1 CS858765A CS876585A CS254480B1 CS 254480 B1 CS254480 B1 CS 254480B1 CS 858765 A CS858765 A CS 858765A CS 876585 A CS876585 A CS 876585A CS 254480 B1 CS254480 B1 CS 254480B1
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 title claims abstract description 139
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000926 separation method Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 15
- 239000008346 aqueous phase Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000009835 boiling Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010533 azeotropic distillation Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- QLPMOCCEEYMNEC-UHFFFAOYSA-N hexan-1-ol;hydrate Chemical compound O.CCCCCCO QLPMOCCEEYMNEC-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 morpholine Chemical class 0.000 description 1
- FWCHISPFSGCORQ-UHFFFAOYSA-N morpholine;hydrate Chemical compound O.C1COCCN1 FWCHISPFSGCORQ-UHFFFAOYSA-N 0.000 description 1
- BGEHHDVYQRNMJB-UHFFFAOYSA-N morpholine;sulfuric acid Chemical compound OS([O-])(=O)=O.C1COCC[NH2+]1 BGEHHDVYQRNMJB-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- HGASFNYMVGEKTF-UHFFFAOYSA-N octan-1-ol;hydrate Chemical compound O.CCCCCCCCO HGASFNYMVGEKTF-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Sposob iddelovania vody z vodných roztokov morfolínu, pri ktorom sa dosiahne podstatné vyššej účinnosti než pri rektifikácii, takže obsah morfolínu v oddelenej vodnej fáze je nižší ako 0,2 % hmot. Zmes obsahujúca morfolín a vodu sa azeotropicky rektifikuje za přítomnosti aspoň jedného C^ až C? - alkoholu. C^ a C^ -alkoholy sa pridávajú v množstve odpovedajúcom ich rozpustnosti v přítomnéj vodě zo zmesi, Cg a C? -alkoholy sa pridávajú vo viacnásobnom množstve. Páry z hlavy kolony sa vedú do koňzenzátora a kondenzát sa privádza do fázovej děličky, z ktorej spodná vrstva s obsahom max. 0,2 % hmot. morfolínu sa odvádza a alkoholová fáza sa vedie sp&ť na hlavu kolony ako reflux. Destilačný zvyšok obsahuje prakticky všetok morfolín a max. 2 % hmot. vody.alebo morfolínu a Cg - alebo C? - alkohol, ktorý sa rozdělí na morfolínovú a alkoholová frakciu rektifikáciou.The method of allocating water from water morpholine solutions in which it is achieved significantly higher efficiency than rectification, so the morpholine content is separate % of the aqueous phase is less than 0.2 wt. A mixture containing morpholine and water is azeotropically rectifies in the presence of at least one C ^ to C? - alcohol. C 1-6 C 1-4 alcohols are added in an amount corresponding to their solubility in the water present in the mixture, Cg and C? -alcohols are added in multiple amount. Vapors from the column head up lead to a condenser and condensate is fed into the phase divider from which the bottom layer with max. 0.2 wt. morpholine is evacuated and the alcohol phase is conducted per column head as reflux. distilling the remainder contains virtually all morpholine and max. 2 wt. or morpholine a Cg - or C? - the alcohol to be separated the morpholine and alcohol fractions by rectification.
Description
Vynález sa týká spósobu oddelovania vody z vodných roztokov morfolínu, připadne pbsahujúcich aj neprchavé látky, pri ktorom sa dosiahne podstatné vyššej účinnosti než pri rektifikácii, takže obsah morfolinu v oddelenej vodnej fáze je nižší než 0,2 i hmot.The present invention relates to a process for separating water from aqueous morpholine solutions, optionally containing non-volatile substances, which results in a substantially higher efficiency than rectification, so that the morpholine content of the separated aqueous phase is less than 0.2% by weight.
Vodné roztoky morfolínu možno zakoncentrovávať rektifikáciou, ktorá sl však vyžaduje vysokoúčinnú kolonu a velký refluxný poměr, čím proces sa stává nehospodárnym. V patente NSR č. 2 405 911 sa preto doporučuje primárné alebo sekundárné aminy, ku ktorým patří aj morfolin, izolovat z vodného organického roztoku destiláciou alebo extrákclou za přítomnosti oxidu uhličitého. Reakciou oxidu uhličitého s primárnými alebo sekundárnými amínml sa znižuje ich prchavosti, zatiaí čo prohavost vody a ostatných organických zlúčenín ostává neznamená. Znižuje sa tiež ich rozpustnost v organických rozpúšťadlách.Aqueous solutions of morpholine can be concentrated by rectification, which however requires a high-efficiency column and a large reflux ratio, making the process uneconomical. In German patent no. No. 2,405,911 it is therefore recommended to isolate primary or secondary amines, including morpholine, from an aqueous organic solution by distillation or extraction in the presence of carbon dioxide. The reaction of carbon dioxide with the primary or secondary amines decreases their volatility, while the water and other organic compounds remain intact. Their solubility in organic solvents also decreases.
Rektifikácia za přítomnosti oxidu uhličitého má sice nižšie nároky na účinnost kolony a na refluxný poměr, avšak ako sa uvádza v patentovom spise, pri delení sa vyžaduje fúkat do delenej zmesi také množstvo oxidu uhličitého, aby bol poměr G„n : ’ 1,8 až 2,5,Although rectification in the presence of carbon dioxide has lower requirements for column efficiency and reflux ratio, however, as stated in the patent specification, the amount of carbon dioxide required to blow into the split mixture is such that the ratio G " n : " 2.5.
CUq paia pričom destilát - voda obsahuje 0,1 i morfolínu a destllačný zbytox 99,2 % morfolínu. Kolona má 15 teoretických etáží nad vstupom CO^. Nevýhodou tohto procesu je nutnost cirkuláoie velkého prúdu oxidu uhličitého, čo si vyžaduje velké investície a prevádzkové náklady.CUq paia wherein the distillate-water contains 0.1% morpholine and a distillation zbytox of 99.2% morpholine. The column has 15 theoretical plates above the CO 2 inlet. The disadvantage of this process is the need to circulate a large stream of carbon dioxide, which requires large investments and operating costs.
Plynný oxid uhličitý zhoršuje tiež přestup tepla pri kondenzácii destilátu.Gaseous carbon dioxide also worsens the heat transfer during condensation of the distillate.
Podlá patentu USA č. 2 776 972 sa morfolin získává zo zriedeného vodného roztoku pomocou alkalického hydroxidu, s ktorým po zmiešaní sa vytvoria dve fázy, jedna obsahujúca v podstatě všetok morfolin a druhá pozostávájúca z relativné zriedeného alkalického roztoku. Po oddělení fáz,'morfolínová fáza sa 3alej spracováva destiláciou a hydroxidová fáza sa použije na neutralizáciu reakčného roztoku obsahujúceho morfolínsulfát a kyselinu sírovú.According to U.S. Pat. No. 2,776,972, morpholine is obtained from a dilute aqueous solution by means of an alkaline hydroxide with which, after mixing, two phases are formed, one containing substantially all of the morpholine and the other consisting of a relatively dilute alkaline solution. After phase separation, the morpholine phase is further processed by distillation and the hydroxide phase is used to neutralize the reaction solution containing morpholine sulfate and sulfuric acid.
Pri realizácii tohto spósobu na ziskanie morfolínu z vodných roztokov vzniká nový problém, ako spracovať a využit relativné koncentrovaný roztok hydroxidu, ak nie je preň použitie. Tiež dalšie zakoncentrovávanie morfolínovej fáze destiláciou je málo účinné, ve3 právě preto sa hladajú nové a účinnejšie spósoby.In carrying out this process for recovering morpholine from aqueous solutions, a new problem arises of how to process and utilize a relatively concentrated hydroxide solution when not used. Also, further concentration of the morpholine phase by distillation is poorly effected, which is why new and more efficient methods are sought.
Sposob výroby a izolácie morfolínu je predmetom aj čs. patentu č. 146 401. Morfolin podlá něho sa získá kondenzačnou reakciou dietanolamínu, pomocou nadbytku kyseliny sírovej. Vzniknutý morfolin po uvolnění neutralizáciou hydroxidom sodným sa izoluje azeotropickou destiláciou za použitia organickéhc^rozpúšťadla alebo zmesi rozpúšťadiel miešatelných s morfolínom a s výhodou miešatelných s vodou, s teplotou varu aspoň 10 °C pod teplotou varu morfolínu a tvoriacioh azeotropiokú zmes s vodou, o teplote varu aspoň 10 °C pod teplotou varu rozpúšťadla, ako je napr. benzén, cyklohexán, trichlóretylén.The method of production and isolation of morpholine is also subject to MS. U.S. Patent No. 5,768,549; 146 401. Morpholine according to this invention is obtained by the condensation reaction of diethanolamine, with an excess of sulfuric acid. The resulting morpholine after release by neutralization with sodium hydroxide is isolated by azeotropic distillation using an organic solvent or mixture of solvents miscible with morpholine and preferably miscible with water, boiling at least 10 ° C below the boiling point of morpholine and forming an azeotropic mixture with water, boiling at least 10 ° C below the boiling point of the solvent, e.g. benzene, cyclohexane, trichlorethylene.
Podlá údajov uvedených v příklade 5 destilácia sa robí bez kolony za použitia azeotropického nástavce. Pri azeotroplckej destilácii s benzénom, v oddelenej vodě je okolo 3 % morfolínu, pri destilácii s toluénom je v oddelenej vodě až 10 až 11 S morfolínu a pri destilácii s trlchlóretylénom obsah morfolínu v oddelenej vodě je 2 až 3 %. Takéto oddelovanie vody od morfolínu je nedostatočné, vodu nemožno vypustit z ekologických dóvodov do odpadných vód a představuje tiež značnú stratu na výrobných nákladoch.According to the data given in Example 5, distillation is performed without a column using an azeotropic adapter. In azeotropic distillation with benzene, in separated water there is about 3% morpholine, in distillation with toluene in separated water up to 10 to 11 S morpholine and in distillation with trichlorethylene the morpholine content in separated water is 2 to 3%. Such separation of water from morpholine is insufficient, water cannot be discharged from ecological reasons into wastewater and also represents a considerable loss in production costs.
Uvedené nedostatky odstraňuje sposob oddelovania vody z vodných roztokov morfolínu, připadne obsahujúcich aj neprchavé látky, podlá tohto vynálezu, pri ktorom zmes obsahujúca morfolin a vodu sa azeotropioky rektifikuje v kolóne za přítomnosti aspoň jedného z až C?,alkoholov, pričom C4. a C5 alkoholy sa pridávajú do delenej zmesi v množstve odpovedajúcom rozpustnosti týchto alkoholov v přítomnéj vodě vo zmesi, Cg- a C^~ alkoholy· sa s výhodou pridávajú do delenej zmesi morfolínu a vody vo viacnásobnom množstve než odpovedá rozpustnosti v přítomnéj vodě, spravidla do 50 % celkového množstva motfolíno-vodnej zmesi, páry z hlavy kolony sa vedú do kondenzátora a kondenzát, s výhodou po ochladení, sa privádza do fázovéj děličky, z ktorej spodná vodná fáza, nasýtená alkoholom, obsahujúca do 0,2 % hmot. morfolinu sa odvádza zo systému na dalšie spracovanie alebo použitie a alkoholová fáza sa vedie sp3t na hlavu kolóny ako reflux, spodkový produkt kolony- destllačný zbytok, obsahuje prakticky všetok morfolín,a max. 2 % hmot. vody alebo morfolín a Cgalebo C? - alkohol , ktorý sa rozdělí na morfolínovú a alkoholovú frakciu rektifikáciou.The above drawbacks overcome the process of separating water from aqueous morpholine solutions, optionally containing nonvolatiles, according to the present invention, wherein the mixture containing morpholine and water is rectified azeotropiically in the column in the presence of at least one of C to C ? alcohols, wherein C 4 . a C 5 alcohol is added to the split composition in an amount corresponding to the solubility of these alcohols in the present water in the composition, C g - and C ^ ~ alcohols · are preferably added to split a mixture of morpholine and water in a multiple amount than corresponds to the solubility in the present of water, as a rule up to 50% of the total amount of motpholino-water mixture, the vapors from the top of the column are fed to the condenser and the condensate, preferably after cooling, is fed to a phase divider from which the lower aqueous phase saturated with alcohol contains 0.2 wt. the morpholine is removed from the system for further processing or use and the alcohol phase is fed back to the top of the column as reflux, the bottom product of the column-distillation residue, contains practically all morpholine, and max. 2 wt. water or morpholine and Cg or C ? an alcohol which is separated into the morpholine and alcohol fractions by rectification.
Z rovnovážných údajov kvapalina - para zmesi voda - morfolín vyplývá, fe relativná prchavost vody klesá so stúpajúcou koncentráciou vody, a preto je obtiažnejšie pri rektifikácii získat na hlavě kolóny čistú vodu /resp. nižší obsah morfolínu v destiláte než 0,1 % hmot./, ako na spodku kolóny čistý morfolín /resp. nižší obsah vody v destilačnom zbytku než 0,1 % hmot./. TZ ekologických a ekonomických dóvodov je však žiadúce, aby destilát, ak sa má vypustit do opadných vod, obsahoval menej než 0,1 % hmot. vody.The equilibrium data of the liquid - steam of the water - morpholine mixture shows that the relative volatility of the water decreases with increasing water concentration and therefore it is more difficult to obtain pure water / resp. lower morpholine content in the distillate than 0.1% w / w than on the bottom of the column pure morpholine (resp. less than 0.1% w / w water in the distillation residue. However, it is desirable that the distillate, if it is to be discharged into waste water, contain less than 0.1% by weight of ecological and economic reasons. water.
Je známe, že prídavkom tretej zložky do zmesi voda - morfolín je možno relatívnu prchavost vody zvýšit· Stane sa tak napr. prídavkom látky tvoriacej s vodou azeotropickú zmes. s min. teplotou varu. Pri homologickej skupině látok ovplyvnenie relatívnej prchavosti vody vzhladom k morfolínu je tým váčšie, čím přidaná látka /azeotropické médium/ má nižšiu teplotu varu. To má však aj negativny dósledok, totiž tým klesá obsah vody v parnej fáze a stúpa obsah azeotropického média.It is known that the addition of a third component to a water-morpholine mixture can increase the relative volatility of water. adding an azeotropic mixture with water. s min. boiling point. For a homologous group of substances, the affecting of the relative volatility of water relative to morpholine is all the more severe as the added substance (azeotropic medium) has a lower boiling point. However, this also has a negative effect, namely that the water content in the vapor phase decreases and the azeotropic medium content increases.
Ešte viac než teplota varu azeotropického media relatívnu prchavost vody ovplyvní povaha látky, jej polarita, schopnost vytváraí vodíkové mostíky, resp. reagovat na nestále zlúčeniny, ktoré sa pri teplote varu rozkladajú na póvodne látky.·Zistili sme, že takéto vlastnosti majú alkoholy, z ktorých výhodné sú najmS tie, ktoré majú obmedzenú rozpustnost s vodou, tvoria s ňou azeotropickú zmes s relativné vysokým obsahom vody a refluxovaním alkoholickéj fázy z kondenzátu pár z hlavy kolóny zaistujú dobré delenie vody a morfolínu v kolóne.Even more than the boiling point of an azeotropic medium, the relative volatility of water will be influenced by the nature of the substance, its polarity, its ability to form hydrogen bridges, or the like. react to volatile compounds which decompose to the parent substances at boiling point · We have found that such alcohols have such properties, of which the most advantageous are those with limited water solubility, forming an azeotropic mixture with a relatively high water content, and by refluxing the alcoholic phase from the condensate vapor from the top of the column, they ensure good separation of water and morpholine in the column.
Teplota varu alkoholov pre volbu azeotropického média nie je rozhodujúca. Móžu to byt alkoholy s teplotou varu nižšou, rovnakou alebo vyššou než je teplota varu morfolínu. teplota varu alkoholu, resp. jeho relativná prchavost vzhladom k morfolínu má však význam pre volbu pracovného postupu azeotropickéj rektifikácie.The boiling point of the alcohols is not critical to the choice of azeotropic medium. They may be alcohols with a boiling point lower, equal to or higher than the boiling point of morpholine. the boiling point of alcohol, respectively. however, its relative volatility relative to morpholine is important for the choice of the azeotropic rectification process.
Tie alkoholy, ktoré majú rovnakú /alebo blízku/ teplotu varu ako morfolín alebo rektifikáciou sa nedajú od morfolínu oddělit, pridávajú sa ako azeotropické médium do delenej zmesi morfolínu a vody iba v takom množstve, aby sa stačili zo systému totálně odviest v rozpustenej alebo aj čiastočne emulgovatelnej formě vo vodnej fáze, ktorá sa odoberá z kolóny ako destilát. Sú to C^- a -alkoholy, ktoré třeba přidávat ako azeotropické médium na delenie zmesi morfolín - voda v množstve odpovedajúcom iba idtiahnutému množstvu s destilátorom - vodnou fázou. Potom destilačný zbytok je prostý alkoholov a móže sa považovat za produkt.Those alcohols having the same / or near / boiling point as morpholine or cannot be separated from the morpholine by rectification, are added as an azeotropic medium to the divided mixture of morpholine and water only in such a quantity as to be totally withdrawn from the system in dissolved or partially emulsifiable form in the aqueous phase, which is taken from the column as a distillate. These are the C ^ --alcohols which need to be added as an azeotropic medium to separate the morpholine-water mixture in an amount corresponding only to the amount withdrawn with the water-phase distiller. Then the distillation residue is free of alcohol and can be considered as a product.
Cg- alkoholy a vyššie majú vyšiu teplotu varu než morfolín, ktorý sa dá od nich oddělit poměrně lahko rektifikáciou.The C8-alcohols and above have a higher boiling point than morpholine, which can be separated relatively easily by rectification.
Tieto alkoholy vytvárajú s vodou azeotropickú zmes s relativné vysokým obsahom vody a nízkým obsahom alkoholu /1-hexanol-voda 75 % hmot. vody, 1-oktanol-voda 90 % hmot. vody/, preto je výhodnějšie přidávat ich ako azeotropické médiem do zmesi morfolín τ voda vo váčšom množstve než odpovedá rozpustnosti v odtahovej vodě ako destilát. Týmto spósobom pri kontinuálnej azeotropickéj rektifikácii alkohol stéká celou kolonou až do varáka, zvyšuje efekt rektifikácie v spodnej časti kolóny a kompenzuje takto znížený efekt vo vrchnej časti kolóny, vyvolaný zníženým refluxom alkoholickéj fázy. Priaznivý vplyv sa prejavuje aj pri diskontinuálnej azeotropickéj rektifikácie, nakolko vo vařáku znižuje relatívnu prchavost morfolínu. Spodkový produkt kolóny /alebo vařákový/ nie je však v tomto případe čistý morfolín, ale zmes morfolínu a alkoholu, ktorá sa lahko rozdělí rektifikáciou.These alcohols form an azeotropic mixture with water with a relatively high water content and a low alcohol / 1-hexanol-water content of 75% by weight. % water, 1-octanol-water 90 wt. It is therefore preferable to add them as azeotropic media to the mixture of morpholine τ water in a quantity greater than that corresponding to the solubility in the withdrawal water than the distillate. In this way, in continuous azeotropic rectification, the alcohol flows through the entire column up to the reed, increasing the rectification effect at the bottom of the column and compensating for the reduced effect at the top of the column caused by the reduced reflux of the alcohol phase. The discontinuous azeotropic rectification also has a beneficial effect, as it reduces the relative volatility of morpholine in the digester. However, the bottom product of the column (or reboiler) is not pure morpholine in this case, but a mixture of morpholine and alcohol, which is readily separated by rectification.
Spósob oddelovania vody z vodných roztokov morfolínu podlá vynálezu možno použit v kontinuálnom alebo diskontinuálnom usporiadaní ako sa to ilustruje v nasledovných príkladoch.The method of separating water from the aqueous morpholine solutions of the invention can be used in a continuous or discontinuous arrangement as illustrated in the following examples.
Příklad 1 /porovnávací/Example 1 (comparative)
Do 4. článku kontinuálnej rektifikačnej kolony, pozostávajúcej z 8 článkov vnútorného priemeru 100 mm, výšky 1 000 mm, naplněných keramickými Rasohigovými krúžkami 10 x 10 mm, sa nastrekuje predohriata zmes 50 % hmot. vody a 50 % hmot. morfolínu. Teplo na oddestilovanie vody zo zmesi sa dodává do cirkulačného vařáku regulované vykuřovaného nepriamou parou. Páry, vystupujúce z hlavy kolony torálne kondenzujú v spátnom kondenzátore a horúci kondenzát sa dělí v elektromagneticky regulovanom děliči refluxu na destilát a reflux, ktorý sa vracia spát na hlavu kolony. Refluxný poměr pri rektifikácii je 2,3. Destilačný zbytok r.a kontinuálně odoberá z varáka cez sifonový přepad do zísobníka destilačného zbytku. Po ustálení chodu kolony sa odoberú vzorky destilátu a destilačného zbytku, ktoré vykazujú následovně zloženie: destilát 98,2 % hmot. vody, 1,8 % hmot. morfolínu; destilačný zbytok 91,2 % hmot. morfolínu a 8,8 hmot. % vody.A prewarmed mixture of 50 wt.% Was injected into a fourth cell of a continuous rectification column consisting of 8 cells of 100 mm internal diameter, 1000 mm height, filled with 10 x 10 mm ceramic Rasohig rings. water and 50 wt. morpholine. The heat to distill the water from the mixture is supplied to a controlled recycle steam boiler. The vapors exiting the top of the column condensate condensate in the back condenser, and the hot condensate is separated in the electromagnetically controlled reflux divider into distillate and reflux, which returns back to the column head. The reflux ratio at rectification is 2.3. The distillation residue r.a is continuously withdrawn from the reboiler via a siphon overflow into the distillation residue receiver. After the column has stabilized, samples of the distillate and distillation residue are taken which have the following composition: distillate 98.2% by weight. water, 1.8 wt. morpholine; distillation residue 91.2 wt. morpholine and 8.8 wt. % water.
Příklad 2Example 2
Na tejže koloně ako v příklade 1, sa robí azeotropická rektifikácia. Do kolony sa nasktrekuje zmes 46 i hmot. vody, 50 % hmot. morfolínu a 4 % hmot. 1-butanolu. Kondenzát vzniklý kondenzáciou pár z hlavy kolony sa vedie cez dochladzovač do fázovéj deličky, kde sa rozdělí na spodnú vodnú fázu a vrohnú butanolovú fázu. Vodná fáza sa kontinuálně odvádza do zásobníka destilátu a butanolová fáza na hlavu kolony ako reflux. Obsah morfolínu vo vodnej fáze je 0,02 % hmot. a v destilačnom zbytku 99,2 í hmot.Azeotropic rectification is performed on the same column as in Example 1. A mixture of 46% by weight was injected into the column. water, 50 wt. % morpholine and 4 wt. 1-butanol. The condensate formed by the condensation of the vapors from the top of the column is passed through a quencher into a phase separator where it is separated into the lower aqueous phase and inhale the butanol phase. The aqueous phase is continuously discharged to the distillate reservoir and the butanol phase to the top of the column as reflux. The morpholine content of the aqueous phase is 0.02% by weight. and in the distillation residue 99.2% by weight.
Příklad 3Example 3
Podobným sposobom a na tejže aparatúre ako v příklade 2 sa robí azeotropická rektifikácia s tým rozdielom, že miesto 1-butanolu sa použije 2-metyl-l-propanol. Obsah morfolínu vo vodnej fáze je 0,005 % hmot. a v destilačnom zbytku 99,6 % hmot.In a similar manner and on the same apparatus as in Example 2, azeotropic rectification was performed except that 2-methyl-1-propanol was used instead of 1-butanol. The morpholine content of the aqueous phase is 0.005% by weight. and in the distillation residue 99.6 wt.
Příklad 4Example 4
Laboratórna kontinuálna azeotropická rektifikácia zmesi voda-morfolín za přítomnosti technického 3-metyl-1-butanolu. Kolona má vnútorný priemer 30 mm, výšku 2 x 350 mm a je naplněná kovovými Spirálkami já 2,5 mm. Účinnost kolony podfa zataženia je 20 až 25 teoretických etáží. Použitý alkohol a obsahuje 80 % hmot. 3-metylbutanolu-l-a 20 % hmot. 2-metylbutanolu-1. Poměr vody k morfolínu v nástreku je 1:1 a zmes obsahuje 2,5 i hmot. alkoholu, počítané na množstvo vody. Pri azeotropiokej rektifikácii zmes uvedeného zloženia sa predohrieva na 90 °C a rovnoměrně sa nastrekuje do středu kolony. Po kondenzácii pár odchádzajúcich z hlavy kolony, vodná fáza sa odoberá ako destilát a alkoholová fáza sa vracia do kolony ako reflux. Po dosiahnutí rovnováhy destilát obsahuje 0,12 % morfólínu a destilačný zbytok 99,53 % morfolínu.Laboratory continuous azeotropic rectification of water-morpholine mixture in the presence of technical 3-methyl-1-butanol. The column has an inner diameter of 30 mm, a height of 2 x 350 mm, and is filled with metal coils 2.5 mm. The load efficiency of the column is 20 to 25 theoretical plates. The alcohol used contains 80 wt. % 3-methylbutanol-1- and 20 wt. 2-methylbutanol -1. The ratio of water to morpholine in the feed is 1: 1 and the mixture contains 2.5% by weight. alcohol, calculated on the amount of water. For azeotropiectic rectification, the mixture of the above composition is preheated to 90 ° C and injected evenly into the center of the column. After condensation of the vapors leaving the top of the column, the aqueous phase is collected as a distillate and the alcohol phase is returned to the column as reflux. Upon reaching equilibrium, the distillate contains 0.12% morpholine and the distillation residue 99.53% morpholine.
Příklad 5Example 5
Na tejže kolóne v příklade 4 sa urobí diskontinuálna azeotropická rektifikácia zmesi voda-morfolín za přítomnosti 1-hexanolu ako azeotropického média. Do zmesi voda-morfolín sa přidá 16,7 % hmot. 1-hexanolu a zmes v destilačnej banke sa uvedie do varu. Páry stúpajú kolonou, do ktorej zvrchu sa privádza hexanolová fáza ako reflux z azeotropickej destilačnej hlavy. Vodná fáza - destilát, sa odoberá z azeotropickej hlavy po .frakciách, v ktorých sa stanovuje obsah morfolínu. Po vydestilovaní vody a zastavení prírastku vodnej fázy azeotropická destilačná hlava sa vymění za normálnu destilačnú hlavu s elektromagnetickou reguláciou refluxného poměru.On the same column in Example 4, a discontinuous azeotropic rectification of the water-morpholine mixture is performed in the presence of 1-hexanol as an azeotropic medium. To the water-morpholine mixture was added 16.7 wt. 1-hexanol and the mixture in a distillation flask are brought to boiling. The vapors rise through a column into which a hexanol phase is fed as a reflux from the azeotropic distillation head. The aqueous phase - distillate, is taken from the azeotropic head after fractions in which the morpholine content is determined. After distilling off the water and stopping the aqueous phase increment, the azeotropic distillation head is replaced with a normal distillation head with electromagnetic reflux ratio control.
Ďalej sa pokračuje v rektifikácii pri refluxnom pomere 5:1 a dalej sa odoberá analyzujú frakcie destilátu.The rectification is continued at a reflux ratio of 5: 1 and the fractions of the distillate are collected and analyzed.
Výsledky sú následovně:The results are as follows:
a/ azeotropická rektifikáciaand / azeotropic rectification
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| CS858765A CS254480B1 (en) | 1985-12-02 | 1985-12-02 | Separation method of water from water solutions of morpholine |
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| CS858765A CS254480B1 (en) | 1985-12-02 | 1985-12-02 | Separation method of water from water solutions of morpholine |
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