CS233464B1 - Continual production of esters - Google Patents
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- CS233464B1 CS233464B1 CS824193A CS419382A CS233464B1 CS 233464 B1 CS233464 B1 CS 233464B1 CS 824193 A CS824193 A CS 824193A CS 419382 A CS419382 A CS 419382A CS 233464 B1 CS233464 B1 CS 233464B1
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- 150000002148 esters Chemical class 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 150000001298 alcohols Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- 235000005985 organic acids Nutrition 0.000 claims abstract description 5
- 230000032050 esterification Effects 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 238000010924 continuous production Methods 0.000 abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 39
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 9
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- -1 ternary Chemical compound 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Vynález rieSi spBsob kontinuálnej výroby esterov organických kyselin. Podstatou sposobu kontinuálnej výroby esterov podTs vynálezu, najma esterov s počtom uhlíkov v molekule 6 až 12 z organických kyselin a alkoholov jo, že do esteriflkačného systému sa privédsajii, s výhodou ako zmes, suroviny nevySe s vodou a/alebo s vodnou fésou z dostilécie esteru v množstvo 2 nž 90 % hmot. vody na suroviny, s výhodou podTa množstva vody v destiláte zníženej o množstvo vody vsnikajúco ostoririkéciou.The invention provides a method of continuous production esters of organic acids. The essence of continuous production esters of the invention, especially esters with a number of carbons in the molecule of 6-12 from organic acids and alcohols do that to esterify of the system is advantageous as a mixture, the raw materials are not washed with water and / or with an aqueous ester from the ester addition in an amount of 2 to 90 wt. water for raw materials preferably according to the amount of water in the distillate reduced by the amount of water that is highly ostorous.
Description
Vynález rležl spOzob kontinuálnej výroby ostorov organických kyselin, najma počtom uhlíkov v molekule 6 až 12.The present invention relates to a process for the continuous production of organic acid islands, in particular by the number of carbons in the molecule of 6 to 12.
Pra přípravu estarov z organických kyselin a alkoholov sa používajú katalytické i nokatalytieká postupy (Beilstein: Handbuch dar organischen Chemie, 4. vydanie, třetí doplmok, diel II. 234, Sprlngar Verlag. Berlin 1960). Sú známe dlskontinuélně i kontinuálna postupy přípravy. Pri diskontinuálnom epdaobe výroby sa zmes kyseliny, alkoholu a kyslého katalyzátore nadávkuje do varáka kolony s nadbytkem alkoholu. Po dvoch hodinách rafluxovania pri totálnom reflexe aa začne s azeotropickým oddestilovaním vody takou rýchlostou, aby na hlava koldny nastúpla koncentrácia kyseliny vo vodnej fáze nad 0,5 % hmot. Vodná vrstva sa odpúžta a organická sa vadle ako raflux na hlavu koldny.Catalytic and nocatalytic processes are used to prepare estars from organic acids and alcohols (Beilstein: Handbuch dar organischen Chemie, 4th edition, third supplement, Volume II. 234, Sprlngar Verlag. Berlin 1960). Continuous and continuous processes are known. In the discontinuous epdaobe of manufacture, the mixture of acid, alcohol and acid catalyst is metered into a column of excess alcohol. After two hours of refluxing under total reflection aa, the water is azeotropically distilled off at a rate such that an acid concentration in the aqueous phase of above 0.5 wt. The aqueous layer is peeled off and the organic layer is boiled as a reflux for the head of the furnace.
Z koldny destiluje ternár voda, alkohol a ester. Kaj přestane destilovat voda, je esterifikáela ukončená a zmes aa po nautralizácil rozdestlluje. Kontinuálna esterlfikácia prebieha tak, ža zmes kyseliny, přebytku alkoholu a katalyzátore sa vedla do koldny, ktorá bývá kontinuálna etážová. Voda ea odoberá ako azetrop ternár voda, alkohol, ester na hlava kolony, zatial čo surový ester sa odoberá zo spodu kolony. Surový ester aa po nautralizácil rozdestlluje (NSR zverejnený spis 2 756 748). Tento postup sa dá použit pre kyseliny a 1 až 8 atómaai uhlíka v molekule a alifatické alebo cykloallfatické alkoholy a 3 až 10 atóaaml uhlíka. Zatial čo množstvo tepla potřebné na destiláciu aaeotropu je spriahnuté v jednom případe a tlakom pár v kolona, v inom případe podía množstva vznikajúceho produktu.The ternary distillates water, alcohol and ester. When the water ceases to distill, the ester is complete and the mixture is distilled after neutralization. The continuous esterification is carried out in such a way that the mixture of acid, excess alcohol and catalyst is led to a coke which is usually a continuous tray. Water ea withdraws as azetrop ternary water, alcohol, ester to the top of the column, while the crude ester is withdrawn from the bottom of the column. The crude ester aa distilled off after neutralization (DE-A-2,756,748). This procedure is applicable to acids and 1 to 8 carbon atoms per molecule and aliphatic or cycloalphatic alcohols and 3 to 10 carbon atoms. While the amount of heat required for distillation of the aaeotrope is coupled in one case and the vapor pressure in the column, in another case according to the amount of product formed.
Ja snámy tiež spdsob, kde sa regulácia robí podía množstva vznikajúcej vody (ZSSR autorská osvědčenis 509 577). Iné kontinuálna postupy na přípravu eaterov používajú přebytek kyseliny voči alkoholu. Nezreagovaný alkohol sa odstráni ako azeotrop alkohol - ester, a zvytok obsahujúci zmes esteru, kyseliny a vody bez alkoholu sa frakčne rozdestlluje. (NSR zvěrajnený spis 2 904 822). V inom kontinuálnom postupe sa dávkujú suroviny, alkohol a kyselina do vařáku esterifikačnej kolony, v ktorej je anorganická kyselina, najčastejžie kyselina sírová ako katalyzátor.I also know how regulation is done according to the amount of water produced (USSR Author's Certificate 509 577). Other continuous processes for preparing the eater use an excess of acid to alcohol. The unreacted alcohol is removed as an alcohol-ester azeotrope, and the residue containing a mixture of ester, acid and water without alcohol is fractionally distilled off. (German published publication 2 904 822). In another continuous process, feedstock, alcohol, and acid are fed to the bottom of an esterification column in which the inorganic acid is most commonly sulfuric acid catalyst.
Vznikajúci ester spolu a vodou a častou alkoholu, ako ternár sa kontinuálna oddestiluje· Po- oddělení organickej fázy od vodnej sa část vody vedle ako raflux na obohacujúcu část kolony, zatial čo organická fáza sa neutralizuje, suší a destiluje, pričom aa získává vyaokokoncantrovaný ester a zmes esteru s alkoholom. (V. V. Beragových,The resulting ester together with water and a portion of the alcohol, such as ternary, is continuously distilled off. · After separating the organic phase from the aqueous and a portion of water besides as a reflux for the enrichment part of the column, the organic phase is neutralized, dried and distilled. ester / alcohol mixture. (V. V. Berag,
V. S. Tiaofeev, O. V. Vaeiljeva, L. A. Serafimov: Chim. prom. No 3, 189 (1973)). Zatial, čo pri prvom apOaobe přípravy, t. j. pri použití přebytku kyseliny na přípravu estarov sú snačná straty kyseliny, ktorá sa z produktu odstraňuje chemickým spdsobom, t. j. nsutraliaáeiou ako i zvláStna kongtrukcia kolony (NSR pat. 2 756 748), pri druhom epdaobe, t. j. pri použití přebytku alkoholu je potřebné čest vydestilovanej vody po rozdělaní ternárneho azeotropu vracat do kolony, aby sa neposúvalo zloženie destilátu 1 násady.V. S. Tiaofeev, O. V. Vaeiljeva, L. A. Serafimov: Chim. prom. No. 3, 189 (1973)). While in the first apoaobe preparation, i. j. when using excess acid for the preparation of estars, there is a considerable loss of acid which is removed from the product by chemical means, i. j. by neutralization as well as by special construc- tion of the column (German Pat. No. 2,756,748), at the second epdaobe, i. j. when using an excess of alcohol, the distilled water honor must be returned to the column after the ternary azeotrope has been separated in order not to shift the composition of the feed distillate 1.
V tomto případe je potřebné spriahnut regulačnými prlstrojmi množstvo vracajúcej sa vody do kolony s množstvom nástreku a množstvom páry potrebnej na destiláciu. Uvedený spdsob js náročný na meranie a reguláciu (ZSSR autorské osvedčenle 451 679, V. Brit. pat. 1 436 410, ZSSR autorské osvedčenle 619 910, 509 577).In this case, the amount of returning water to the column with the amount of feed and the amount of steam required for distillation is to be coupled by means of control devices. This method is difficult to measure and regulate (USSR Author's Certification 451 679, UK Patent No. 1,436,410, USSR Author's Certification 619 910, 509 577).
Uvedená nevýhody odstraňuje spdsob kontinuálnej výroby eaterov podía vynálezu, najma eaterov e počtom uhlíkov v molekule 6 až 12,' z organických kyselin a alkoholov, tak, že do eeterifikačného systému sa privádzajú, s výhodou ako zmes, surovinyinavyže s vodou a/alebo a vodnou fázou z daatilácie esteru v množstve 2 až 90 % hmot. vády na suroviny, s výhodou podía množstva vody v destiláte zníženej o množstvo vody vznikajúee esteriflkáeiouThe above disadvantages are avoided by the process for the continuous production of the eateres according to the invention, in particular of the number of carbons in the molecule of 6 to 12, from organic acids and alcohols by introducing, preferably as a mixture, raw materials with water and / or aqueous % of ester daatilization in an amount of 2 to 90 wt. defects in raw materials, preferably according to the amount of water in the distillate reduced by the amount of water produced by esterification
Uvedený spSsob zlepšuje celkový technologický postup, nakoTko umožňuje přesné dávkavanie jednotlivých zložiek, t. j. zachovanle požadovaného poměru zložiek, ktoré nezávisí navýše od kolísania celkového prletoku zmesi. Tento systém umožňuje zjednodušenle celého spSsobu dávkovania i regulácie prletoku surovin, čím stabilizuje priebeh esterifikácie, zloženie esterifikačnej zmesi a tým zabezpečuje stabilizáciu podmienok rektifikácie zmesi a zloženie destilátu.Said method improves the overall technological process, since it allows accurate dosing of the individual components, i. j. while maintaining the desired ratio of ingredients that does not depend on the variation in the total flow of the mixture. This system simplifies the whole way of dosing and regulating the flow of raw materials, thereby stabilizing the process of esterification, the composition of the esterification mixture and thus ensuring stabilization of the rectification conditions of the mixture and the composition of the distillate.
SpSsob pripravy surovinovej zmesi záleží od druhu použitých kyselin a alkoholov.The method of preparing the raw material mixture depends on the type of acids and alcohols used.
V případe esterifikácie n-butanolu kyselinou octovou dávkujeme obe suroviny v molárnom pomere blízko jednej, napr. 1,00 až 1,05 ku jednej. Nakolko azeotropické zmes ester, voda vrie pri 90,2 °C a má zloženie 73,3 « hmot. esteru a 26,7 % hmot. vody, zatiaT čo reakciou vzniká len 13,4 % hmot. vody je potřebné navýše množstvo vody dávkovať spolu so surovinami, okolo 17 % hmot. v zmesi. V takomto pomere eú zložky zmesi, t. j. kyselina octová, butanol a voda navzájom miešatelná a teda je ju možná pripraviť do dávkovacieho zásobníka a spoločne dávkovať do esteriflkačného zariadenia.In case of esterification of n-butanol with acetic acid, we feed both raw materials in a molar ratio near one, e.g. 1.00 to 1.05 to one. Because of the azeotropic ester mixture, the water boils at 90.2 ° C and has a composition of 73.3% by weight. % ester and 26.7 wt. water, while the reaction produces only 13.4 wt. In addition to the amount of water, it is necessary to add the amount of water together with the raw materials, about 17% by weight. in the mixture. In such a ratio, the components of the mixture, e. j. acetic acid, butanol, and water miscible with each other and thus can be prepared into a dispenser container and co-dispensed into an esterification apparatus.
Ako esterifikačná zariadenie slúži obyčajne esterifikačná kolona s varákom, v ktorom je katalyzátor, a to anorganická kyselina, najčastejšie kyselina sírová, alebo ich zmes, připadne i iné známe esterifikačná katalyzátory s inhibltormi korázle a pod. Vzhladom k tomu, že v surovinách bývajú rozpustná i kej v malých množstvách rozličná ióny železa, vápnika, horčíka napr. ve formě solí s kyselinou, časť kysláho katalyzátora sa z reakcie postupné odčerpává.The esterification column is usually an esterification column with a reboiler in which the catalyst is present, namely an inorganic acid, most often sulfuric acid, or a mixture thereof, or other known esterification catalysts with cadmium inhibitors and the like. Due to the fact that in the raw materials are also soluble in small quantities of different ions of iron, calcium, magnesium, e.g. in the form of acid salts, part of the acid catalyst is gradually pumped out of the reaction.
Z uvedených dSvodov je vhodné určité malé množstvo katalyzátora pridávať priamo do surovin a kontinuálně ho dávkovať do estefifikačného zariadenia, alebo dávkovanie katalyzátora roblť periodicky. V případe, že sa připravuje ester z izobutanolu a kyseliny octovej vzhTadom k nižšieau obsahu vody v destiláte okolo 20 % je potřebná pridať spolu eo surovinami nižšie množstvo vody a to okolo 7 « hmot. V případe použitia kyseliny proplónovej a n-propylalkoholu azeotrop obsahuje 23 % hmot. vody, zatiaT čo reakciou vzniká len 13,4 % hmot. vody, t. j. so surovinami sa dávkuje 10 % hmot. vody. V případe pripravy amylaeetátu azeotrop mé 41 % obsah vody, t. j. do nástreku je potřebné použiť až 29 % vody.Of these reasons, it is advisable to add a small amount of catalyst directly to the feedstocks and continuously feed it to the artification apparatus, or to meter the catalyst periodically. In the case where an ester is prepared from isobutanol and acetic acid because of the lower water content in the distillate of about 20%, it is necessary to add a lower amount of water and about 7% by weight of the raw materials. In the case of proplonic acid and n-propyl alcohol, the azeotrope contains 23 wt. water, while the reaction produces only 13.4 wt. water, t. j. 10% wt. water. In the case of the preparation of amylaeetate azeotrope my 41% water content, t. j. up to 29% water should be used in the spray.
NakoTko pri použití kyselin a alkoholov s vyššou molekulovou hmotnosťou je už miešateTnosť s vodou značné Obmedzené, v týchto prípadoch je potřebné zabezpečiť stále miešanie zmesi v zásobníku, napr. cirkuláciou celej zmesi výkonným čerpadlom. Připadne okrem zmesi kyseliny a alkoholu sa voda samostatné dávkuje do reaktora, přitom však musí byť zachovaný poměr medzi vodou a esterifikačnou zmesou. Známe namerané azeotropické zmesi, t. j. s ohladom na obsah vody je len orientačná a je potřebné pre každý druh použitých surovin si ho upresniť.Since the use of higher molecular weight acids and alcohols, miscibility with water is already very limited, in these cases it is necessary to ensure that the mixture is constantly mixed in the container, e.g. by circulating the entire mixture through a powerful pump. In addition to the acid / alcohol mixture, water is separately fed into the reactor, but the ratio between water and esterification mixture must be maintained. Known azeotropic mixtures, e.g. j. with regard to the water content is only approximate and it is necessary for each type of raw materials used to specify it.
Zatial čo zmes do dávkovacieho zásobníka sa zarába z čistých surovin, připadne surovin získaných z delenia esteru, ako vodu je najvhodnejšie použiť vodnú fázu po oddělení organickej fázy z esteriflkačného produktu, najčastejšie destilátu. Ako reflux na hlavu kolony je možná použiť časť predkondenzátu, alebo tiež vhodnú frakeiu z dalšieho delenia esteru.While the mixture in the dispenser is made up of pure raw materials or raw materials obtained from separation of the ester such as water, it is best to use the aqueous phase after separation of the organic phase from the esterification product, most often the distillate. Part of the precondensate or a suitable fraction from further ester separation may be used as reflux to the top of the column.
Na přípravu esterov podTa tohto vynálezu je vhodná použiť také kyseliny a alkoholy, ktorých estery vytvárajú s vodou azeotropy, v ktorých je obsah vody vyšší, ako množstvo vody vznikajúce reakciou. Sú to najma estery s počtom uhlíkov 6 až 12.For the preparation of the esters according to the invention, it is suitable to use those acids and alcohols whose esters form azeotropes with water in which the water content is higher than the amount of water produced by the reaction. They are in particular esters having a carbon number of 6 to 12.
Ďalšie výhody ako aj spSsob prevedenia je zřejmý z príkladov, ktoré však nevyčerpávajú všetky možné spOsoby použitia.Other advantages as well as methods of implementation are apparent from the examples, which, however, do not exhaust all possible uses.
PřikladlEXAMPLE
Do vařáku laboratórnej esterifikečnej kolony sme privádaall. kontinuálna zmes kyseliny octovej, butanolu a vody o obsahu 36,5 % hmot, kyseliny oetovej, 46,2 % hmot, butanolu a 17,3 % hmot. vody. Vo vařáku bola predsadená zmes 300 g 45 % hmot. kyseliny octovej, % hmot. butanolu, 13 % hmot. vody a 37 % hmot. butylaeetátu. Ako katalyzátor sa použila kyselina sírová v množstve 0,5 % hmot. ne násadu.We were fed to the digester of the esterification column. a continuous mixture of acetic acid, butanol and water containing 36.5% by weight, acetic acid, 46.2% by weight, butanol and 17.3% by weight; water. A 300 g 45 wt. % acetic acid, wt. % butanol, 13 wt. water and 37 wt. butyl acetate. 0.5% w / w sulfuric acid was used as the catalyst. not the handle.
Nástrek surovin bol 170 g/h, vyhrievanie vařáku bolo volené tak, aby bola hladina vo vařáku konitantná. Počas 100 h kontinuálneho chodu sa zloženie vařáku a destilátu prakticky nezměnilo a destilát obsahoval v organickéj fáse 90 až 95 % butylaeetátu, 5 až 7 % butanolu, menej ako 0,1 % hmot. kyseliny octovej a 1,5 % hmot. vody. Přitom na 4,5 kg zmesi nástreku sme přidávali do nástreku 1 g kyseliny sírovej. Obsah vodnéj fázy v destiláte bol 27,5 * hmot.The feed rate was 170 g / h, the digester heating was chosen so that the level in the digester was constant. During 100 hours of continuous operation, the composition of the digester and distillate remained virtually unchanged, and the distillate contained in the organic phase 90 to 95% butyl acetate, 5 to 7% butanol, less than 0.1% by weight. % acetic acid and 1.5 wt. water. We added 1 g of sulfuric acid to the feed for 4.5 kg of the feed mixture. The aqueous phase content of the distillate was 27.5% by weight.
Příklad 2Example 2
Postup v příklade 1 eae modifikovali tým spOsobom, že pri začiatku pokusu sme do varákm predsadili len butanol, kyselinu oetovú a vodu s katalyzátorom. Obsah zložiek v zmesi bol nasledovný: kyselina octová 61 % hmot., butanol 29 % hmot., 9,8 % hmot. vody z 0,2 % hmot. kyseliny p-toluán sulfonovej. Po 30 minútach refluxováním zmesi pri totálnom refluxe sme začali a nástrekoa surovin, samospádem zo zásobnlka s konžtantným tlakom kvapaliny pri výpustnom ventile. Nástrek posostával zo zmesi kyseliny octovej a butanolu ó molárnom pomere 1:1,0. Obsah vody v násadě sme měnili od 15 do 22 % hmot., pričom ako vodu sme používali vodnú fásu a destiláele. Pri uvedenom nástreku sme sledovali zloženie varáka a destilátu. NajvýhodnejSie z hladiska stability koncentrácie jednotlivýoh zložiek sz javí obsah vody v nástreku 17 až 17,5 % hmot. Po zdávkovaní 5 kg nástreku se do vařáku * prlvádsal jednorázové gram kyseliny sírovej.The procedure in Example 1 e and e was modified so that at the start of the experiment only butanol, acetic acid and water with catalyst were introduced into the cookers. The content of the ingredients in the mixture was as follows: acetic acid 61 wt.%, Butanol 29 wt.%, 9.8 wt. water from 0.2 wt. sulfonic acid. After 30 minutes of refluxing the mixture at total reflux, we started and injected the feedstock, by gravity from a reservoir with a constant liquid pressure at the discharge valve. The feed consisted of a 1: 1.0 molar ratio of acetic acid and butanol. The water content of the batch was varied from 15 to 22% by weight, using water phase and distillate as the water. During the above spraying we monitored the composition of the reed and distillate. Most preferably, from the point of view of the stability of the concentration of the individual components, the water content of the feed appears to be 17 to 17.5% by weight. After dosing 5 kg of feed, a single gram of sulfuric acid was added to the digester *.
Přiklad 3 zariadení ako v příklade 1 sme připravovali isobutylacetát esterifikáciou isobutylalkoholu kyselinou Octovou. Do vařáku sme predsadili zmes 180 g kyseliny octovej, g isobutylalkoholu, 6 g vody a 1 g kyseliny sírovej a 0,5 g síranu meňnatého. Ako nástrek eae použili zmes izobutylelkoholu a kyselinou octovou v molárnom pomere 1,02 ku 1,00 e prídavkom 7,5 % hmot. vody na násadu. Za uvedených podmienok bolo zloženie vařáku destilátu počas 100 h reakcie přibližné rovnaká, pričom destilát obsahoval v organickéj fáae eoa 95 % hmot. isobutylaoetátu. Do nástreku na 5 kg zmesi sa přidával 1 g kyseliny sírovej.Example 3 devices as in Example 1 were prepared by isobutyl acetate by esterification of isobutyl alcohol with acetic acid. We added a mixture of 180 g of acetic acid, g of isobutyl alcohol, 6 g of water and 1 g of sulfuric acid and 0.5 g of copper sulphate to the digester. As a feed eae they used a mixture of isobutyl alcohol and acetic acid in a molar ratio of 1.02 to 1.00 e by addition of 7.5 wt. water on the shaft. Under the above conditions, the composition of the distillate digester was approximately the same over 100 h of reaction, with the distillate containing 95% by weight of the organic phase. isobutylaoetátu. 1 g of sulfuric acid was added to the 5 kg feed mixture.
Příklad 4Example 4
Do vařáku eae nasadili amea iaoamylalkoholu e kyseliny propiónovej s obsahom 68 % hmot kyseliny propiónovej a 32 % alkoholu a 0,2 hmot. kyseliny p-toluánsulfónovej ako katalysátora a 0,2 % hmot. síranu aeďnatého ako inhibitore kordsie. Po 1 hodinovoa refluxovanl pri totálnom refluxa sme do zmesi vařáku začali nestrekovať zmes kyseliny propiónovej a Isoaaylalkoholu s obsahom 54,5 * hmot. iaoamylalkoholu a a ňalčieho zásobnlka vodnú fásu a děličky destilátu v množstve 72 % hmot. ne nastrekovenú směs alkoholu a kyseliny.Amea ioamyl alcohol e propionic acid containing 68% by weight of propionic acid and 32% by weight of alcohol and 0.2% by weight of ammonium alcohol was added to the digester eae. % p-toluenesulfonic acid catalyst and 0.2 wt. copper sulfate as a cordsia inhibitor. After refluxing for 1 hour at total reflux, we started not spraying a mixture of propionic acid and isoalcohol with a content of 54.5% by weight. % of ia-amyl alcohol and a further reservoir of water phase and distillate separator in an amount of 72% by weight; not sprayed mixture of alcohol and acid.
Z hlavy kolony sme odoberali destilát o obsahu 95 až 97 % hmot. iaoamylpropionátu a až 5 * hmot. Isoaaylalkoholu v organiekej fáse.A distillate of 95-97% by weight was collected from the top of the column. iaoamyl propionate and up to 5 wt. Isoaaylalcohol in organic phase.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS824193A CS233464B1 (en) | 1982-06-07 | 1982-06-07 | Continual production of esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS824193A CS233464B1 (en) | 1982-06-07 | 1982-06-07 | Continual production of esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS419382A1 CS419382A1 (en) | 1984-02-13 |
| CS233464B1 true CS233464B1 (en) | 1985-03-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS824193A CS233464B1 (en) | 1982-06-07 | 1982-06-07 | Continual production of esters |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS233464B1 (en) |
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1982
- 1982-06-07 CS CS824193A patent/CS233464B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS419382A1 (en) | 1984-02-13 |
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