SU550973A3 - The method of obtaining monomethyl terephthalate - Google Patents
The method of obtaining monomethyl terephthalateInfo
- Publication number
- SU550973A3 SU550973A3 SU1791393A SU1791393A SU550973A3 SU 550973 A3 SU550973 A3 SU 550973A3 SU 1791393 A SU1791393 A SU 1791393A SU 1791393 A SU1791393 A SU 1791393A SU 550973 A3 SU550973 A3 SU 550973A3
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- toluic
- acid
- toluic acid
- xylene
- monomethyl terephthalate
- Prior art date
Links
- REIDAMBAPLIATC-UHFFFAOYSA-M 4-methoxycarbonylbenzoate Chemical compound COC(=O)C1=CC=C(C([O-])=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-M 0.000 title description 5
- 238000000034 method Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UXUYPXITXYMYLZ-UHFFFAOYSA-N 1-methylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound OC(=O)C1(C)CC=CC=C1 UXUYPXITXYMYLZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation 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
- 239000012065 filter cake Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- -1 methyl 1-toluic acid ester Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
(54) СПОСОБ ПОЛУЧЕНИЯ МОНОМЕТИЛТЕРЕФТАЛАТА(54) METHOD FOR OBTAINING MONOMETHYL TREATELATE
рованной л-толунловой кислоты, котора в последующей колонне при 220-260°С полностью этерифицируетс парообразным метанолом до метилового эфира д-толуиловой кислоты . Последующее окисление метил-л-толуилата в монометилтерефталат в присутствии каталитических количеств растворимых солей кобальта осуществл етс при 14U-170 С и давлепии 1-4 атм до степени иревращени метилового эфира rt-толуиловой кислоты 20- 457о. Выделенный из реакционной среды монометилтерефталат промываетс метанолом или хлороформом, раствор етс при нагревапии до 60-SQ C в указанных выше растворител х и ироиускаетс через активированный уголь дл очистки от окрап1енных примесей. Очищенный раствор охлаждаетс и выкристаллизовывающийс при этом монометилтерефталат отдел етс от растворител и высущиваетс . Кислотное число полученного монометилтерефталата 311,5±1, эфирное число 311,5±1,т. пл. 220-22ГС.l-tolunoic acid, which in the subsequent column at 220-260 ° C is completely esterified with vaporous methanol to d-toluic acid methyl ester. The subsequent oxidation of methyl l-toluylate to monomethyl terephthalate in the presence of catalytic amounts of soluble salts of cobalt is carried out at 14 U-170 C and pressure of 1-4 atm to the extent and rotation of rt-toluic acid methyl ester 20-47 °. The monomethyl terephthalate recovered from the reaction medium is washed with methanol or chloroform, dissolved on heating to 60-SQ C in the above-mentioned solvents, and evaporated through activated charcoal to remove impurities. The purified solution is cooled and the monomethyl terephthalate that crystallizes out is separated from the solvent and dried. Acid number of monomethyl terephthalate obtained is 311.5 ± 1, ethereal number 311.5 ± 1, t. square 220-22GS.
Пример 1. Окисление п-ксилола в п-толуиловую кислоту. Example 1. Oxidation of p-xylene to p-toluic acid.
Пеирерывное взаимодействие жидкого «-ксилола с воздухом до образовани л-толуиловой (КИСЛОТЫ осуще,етвл етс при ±30°С и давлении 6 атм в снабженном охлаждающими и нагревающими элементами реактора барботажного тииа, высота которого составл ет 120 см и диаметр 10 см. Предварительно подогретый до температуры реакции воздух раздробл ют на отдельные иузырьки иа ситчатой тарелке. Реактор заполн ют 4500 г /г-ксилола, к которому добавлен кобальтовый катализатор в форме растворимых солей кислот жирного р да, а именно в концентрации 60 мг Со на 1 кг /г-ксилола. /г-Ксилол при температуре реакции 130°С окисл етс воздухом, который пропускаетс со скоростью 1500 и. л/ч до тех пор, пока не достигнут концентрации /1-толуиловой кислоты 33 вес. %. Затем начинаетс непрерывна подача /г-ксилола и непрерывный отвод продукта окислени .The interfacial interaction of the liquid α-xylene with air to form l-toluic acid (the ACID is carried out at ± 30 ° C and a pressure of 6 atm in a bubbling thiaa reactor equipped with cooling and heating elements with a height of 120 cm and a diameter of 10 cm. Previously the air heated to the reaction temperature is divided into individual izirkas on a sieve tray.The reactor is filled with 4500 g / g xylene, to which a cobalt catalyst in the form of soluble salts of fatty acids is added, namely at a concentration of 60 mg Co per kg (g-xylene) / g-xylene, at a reaction temperature of 130 ° C, is oxidized by air, which is passed through at a rate of 1500 and .l / h until a concentration of (1-toluic acid) reaches 33% by weight. Then it starts continuously feed / g-xylene and continuous removal of the oxidation product.
В стационарном режиме, который поддерживаетс свыше 60 ч, подаетс 670 г/ч п-ксилола вместе с 2650 г/ч возвратного продукта в реактор , одновременно из реактора выводитс 3760 г/ч продуктов окислени , имеющих следующий состав, вес. %:In stationary mode, which is maintained for more than 60 hours, 670 g / h of p-xylene is fed together with 2,650 g / h of the return product to the reactor, while 3,760 g / h of oxidation products having the following composition, weight, are withdrawn from the reactor. %:
Толуол0,2Toluene 0,2
/г-Ксилол57,9/ g-Xylene57.9
/г-Толуиловый спирт1,4/ g-Toluic alcohol1,4
/г-Толуиловый альдегид3,9/ g-Toluic aldehyde3,9
/г-Толуилова кислота34,4/ g-Toluic acid 34,4
Терефталевый альдегид0,05Terephthalic aldehyde0.05
Терефталева кислота0,5Terephthalic acid 0.5
«-Толуиловый эфир"-Toluyl ether
/г-толуиловой кислоты0,3/ g-toluic acid
Высококип щие, включа терефталевую альдегидкислоту1 ,5. Фильтровальный осадок, выпадающий в количестве 1400-1450 г/ч, имеет следующий состав , вес. %:High boilers including terephthalic aldehyde acid 1, 5. The filter cake, falling out in the amount of 1400-1450 g / h, has the following composition, weight. %:
/г-Толуилова кислота86,3/ g-Toluic acid86,3
Терефталева кислота1,6Terephthalic acid1,6
Высококип щие, включа терефталевую альдегидкислоту1 ,1 «-Ксилол 11,0. Путем окислени превращаемых в целом каждый час 1070 г п-ксилола можно получить 1280 г/ч /г-толуиловой кислоты, это соответствует выходу примерно 93,5% от теоретического .High boilers including terephthalic aldehyde acid 1, 1 “-Xylene 11.0. By oxidizing a total of 1070 g of p-xylene which can be converted every hour, 1280 g / h / g-toluic acid can be obtained, this corresponds to a yield of about 93.5% of the theoretical.
Пример 2. Этерификаци п-толуиловой кислоты метанолом с образованием метилового эфира rt-толуиловой кислоты.Example 2. Esterification of p-toluic acid with methanol to form rt-toluic acid methyl ester.
В реактор этерификации ввод т 5,0 кг иродукта , имеющего следующий состав, вес. 7о: /г-Толуилова кислота93,55.0 kg of a product having the following composition, wt. 7o: / g-Toluic acid 93,5
/г-Толуиловый спирт0,7/ g-Toluic alcohol 0.7
/г-Толуиловый альдегид0,5/ g-Toluic aldehyde 0.5
/г-Толуиловый эфир/ g-Toluyl ester
/г-толуиловой кислоты0,8/ g-toluic acid 0,8
Терефталевый альдегид0,1Terephthalic aldehyde 0.1
Терефталева кислота1,7Terephthalic acid1,7
Высококип щие+терефталева альдегидкислота2,7.High-boiling + terephthalic aldehyde acid2,7.
Состо ща в основном из -толуиловой кислоты реакционна смесь сначала нагреваетс вместе с 4 кг метанола до 230°С под давлением , при этом она раствор етс или расплавл етс и выдерживаетс в течение 1 ч при этой температуре. При этом 25% /г-толуиловой кислоты превращаютс в метиловый эфир /1-толуиловой кислоты. Затем преобладающую часть избыточиого метанола отгон ют.The reaction mixture composed mainly of α-toluic acid is first heated together with 4 kg of methanol to 230 ° C under pressure, while it dissolves or melts and is kept for 1 hour at this temperature. With this, 25% / g-toluic acid is converted to methyl 1-toluic acid ester. Then, the majority of the excess methanol is distilled off.
Реакционна масса нагреваетс до 240°С, причем максимально допустимым давлением в реакторе вл етс давленне 30 бар. После того, как достигнута температура 240°С, метанольными парами непрерывно питают реактор снизу вверх. Количество подводимых метанольных паров измен етс от первоначально примерно 0,5 кг/ч до 0,1 кг/ч в конце превращени . Этерификаци прекращаетс после того , как реакционна смесь в течение 9,5 ч выдержана при 240°С. Получают 5,50 кг продукта реакции. Этерифпкаци повтор етс описанным образом 15 раз, так что в целом пмеют 82,5 кг продукта реакции следующего состава, вес. %:The reaction mass is heated to 240 ° C, with the maximum allowable pressure in the reactor being 30 bar. After the temperature has reached 240 ° C, methanol vapors are continuously fed from the bottom up. The amount of methanol vapor supplied varies from initially about 0.5 kg / h to 0.1 kg / h at the end of the transformation. The esterification is stopped after the reaction mixture is kept at 240 ° C for 9.5 hours. 5.50 kg of reaction product are obtained. The esterification is repeated 15 times in the described manner, so that, in general, 82.5 kg of the product of the following composition weigh, by weight. %:
Метиловый эфирMethyl ester
/г-толуиловой кислоты93,6/ g-toluic acid 93,6
Метиловый эфир терефталевой альдегидкислоты2 ,0 Диметилтерефталат1,8 Терефталевый альдегид 0,1 -Толуиловый эфирTerephthalic aldehyde acid methyl ester2,0 Dimethyl terephthalate1,8 Terephthalic aldehyde 0.1 -Toluyl ether
/г-толуиловой кислоты0,4/ g-toluic acid 0,4
«-Толуиловый альдегид0,6"-Toluic aldehyde 0.6
/г-Толуиловый спирт0,8/ g-Toluic alcohol0,8
«-Толуилова кислота0,4"-Toluic acid 0.4
Высококип шие0,4.High boiling grade0.4.
Этот продукт подвергают ректифицированной иерегонке ири пониженном давлении, причем в целом получают 76,87 кг метиловогоThis product is subjected to rectified distillation and reduced pressure, with a total of 76.87 kg of methyl
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712127737 DE2127737C3 (en) | 1971-06-04 | Process for the production of monomethyl terephthalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU550973A3 true SU550973A3 (en) | 1977-03-15 |
Family
ID=5809816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU1791393A SU550973A3 (en) | 1971-06-04 | 1972-06-02 | The method of obtaining monomethyl terephthalate |
Country Status (18)
| Country | Link |
|---|---|
| AT (1) | AT321286B (en) |
| AU (1) | AU466962B2 (en) |
| BE (1) | BE784311A (en) |
| BG (1) | BG24946A3 (en) |
| BR (1) | BR7203612D0 (en) |
| CA (1) | CA978542A (en) |
| CS (1) | CS172947B2 (en) |
| DD (1) | DD96701A5 (en) |
| EG (1) | EG10582A (en) |
| ES (1) | ES403479A1 (en) |
| FR (1) | FR2140202B1 (en) |
| GB (1) | GB1385561A (en) |
| IT (1) | IT956024B (en) |
| NL (1) | NL7207546A (en) |
| RO (1) | RO65164A (en) |
| SE (1) | SE391331B (en) |
| SU (1) | SU550973A3 (en) |
| TR (1) | TR18815A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952019B (en) * | 2011-08-17 | 2014-07-09 | 张炜海 | Dioctyl phthalate production line and DOTP production method |
-
1972
- 1972-05-31 IT IT2508972A patent/IT956024B/en active
- 1972-05-31 CS CS376272A patent/CS172947B2/cs unknown
- 1972-06-01 SE SE718372A patent/SE391331B/en unknown
- 1972-06-02 TR TR1881572A patent/TR18815A/en unknown
- 1972-06-02 NL NL7207546A patent/NL7207546A/xx unknown
- 1972-06-02 SU SU1791393A patent/SU550973A3/en active
- 1972-06-02 BE BE784311A patent/BE784311A/en unknown
- 1972-06-02 GB GB2587872A patent/GB1385561A/en not_active Expired
- 1972-06-02 BG BG020638A patent/BG24946A3/en unknown
- 1972-06-02 FR FR7219929A patent/FR2140202B1/fr not_active Expired
- 1972-06-02 DD DD16338072A patent/DD96701A5/xx unknown
- 1972-06-03 RO RO7271130A patent/RO65164A/en unknown
- 1972-06-03 ES ES403479A patent/ES403479A1/en not_active Expired
- 1972-06-04 EG EG24672A patent/EG10582A/en active
- 1972-06-05 BR BR361272A patent/BR7203612D0/en unknown
- 1972-06-05 AU AU43108/72A patent/AU466962B2/en not_active Expired
- 1972-06-05 AT AT481472A patent/AT321286B/en active
- 1972-06-05 CA CA143,855A patent/CA978542A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES403479A1 (en) | 1975-05-01 |
| CA978542A (en) | 1975-11-25 |
| FR2140202A1 (en) | 1973-01-12 |
| NL7207546A (en) | 1972-12-06 |
| DE2127737B2 (en) | 1976-06-10 |
| AT321286B (en) | 1975-03-25 |
| BE784311A (en) | 1972-10-02 |
| BG24946A3 (en) | 1978-06-15 |
| DD96701A5 (en) | 1973-04-05 |
| RO65164A (en) | 1980-05-15 |
| BR7203612D0 (en) | 1973-06-14 |
| DE2127737A1 (en) | 1972-12-14 |
| SE391331B (en) | 1977-02-14 |
| FR2140202B1 (en) | 1978-07-21 |
| AU4310872A (en) | 1973-12-13 |
| AU466962B2 (en) | 1973-12-13 |
| TR18815A (en) | 1977-11-01 |
| CS172947B2 (en) | 1977-01-28 |
| IT956024B (en) | 1973-10-10 |
| GB1385561A (en) | 1975-02-26 |
| EG10582A (en) | 1976-06-30 |
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