PL106277B1 - METHOD OF MAKING HIGH PURITY DIMETHYLTERETHALATE - Google Patents
METHOD OF MAKING HIGH PURITY DIMETHYLTERETHALATE Download PDFInfo
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- PL106277B1 PL106277B1 PL19491276A PL19491276A PL106277B1 PL 106277 B1 PL106277 B1 PL 106277B1 PL 19491276 A PL19491276 A PL 19491276A PL 19491276 A PL19491276 A PL 19491276A PL 106277 B1 PL106277 B1 PL 106277B1
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- Prior art keywords
- dmt
- methanol
- oxidation
- pte
- temperature
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- 238000004519 manufacturing process Methods 0.000 title description 7
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 claims 1
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 claims 1
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 20
- 238000009835 boiling Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 150000004702 methyl esters Chemical class 0.000 description 4
- -1 terephthalate ester Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- JLWMMYZWEHHTFF-UHFFFAOYSA-N 2-[6-(3-carbamimidoylphenoxy)-4-[di(propan-2-yl)amino]-3,5-difluoropyridin-2-yl]oxy-5-(2-methylpropylcarbamoyl)benzoic acid Chemical compound OC(=O)C1=CC(C(=O)NCC(C)C)=CC=C1OC1=NC(OC=2C=C(C=CC=2)C(N)=N)=C(F)C(N(C(C)C)C(C)C)=C1F JLWMMYZWEHHTFF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000003176 fibrotic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób prowadze¬ nia procesu utleniania pnkisylenu i jego pochod¬ nych do kwasu p-toluilowego (KpT) i tereftalo¬ wego (KTT) oiraiz do estru mohometylotereftalo¬ wego lanu (DMT) od produktów bardziej od niego lot¬ nych oraz sposób oczyszczania tzw. surowego dwuimetylotereftalanu na drodze, krystalizacji z roztwoiru .metanolu.The subject of the invention is a process the process of oxidation of p-pnysylene and its derivatives to p-toluic acid (KpT) and terephthalate tet (KTT) to the mohomethyl terephthalate ester wego peroxide (DMT) than more volatile products and the method of cleaning the so-called raw dimethyl terephthalate by crystallization from methanol solution.
W procesie wytwarzania dwumetylotereftalanu metoda Witten do tej pory rozdzial ^estryfikowa¬ nych metanolem produktów utleniania pnksylenu i jego pochodnych, w tym glównie estru metylo¬ wego kwasu p-toluilowego (pTE) od DMT odbywal sie na drodze rektyfikacji, przy czym nie zwra¬ cano szczegóilinej uwagi na zawartosc w cieczy wyczerpanej (stanowiacej glównie mieszanine dwu- meityloiteireftalanu i substancji od niego wyzej wrzacych) takich zwiazków jak ester metylowy kwasu p-toluilowego, ester metylowy kwasu ben¬ zoesowego (BE), ester metylowy kwasu p-formy- lobenzoesowego (TAE), aldehydu tereftalowego.In the production of dimethyl terephthalate the Witten method so far has been esterified products of p-xylene oxidation with methanol and its derivatives, including mainly the methyl ester p-toluic acid (pTE) from DMT took place rectified, but not returned cano pay special attention to the content in the liquid exhausted (constituting mainly a mixture of two meityliterephthalate and substances above boiling) compounds such as methyl ester p-toluic acid, petroleum acid methyl ester zoic acid (BE), p-form- acid methyl ester lobenzoic acid (TAE), terephthalaldehyde.
Zawartosc tych zwiazków wynoisi na ogól 2—4% wag. skladu otrzymywanej cieczy wyczerpanej (surowego DMT), w tym zawartosc pTE wynosi I-i-1,5% wag.The content of these compounds is generally 2-4% wt. composition of the obtained exhausted liquid (raw DMT), including the pTE content is 1-1.5 wt.%
Wymienione wyzej zwiazki chemiczne sa na o- gói oddzielane oid DMT na drodze krystalizacji (ma ogól dwustopniowej) z roztworu metanolowego, le 1S jednak istnieje zawsze mozliwosc ich przedosta¬ wania sie w pewnym stopniu do produktu final¬ nego, do DMT, bedacego surowcem do wytwarza¬ nia politereftalanu etylowego, wlóknotwcirczego, jak równiez dla potrzeb folii poliestrowej. Obec¬ nosc w DMT czystym takich zwiazków jak pTE, BE, TAE powoduje klopoty w procesie poliikon- denisacji dwuiglikolotereftalainu, objawiajace sie glównie w postaci zaburzen we wzroscie lancucha polimerowego oraz w barwie podimeru.The above-mentioned chemical compounds are top separated by DMT oid by crystallization (ma general two-stage) from methanol solution, le 1S however, there is always the possibility of getting through to some extent to the final product to DMT, which is the raw material for production polyethylene terephthalate, fibrotic, as well as for the needs of polyester film. Present nosc in pure DMT of compounds such as pTE, BE, TAE causes problems in the polyicon- denization of diiglycolyterephthalene, manifested mainly in the form of disturbances in the growth of the chain polymer and in the color of the podimer.
Na podstawie wykonanych doswiadczen w sikali laboratoryjnej i technicznej stwierdzono ponadto, ze w procesie krystalizacji DMT z roztworu me¬ tanolowego, w obecnosci pTE, BE i TAE, zwieksza sie w pewnym stopniu rozpuszczalnosc DMT w lugu pokirystalicznym.Based on experiments performed in piss laboratory and technical studies, it was also found that in the process of crystallization of DMT from a solution of tanole, in the presence of pTE, BE and TAE, increases to some extent the solubility of DMT in post-crystalline lug.
Proces krystalizacji prowadzi sie na. ogól w ten sposób, ze roztwór DMT w metanolu o tempera¬ turze oik 100°C oziebia sie do^ temperatury ok. 64°C przez adiabatyczne odparowanie rozpuszczal¬ nika, a nastepnie do> temperatury ok. 35—40°C chlodzi przepoinowo', ^przy pomocy medium chlod¬ niczego. Przy chlodzeniu przeponowym nalezy zwrócic uwage, by utrzymywac mala róznice tem¬ peratur miedzy roztworem a powierzchnia chlo¬ dzaca. Powoduje to nadmierne wydluzenie cyklu krystalizacji i zmniejsza przepustowosc aparatury produkcyjnej. Ponadto w wyniku zbyt glebokiego wychlodzenia mieszaniny krystalizacyjnej istnieje 106 277106 277 niebezpieczenstwo, zwlaszcza w koncowej fazie procesu w zakresie 45-^35^C wydzielania sie z roz¬ tworu krystalizacyjnego zanieczyszczen do DMT, co powoduje pogorszenie jego jakosci.The crystallization process is carried out at. general this way that a solution of DMT in methanol at a temperature of It cools down to a temperature of about 100 ° C. 64 ° C. by adiabatic evaporation of the solvent then to> a temperature of about 35-40 ° C has a diaphragm cooling, with a cooling medium nothing. It is necessary to use membrane cooling pay attention to keep the temperature difference a little the temperature between the solution and the surface of the chloride work. This causes the cycle to be too long crystallization and reduces the throughput of the apparatus production. In addition, as a result of being too deep cooling of the crystallization mixture exists 106 277 106 277 danger, especially in the final stage process in the range of 45-35 ° C separation with dilution crystallization formation of impurities to DMT, which deteriorates its quality.
Zadaniem wyinailazku jest maksymalne .usunie- cie zwiajzkolw nizej wrzacych od DMT na drodze rektyfikacji produktów utlenianfa i estiryfikacji metanolem przez takie ustalenie sposobu prowa¬ dzenia rektyfikacji, aby _w cieczy wyczeTpanej za¬ wartosc pTE mie byla wyzsza od 0,1%, zawartosc TAE nie byla wyzsza od 0,9%, natomiast zawar¬ tosc BE i innych zwiazków lotniejszych od DMT niewyfcrywalna cbromatograricwiie. Powyzszy sklad syirowego DMT mozna osiagnac przez odpowiedz nie parametry procesu rektyfikacji (dobór refuk- su, temperatur góiry i dolu kolumny, ilosc odbie- ranej cieczy wyczerpanej, ustalenie odpowiedniej entaJipii surowca zasilajacego* koliumne), przy czym spowoduje to pewien wzrost zawartosci DMT w rektyfikacie, którego glównym skladnikiem jest pTE. Tajk uzyskany suorowy DMT poddaje sde na¬ stepnie procesowi krystalizacji z roztworu meta¬ nolu.The task of an account is to remove as much as possible You know, less boiling compounds than DMT on the road rectification of oxidation products and esterification with methanol by such an arrangement of the method rectification so that the drained liquid is the pTE value was greater than 0.1%, the content TAE was not higher than 0.9%, but it was tosc of BE and other compounds more volatile than DMT ineffective cbromatograricwiie. The above composition syir DMT can be achieved by answer parameters of the rectification process (selection of temperature, temperature at the top and bottom of the column, the number of wound fluid exhausted, determining the appropriate entaJipii of feed * koliumne), where this will cause some increase in DMT content in rectificate, the main ingredient of which is pTE. The Tajk obtained from crude DMT is subjected to the test stepwise the process of crystallization from the meta solution nolu.
Druga faze przeponowego chlodzenia roztworu irtetanoiowego prowadzi sie. jecrynie do tempera¬ tury 55—45°C, co zapewnia uzyskanie wysokiej jakosci prodiukitu finalnego^ W wyniku zmniejsze¬ niu zawatrtoscd zwiazków nizej wrzacych w DMT surowym oraz podwyzszenia koncowej temperatu¬ ry procesów krystalizacji zmniejsza sie przede wszystkim w produkcie finalnym zawartosc ta¬ kich zwiazków jak pTE, BE i TAE. W procesie wg wynalazku zawartosc pTE wynosi ok. 10 ppm, BE 2 ppm i TAE 13 ppm. Stancwi to< obnizke tych zandeczyszczen o ok.60%. c ^^wynTfcu wyzszej temperatury koncowej kry¬ stalizacji wzrasta zawartosc DMT w stuchej pozo-_ stalosci po odparowaniu z filtratu metanolem.Second phase of diaphragm cooling of the solution irtetanoia is carried out. jerry to temperature temperature 55-45 ° C, which ensures a high the quality of the final product low-boiling compounds in DMT raw and increasing the final temperature Most of the crystallization processes are reduced all in the final product the content is equal some compounds like pTE, BE and TAE. In the process according to of the invention, the pTE content is about 10 ppm, BE 2 ppm and TAE 13 ppm. This will reduce these and post-treatment by about 60%. c at a higher end temperature of the flange In the process of stabilization, the DMT content in the remaining stability after evaporation from the filtrate with methanol.
Miara zawartosci DMT Jest stosunek udzialu wa¬ gowego DMT i jego izomerów do pozostalych zwiazków,^Wynoszacych w stjposobie wg wynalaz¬ ku ok. 20 — jest wyzszy o ok. 30% w stosunku do procesu z wyzsza zawartoscia zwiazków nizej wrzacych w DMT surowym oraz koncowa tempe¬ ratura krystalizacji ponizej 45GC.A measure of DMT content There is a ratio of the share of the shaft DMT and its isomers to the others compounds, rising in the manner of the invention towards approx. 20 - is higher by approx. 30% in relation to process with higher compound content below boiling in crude DMT and final temperature crystallization rate below 45GC.
PozostaJosd po odparowaniu^ metanolu z filtra¬ tu po krystalizacji DMT jest laczona z innymi strumieniami technologicznymi posiadajacymi zwiazki utleniajace sie i recyrkulowana do sta¬ dium utleniania lacznie z p^ylenem. W dotych¬ czasowych sposobach realizacji procesu wytwarza¬ nia DMT metoda Witten ilosc zawracanego DMT i jego izomerów stanowila na ogól ponizej 10%. wsadu reakcyjnego /reaktora uitleniania. Sposobem wg wynalazku zawartosc DMT i jego izomerów^ alega wzroJSftowi we wsadzie reakcyjnym utlenia¬ nia do ok. 18%.A residue remains after the methanol has been evaporated from the filter here after crystallization, DMT is fused with others technological streams having compounds are oxidized and recirculated to solid dium of oxidation, including oxygen. Until now time methods of carrying out the production process DMT method Witten method amount of DMT recycled and its isomers generally accounted for less than 10%. reaction charge / oxidation reactor. The way according to the invention, the content of DMT and its isomers it alleges growth in the reaction charge oxidizes up to approx. 18%.
Po za^tosowatrmu sposobu wg wynalazku uzysku¬ je sie tniezaleZnie od poprawy jakosci protfufcftu finaiLhego lepsza selektywnosc reakcji utleniania p-ik^emu wtiflruftek ochronnego dzialania ^wprowa¬ dzanego -dodatkowo do reakstora utleniania DMT i jfcgo izt«neT0iw. Zweszenie . zawartosci DMT i jego izfctfiseffów we wsadzie reakcyjnym procesu 40 45 90 utleniania z 10% do 18% podnosi udzial korzyst¬ nych dlla procesu wytwarzania DMT zwiazków w produkcie o ok. 1,2%.After the low temperature of the process according to the invention, the yield was obtained they are cut depending on the improvement of the quality of the protocol finaiLhego better selectivity of the oxidation reaction I have introduced a protective action in addition to the DMT oxidation reactor and jfcgo izt «neT0iw. Suspension. DMT content and its isfctfiseff in the reaction feed of the process 40 45 90 from 10% to 18% of oxidation increases the proportion of the beneficial for the DMT production process in the product by about 1.2%.
Nizej zamieszczony przyklad zilustruje blizej sposób wg wynalazku.The following example will illustrate it more closely the method according to the invention.
Przyklad. Produkty ultleniania p-ksylenu i jego pochodnych zestryfikowano metanolem uzy¬ skujac nastepujacy sklad wagowy zwiazków obo¬ jetnych: p-ksylen — "D,ll%, BE— 2,45%, pTE — 28,28%, zwiazek niezidentyfikowany —0,45%, TAE — 1,47%, dwiumetyloortoftadan (DMO) — 1,35%, suma DMT i dwumetyloizoftalanu (DMI)' — 57,10%, zwiazki wyzej wrzace od DMT (ww> — 8,79%. Dla produktu tego okreslono liczbe kwaso¬ wa równa 5,4 mg KOH/1 g produktu. Sklad pro¬ duktów kwasnych stanowil glównie KpT, MMT.Example. P-xylene oxidation products i its derivatives were esterified with methanol with the following weight composition of obo jetnych: p-xylene - "D, II%, BE— 2.45%, pTE - 28.28%, unidentified compound —0.45%, TAE - 1.47%, dimethylorthophthadate (DMO) - 1.35%, sum of DMT and dimethylisophthalate (DMI) '- 57.10%, compounds higher boiling than DMT (above - 8.79%. The acid number was determined for this product weight equal to 5.4 mg KOH / 1 g product. Composition prop The acid products were mainly KpT, MMT.
Mieszanine w ten sposób otrzymanych zwiazków poddano wstepnemu rozdzialowi przez rzutowe odparowanie na faze gazowa i faze ciekla zwana v pozostaloscia. Suma jzawartosci pTE. DMO, DMT, -DMI w pozostalosci wynosila 15,66%.A mixture of the compounds thus obtained was subjected to initial dissection by projective vaporization into a gas phase and a liquid phase called v leftovers. Sum of pTE content. DMO, DMT, -DMI in the remainder was 15.66%.
Faza gazowa zostala nastepnie skondensowana i otrzymane skroplony poddano rektyfikacji w ko¬ lumnie pólkowej — zaworkowej. Liczba pólek teo¬ retycznych kolumny byla rótwna 13,0,, przy czym ilosc pólek rzeczywistych wynosila 22. Kolumna zaopatrzona byla w kondensator calkowicie skrap¬ lajacy, stosowano nawrót 0,6, a temperatura szczytu* kolumny . wynosila 142—144°C przy cisnie¬ niu 40 Torrów. U dolu kolumny zainstalowana byla wyparka podgrzewana przeponowe olejo¬ wym nosnikiem ciepla. Temperatura dolu kolum¬ ny wynosila_224°C.The gas phase was then condensed and the condensed obtained was subjected to rectification in a chamber shelf - valve luminaire. Number of theo-shelves rhe retic column was 13.0, where the number of actual shelves was 22. Column it was equipped with a condenser completely condensed lajacy, relapse of 0.6 was used, and temperature top * of the column. was 142 ° -144 ° C under pressure niu 40 Torres. Installed at the bottom of the column there was a diaphragm oil heated evaporator heat carrier. Bottom temperature of the column it was_224 ° C.
W wyniku przeprowadzonej rektyfikacji uzyska¬ no destylat o skladzie: p-ksyllen — 0,27%, zwia¬ zek niezidentyfikowany — 0,48%, BE — 7,05%, zwiazek niezidentyfikowany — 0,12%, pTE — 86,03%, TAE — 2,62%, suma DMT/DMI/DMO — 3,43%- Ciecz wyczerpana natomiast posiadala sklad:, pTE — 0,02%, TAE — 0,90%, suma^DMT/ /DMI/DMO — 89,27%, ww — 9,81%. Wg dotych¬ czas znanych i stosowanych warunków rozdzialu estrów' otrzymywano mniejsza ilosc destylatu o 1,5%, natomiast ciecz wyczerpana zwana surowym D^IT byla bardziej wzbogacona w skladnika ni¬ zej wrzace od DMT. _ ¦ r ; ' Nastepnie otrzymane wg powyzszego opisu su¬ rowe DMT poddano dwukrotnej, przeciwpradowej krystalizacji w metanolu. Stosowano stosunek wa¬ gowy surowego DMT do metanolu jak 1:2. Naj¬ pierw rozpuszczano DMT w metanolu pod cis¬ nieniem Ok. 3,5 atn. w temperaturze ok, 100°C.As a result of the performed rectification the obtained a distillate of the following composition: p-xylylene - 0.27%, comp unidentified ankle - 0.48%, BE - 7.05%, unidentified compound - 0.12%, pTE - 86.03%, TAE - 2.62%, DMT / DMI / DMO sum - 3.43% - The liquid was exhausted, however composition:, pTE - 0.02%, TAE - 0.90%, sum ^ DMT / / DMI / DMO - 89.27%, cv - 9.81%. According to the previous time of known and applied separation conditions esters, less distillate was obtained by 1.5%, while the depleted liquid is called raw D ^ IT was more enriched in ingredient than down boiling from DMT. _ ¦ r; 'Then obtained as described above su¬ DMT was subjected to a double anti-current crystallization in methanol. The weight ratio was crude DMT to methanol as 1: 2. Best DMT was first dissolved in methanol under cis not ok. 3.5 atm at a temperature of approx. 100 ° C.
W pierwszym etapie oziebiano roztwór do tem¬ peratury ok. 65°C przez odpedzenie metanolu. W drugim eta»pie chlodzono krystaiizattor przepono- wo woda chlodnicza do tamiJeraftury koncowej 55°C. Uzyskana w ten sposób zawiesine DMT^w lugiu krystalicznym zdekaotowano przy pomocz wii/rowki i wsticipnie po slto(pjjeniiu krystalizatu pooV dano go destylacji prózniowej w kolumnie pólkor wej.In the first step, the solution was cooled to a temperature of temperature approx. 65 ° C by expelling the methanol. IN the second stage, the diaphragm crystallizer was cooled cooling water to the final dam 55 ° C. The DMT suspension obtained in this way The crystal lug was decanted at the water wii / grooves and initially after slto (pjjeniiu kryrystalizat pooV it was given to vacuum distillation in a semi-cortex column in.
Gfttrzymany dwutmeltyloitereftalani charakteryzo¬ wal sda bardzo niska zawartoscia zwiazków za¬ nieczyszczajacych, szczególnie nizej wrzacych od<106 277 6 DMT. Przy pomocy specjalnej metody chromato¬ graficznej stwierdzono zawartosc pTE —4 ppm, BE — 1 ppm, TAE — 5 ppm. Sumaryczna zawaT- tosc aldehydów, oznaczona metoda spektrofotome¬ tryczna wynosila 7,5 ppm.The hydrogen-retained diphthalthyl terephthalate was characterized by I am considering a very low level of compounds non-purifying, especially lower boiling from <106 277 6 DMT. By means of a special method of chromatography on the graph, the pTE content was -4 ppm, BE - 1 ppm, TAE - 5 ppm. Cumulative content- the number of aldehydes, determined by the spectrophotometer method the tric acid was 7.5 ppm.
Dwumetylotereftalan otrzymany z surowego DMT o zawartosci .zwiazków nizej wrzacych od DMT w ilosci 3,3% wag., w tym pTE 1,3% wag., krystalizowany w analogicznych wa/runkach do temperatury koncowej 38°C, zawierac: pTE — 27 ppm, BE — 4 ppm, TAE — 11 ppm, laczna za¬ wartosc aldehydów wyniosla 24 ppm.Dimethyl terephthalate obtained from crude DMT with a content of compounds below boiling from DMT in the amount of 3.3% by weight, including 1.3% by weight of pTE, crystallized under analogous conditions to end temperature 38 ° C, contain: pTE - 27 ppm, BE - 4 ppm, TAE - 11 ppm, total content the value of the aldehydes was 24 ppm.
Otrzymany z dekantacji krysztalów DMT fil¬ trat poddano rektyfikacji otrzymujac ciecz wy¬ czerpana o skladzie: pTE — 0,05%, TAE — 3,24%., DMT/DMI/EMCr — 64,06%, ww — 32,65%. Sklad cieczy wyczerpanej z destylacji filtratu bez gleb¬ szego wydzielania zwiazków nizej wrzacych z DMT surowego i przy koncowej temperaturze kry¬ stalizacji 38°C wynosil: pTE — 3,96%, TAE — 6,43%, DMT/DMI/DMO—55,27%, ww — 34,34%.The DMT filter obtained by decanting the crystals the trowel was rectified to obtain an effluent liquid sourced with the composition: pTE - 0.05%, TAE - 3.24%, DMT / DMI / EMCr - 64.06%, ww - 32.65%. Composition the liquid exhausted from the distillation of the filtrate without soil higher secretion of low-boiling compounds with DMT crude and at final flange temperature stabilization of 38 ° C was: pTE - 3.96%, TAE - 6.43%, DMT / DMI / DMO — 55.27%, cv - 34.34%.
Pozostalosc po oddestylowaniu metanolu zmiesza¬ no z destylatem z rektyfikacji mieszanin estrów i z produktami innych stnumieni technologicznych da 'Utleniania. W ten sposób otrzymano t^zw. frak¬ cje pTE^technicznego, która nastepnie utleniano wspólnie z p-ksylenem w stosunku ^wagowym pX: pTE-techniczny = 1:1,5. Reakcje utleniania prowadzono w reaktorze dzialajacym periodycznie, zbudowanym ze stali kwasoodpornej.The residue after methanol distillation is stirred no with distillate from rectification of ester mixtures and with products of other technological streams da 'Oxidation. Thus, the so-called tailcoat technical pTE, which was then oxidized together with p-xylene in a weight ratio pX: pTE-tech = 1: 1.5. Oxidation reactions carried out in a periodically operating reactor, made of acid-resistant steel.
Wsad reaktora wynosil Q,45 kg przy czym jako katalizatora uzywano mieszaniny tluszczanów ko¬ baltu i manganu w ilosci 0,035% sumy metali w stosunku do masy reakcyjnej. W sklad frakcji pTE^technicznego wynoszacej 270 g wchodzilo 42% DMT i jego izomerów (DMI, DMO).The reactor charge was Q, 45 kg with as the catalyst used was a mixture of coconut fatty acids of balt and manganese in the amount of 0.035% of the sum of metals in relative to the reaction mass. The composition of the fraction a technical pTE of 270 g was included 42% DMT and its isomers (DMI, DMO).
Temperatura procesu utleniania wynosila 150°C, cisnienie 5 atn. Czynnikiem utleniajacym byl tlen.The temperature of the oxidation process was 150 ° C, pressure 5 atm. Oxygen was the oxidizing agent.
Proces prowadzono w czasie 6 godzin. W wyniku przeprowadzonej analizy oksydatów stwierdzono pozytywny wplyw zwiekszonego udzialu DMT w mieszaninie reakcyjnej na tworzenie sie zwiaz¬ ków celowych dla wytwarzania DMT. Stwierdzona poprawa selektywnosci utleniania wynosila 1,17% w porównaniu z pTE-technicznym, zawierajacym % DMT i jego izomerów i sporzadzonym na ba- zie pTE z procesu bez dokladnego rozdzielenia zwiazków nizej, wrzacych od DMT oraz z .pozo¬ stalosci po oddestylowaniu metanolu z filtratu, 'który otrzymam o- z procesu krystalizacji DMT. w metanolu przy koncowej temperaturze krystaldza- j.5 cji wynoszacej 38°C.The process was carried out for 6 hours. As a result the analysis of the oxidates was found positive effect of increased DMT participation in the reaction mixture for compound formation targets for DMT production. Stated the improvement of the oxidation selectivity was 1.17% compared to pTE-technical, containing % Of DMT and its isomers and prepared on the basis of green pTE from the process without precise separation compounds below, boiling from DMT and from stability after distilling methanol from the filtrate, 'which I get o- from the DMT crystallization process. in methanol at the final crystal temperature 5 units of 38 ° C.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL19491276A PL106277B1 (en) | 1976-12-30 | 1976-12-30 | METHOD OF MAKING HIGH PURITY DIMETHYLTERETHALATE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL19491276A PL106277B1 (en) | 1976-12-30 | 1976-12-30 | METHOD OF MAKING HIGH PURITY DIMETHYLTERETHALATE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL194912A1 PL194912A1 (en) | 1978-07-17 |
| PL106277B1 true PL106277B1 (en) | 1979-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| PL19491276A PL106277B1 (en) | 1976-12-30 | 1976-12-30 | METHOD OF MAKING HIGH PURITY DIMETHYLTERETHALATE |
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| Country | Link |
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| PL (1) | PL106277B1 (en) |
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1976
- 1976-12-30 PL PL19491276A patent/PL106277B1/en not_active IP Right Cessation
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| PL194912A1 (en) | 1978-07-17 |
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