SU1397445A1 - Method of producing tetrahydrofuran - Google Patents

Abstract

The invention relates to the production of oxygen heterocyclic substances, in particular the preparation of tetrahydrofuran (THF) used in the synthesis of polymers and organic substances. The process is conducted from a mixture of 1,4-butanediol acetate with an amine, where R4 and Rj are the same or different, H, CHj, with their molar ratio of 1: (2-10). This mixture is fed at a space velocity of 1-5 h at 210-320 ° C through 1 - ACO, with beats. surface 350-500 and acidity 80-100 mEq NH, / 100 g -, or through jf -, with beats. surface 220-280 and acidity 56-60 mEq NHj / lOO g y,. The method makes it possible to increase the productivity of more than 2 2.08 kg of THF / h-l and exclude the formation of impurities of the CHClS that is corrosive to the equipment. 17 tab. (L

Description

with so

four

4 SL

The invention relates to an improved method for the preparation of tetrahydrofuran, which is used in polymer chemistry and in organic synthesis.

The chain of the invention is an increase in the production and process hindering due to the use of acetic acid as an initial raw material; Ether of 1,4-butanediol and amine, as catalysts, with a specific surface of 350-500 and an acidity of 80-100 mg eq. Shv / YuO g or y -AljO j with a specific surface of 220-280 and acidity of 156-60 mg-eq g,.

Example 1o Starting material 1,4-: diacetoxybutane (1,4-, CAB) in the amount of; 100 g (Tokipo 108-1 mm Hg 1.4235, d 1.038 g / cm) are served: with napaisM ammonia into a glass reactor filled with 20 cm ka. analyzer -Ij -Al Oj brand A-64 (Sun 220 acidity 56 mEq,

NHg / lOO g J -Al-iO ,, ,, bulk density Oj6 g / cm, the size of extrudates d 2-2.2 mm, h 3-6 mm). Temperature

D

in sl, th catalyst 210 С feed rate 1,4-DAV 1.0 j molar

the ratio of ether g ammonia

The balance of the experiment is given in the tabLOC. Analysis of the reaction products by the method, az-liquid chromatography (GLC) shows that the conversion of esters, 4-butanediol is 99.5% with a selectivity of 99.8 mol%. I From a rectifier kaapizat, 1TGP was isolated with a purity of 99.9%, bp 64.6-

64.8 s, 1.4067, 4 0.889 g / cm Process capacity 0.41 kg THF / h-dm catalyst.

EXAMPLE 2 Anageog, example 1, but using catalyst A-64, j-Al-jOj, is used.

 280, K 60 meq-eq, g -Al-jO s temperature in the catalyst bed 320 ° С, volumetric feed rate of ester 3.5, use dimethylamine (DMA) as a molar ratio with a mole ratio ester: amine equal to 1 :ten,

The balance of the gfie experiment: is one in tabLo2; GLC analysis of the products shows that the conversion of the raw material is 92.7% of the selectivity of TG formation, 96.8 mol%; And the catalyzate was isolated with THF of 99.9% purity, mint. 64-6b with,

. ABOUT

24

Front 1, 4066, d

0.889 g / cm. The productivity of the process is 1,310 kg of THF h-dm catalyst.

PRI me R 3. Analogously to example 2, but using the catalyst ij brand A-64, having - 280 m / g, K 58 mg-eq. g J AljOj, the temperature in the catalyst bed is 280 ° C; the volumetric rate of the ester is 2.5 h; molar ratio “1: 2.

The balance of the experiment is given in tab. Z.

Analysis of the products by the GLC method shows that the conversion of the ether is 100% with a selectivity of formation of THF of 97.9 mol.% 0 From the catapizate, THF with a purity of 99.9%, having a boiling point, was isolated. 64-65.8 ° C, l / i068, d 0.889 g / cm. The productivity of the process is 1.02 kg of THF / h-dm catalyst.

PRI me R 4, Aanapogicheski example 2, but using the catalyst l -AljOj brand A-84, having the Sea 350, K 80 mEq. NHj / lOO g 2-Al20, the temperature in the catalyst bed is 240 ° C, the volumetric feed rate of the ether is 3.8, the molar ratio of the ether gDMA is 1: 4 °

The balance of the experiment is given in table., 4.

Analysis of the reaction products shows that the conversion of the starting 154-DAB is 96.9% with a selectivity of THF formation of 99.9 mol%. From catalysts, THF with a purity of 99.9% was obtained; bp. 64-66 С, p 1.4067, d 0.889 g / cm Process productivity 1.53 THF kg / H dm,

Example5. Analogously to example 2, but using a catalyst brand A-84, having 500, K 100 mEq. NHj / lOO g -AljOj, temperature in the catalyst bed 320 C, molar ratio 1,4-DAV; DMA 1: 5, volumetric feed rate of ether 5.0.

The balance of the experiment is given in table.5.

The analysis of the reaction products shows that the conversion of the raw material is 100% with a selectivity of the formation of THF of 99.8 mol%. From the catalyzate, THF of 99.9% purity is obtained, having a bp. 64-6b with, 1, 4067, d% ° 0.889 g / cm. Process productivity 2.08 kg THF / h-dm.

Example 6. Analogously to example 1, but using catalyst 2, grade A-84, having 8 tons 420 m / g.

K 92 mEq. NH, / JOO r4 ,, temperature in the ZOO C catalyst layer, monomethylamine (MMA) is used as the amine, with a molar ratio of 1,4-DAB: MMA equal to 1: 4, the feed flow rate is 3.5,

The balance of the experiment is given in table.6.

The analysis of the catalyzate by GLC method is 100% with the selectivity of the formation of THF 99.6 mol%. THF (99.9%) was isolated from catalyzate, having a bp. 64-66 C, p 1.4067, d4 0.889 g / cm. Process productivity 1.81 kg THF / h-dm.

Example 10. Analogously to example 4, except that in

It is believed that the conversion of raw materials to the composition of raw materials uses a mixture of composition.

em 100% with a THF formation selectivity of 99.8 mol%. From the reaction products, THF of 99.9% purity, having

bp 64-66 С, п

go and

1.4067, d

20

 0.889 g / cm. Process productivity 1.46 THF kg / h-dm.

Example 7. Analogously to example 6, except that the temperature in the catalyst bed is 320 C, the molar ratio is 1,4-DAB; DMA is 1: 4, the volumetric feed rate of the raw material is 3.3.

The balance of the experiment is given in table.7.

Analysis of the reaction products by GLC shows that the conversion of the raw material is 100% with a selectivity of formation of THF of 97.1 mol%. From the products of the reaction, THF with a purity of 99.9% was isolated, b.p. 64-66 ° C, p

 I, 4068, .d4 ° 0.889 g / cm Process efficiency 1.34 kg THF / h dm.

 Example 8. Analogously to Example 3, except that the mixture of composition, in wt.%, Is fed as mash: 1,4-DAB 72.0; Loxy-4- - acetoxybutane (1,4-MB) 25.5 impurities 2.5, the molar ratio of esters: DMA is 4, the feed rate of the feed is 3.0.

The balance of the experiment is given in table.8. Analysis of the reaction products by GLC shows that the conversion of the feedstock is 100% with selectivity

Analysis of the reaction products shows that raw material conversion is 100% with a selectivity of THF formation of 87.4 mol%. From catalyzate selected

education THF 99.9 mol.%. From kata-. „„., „„ G, ODA,

. on 0-7ТГ Ф purity 99.89%. having a boil

 THF with a purity of 99.9% is isolated, - i / Vc oV gy I / ,, with j-zo g oon /

having ttkip. 64-6bCh, p 1 4067.64-65.80, p, l, 4065, d, 0 889 g / cm.

df 0,889 g / cm Manufacturer- Process performance 0.18 kg

the process is 1.81 THF kg / H dm. II .. / h-dm.

Example 13. Analogously to example 50

Example 9. Analogously to example 4, except that as the raw material serves a mixture of composition, wt.%: 1,4-DAB 72,0j 1,4-MAB 25,5; impurities 2.5; MMA is used as the amine; volumetric feed rate of the feed is 4.0.

The balance of the experiment is given in table.9.

Analysis of the reaction products by GLC shows that the conversion of raw materials

55

7, except that the temperature in the catalyst bed is 330 C.

The balance of the experiment is given in table.

Analysis of the reaction products shows that the conversion of the raw material is 100% at the selectivity of the formation of THF92.4 mol%

From catalyzate, vydapene THF purity 99.9%, having ToKip. 64-65.8 ° C, 1.4064, d, 0.889 g / cm. Pro15

0

wt.%: 1,4-DAB 54, li 1,4-MAB 42.8; 1,4-butanediol (1,4-BD) l, 8j impurity 1.3, volumetric feed rate of the raw material 4.0 h-.

The balance of the experiment is given in table 10.

Analysis of the reaction products shows that the conversion of the raw material is 100% with a selectivity of THF formation of 99.9 mol%. THF, purity 99.9%, was isolated from catalyzate, b.p. 64-66 ° C, 1.4067, d7 0.889 g / cm. Process productivity 1.96 THF kg / h-dm.

Example 11. Similarly to Example 4, except that the volumetric flow rate is 5.5 hours.

The balance of the experiment is given in table.11. :

Analysis of the reaction products shows that the conversion of the starting 1,4-DAB is 84.7% with a selectivity of the formation of THF of 99.9 mol.%. THF, purity 99.9%, was isolated from catalyzate, b.p. 64-66 C, p 1.4067,

0

five

0

  0.889 g / cm% Process productivity 1.94 THF kg / h-dm.

Example 12. Similar to Example 6J except that the volumetric feed rate is 0.5.

The balance of the experiment is given in table.12.

Analysis of the reaction products shows that raw material conversion is 100% with a selectivity of THF formation of 87.4 mol%. From catalyzate selected

to „„., „„ g, ODA,

Example 13. Analogously to example 50

55

7, except that the temperature in the catalyst bed is 330 C.

The balance of the experiment is given in table.

Analysis of the reaction products shows that the conversion of the raw material is 100% at the selectivity of the formation of THF92.4 mol%

From catalyzate, vydapene THF purity 99.9%, having ToKip. 64-65.8 ° C, 1.4064, d, 0.889 g / cm. Productivity of the process is 1.31 kg tGF / chdm

Example 1Angshogichno example 4, except that the volume-E1a feed rate of 2.8, TJeMneparypa in the catalyst bed 200 with G Bapans of the experiment are shown in table.14. : Analysis of the reaction products showed that the conversion was 7.1% with a selectivity of formation of 1 | GF 99., 3 mol%.

From catalyzate, THF is purely 99.9%} having, 64-66 ° C, 1.4064, d4 ° g / cm.

Productivity process. I, 04 T | GF kg / h dm.

EXAMPLE 15. Example 2, except that the temperature of the catalyst bed is 320 ° C, the volume of the speed podachkg e (|:) ira is 3.5 hours, in 1 dimethyl-aJMMH SDMA is used as aNMHa at mole The ratio is 9 | firm: amkk 1:15.

The balance of the experiment is given in table. : Analysis of the products by GLC shows that the conversion of the conversion of the raw material is 81.4% with a selectivity of the formation of THF 92.1 mol.% "From the catalyzate, THF is 99.9% pure, having

t.kip bA-bb C 1.4067, d4 0.889 g / sy. Performance g | process 2.64 kg THF / h l,: Example 16, Anapogicheskii ap- jiy 15, except that the temperature liaTypa in the catalyst bed 280 C, and the feed rate e (| ira 2.5 h Molar ratio e etherdma 1 :.

The balance of the experiment is given in table.

GLC analysis of products shows that the conversion amounts to 67.9% for villages (the formation activity of THF is 88.8 mol.% "From kata

Total

138.05 (100.00)

lysate isolated THF purity of 99.9%, having so kip. 64-6b s, n ° 5.4068,

- PE.

| 10

,

 g / cm Manufacturer

process 1.52 kg THF / H L.

Thus, the proposed 1st method allows to increase the process productivity more than twice, up to 2.08 kg THF / hr. L. And to simplify the process by eliminating formation; corrosive equipment; acetic acid.

Table 17 shows the results of the implementation of the method, according to examples 1-16.

Claims (1)

Invention Formula The method of producing tetrahydrofuran by decomposing 1,4-butanediol acetate ester on alumina at 210-320 ° C in the vapor phase, characterized in that, in order to increase productivity and simplify the process, acetic acid e (1, 4-butanediol is used in a mixture with amine formulas R, NHR, where R and R are the same or different, hydrogen or methyl, with a molar ratio of 1: {2-10), respectively, which is supplied with a bulk velocity of 1.0-5.0 h, 2 - AljOj with a specific surface of 350-500 and an acidity of 80-100 mEq KTHj / lOO g h, or a separate surface of 220-280 m / g and an acidity of 56-60 g if-AlzO ,. Table 1 138.05 (100.00). 1397445 10 Table 3  lO about 00 g about IN g4 00 1L. "About tn 00 - i9 a y m 1L -rif in O r 00 8 s 8 Si  "