RU1836318C - Method for obtaining methyl-tret-butyl ether - Google Patents

Abstract

.Usage: as an additive to fuel. SUMMARY OF THE INVENTION: An improved process for the preparation of methyl tert-butyl ether. Reagent 1: methanol. Reagent 2: olefin fraction d containing 10-70% butadiene. Reaction conditions: temperature 50-55 ° C, the catalyst is a macroporous sulfo-exchange resin in the H-form. feedstock is supplied at a linear velocity of 0.5-2 cm / s as an upward flow under conditions of expansion of the layer from bottom to top. Objective: To reduce the pressure drop and stabilize the conversion of olefin (isobutylene). Conversion of isobutylene 96.8-96.9%. 5 ave.

Description

The invention relates to an improved process for the production of methyl tert-butyl ether (MTBE) by reacting methanol with isobutylene, which is used as a fuel additive.

The aim of the invention is to reduce the pressure drop and stabilize the degree of conversion.

This object is achieved in that in the method for producing methyl tert-butyl ether by treating the methanol with an olefin fraction with a GI hydrocarbon. containing butadiene, in the presence of a macroporous sulfoflumein resin in the N-form, the olefin fraction of C / i hydrocarbons containing 10-70% butadiene is used as a catalyst at a temperature of 50-55 ° C and when reactants are fed from the bottom up to the reactor, and the process is carried out by feeding the feedstock at a linear speed

0.5-2 cm / s as an upward flow under conditions of expansion of the layer.

The invention is illustrated by the following examples.

Example 1. The process is conducted in a tubular reactor with a tube length of 12 m and a diameter of 1 inch; the free space above the catalyst bed at rest is 11% of the total volume of each tube, the particle size of the catalyst is 0.5 mm. V 1 cm / s.

Use the following composition, wt.%:

Isobutane 2.88

n-Butane 4.62

1-Butane 8.2

Jeobuten 9.1

2-Butene 3.6

Butadiene 70.2

2-cis-butene

The feed is mixed with methanol to a molar ratio of isobutene to methanol of 0.85. The mixture is supplied at a flow rate of 14 l / h at 50 ° C in two one-inch tubes

00

so o so

with

with

ki arranged sequentially with a total capacity of 4.5 L, filled with 4 L of a catalyst with a particle size of 0.2 mm, in the presence of a catalyst — a macroporous sulfonic ion-exchange resin with an exchange capacity of 4.8 milliequivalents of dry matter.

Linear flow rate 1 cm / s. The conversion (%) and pressure drops over time are as follows:

24

500

2000

PRI me R 2. The process is repeated with the raw materials of the following composition, May. %: Isobutane 2.0

n-Bhutan 4.2

1-Butane 22.8

Isobutene 32.0

2-trans-butene 7.0

Butadiene25

2-cis-butene. The rest

All other conditions are the same, with the exception of the particle size of the catalyst, which is 1 mm.

The conversion (%) and pressure drops over time are as follows:

The above synthesis with a 70% butadiene content is repeated again with a change in the content of free space (voids) above the catalyst in the tubes so that the empty space is 15% (with a corresponding increase in the length of the tube), the result is the same. The synthesis is repeated with a feed containing 70% butadiene, repeated a third time, the free space 0 under the catalyst in the tubes is 10% (the length of the tubes is proportionally reduced), the result remains the same.

Sample The CA fraction of the following Composition, wt.%:

Propylene 0.46

Isobutane6.87

p-Bhutan11.80

 Butene-111.39

Isobutene 30.19

Butene 23.25

Butadiene 34.43

2-cis-Butene1D55

mixed with methanol to obtain a mixture with a molar ratio of isobutene / meta-5 nol 0.85, which is passed at a speed of 14 l / h at 50 C through two reactors in series with a total capacity of 4.5 l filled with 4 l of catalyst, which serves macroporous sulfonic ion exchange resin with an exchange capacity of 4.8 milliequivalents N + / g dry matter. The flow of reagents is directed from the bottom up and has a linear velocity of 1 cm / s.

The following values of conversion and pressure drop over time were recorded:

5

0

0

5

Time h

Pressure drop 0 in the 1st reactor, kg / cm

The same in the 2nd reactor, kg / cm

24

0.2

0.2

500

2000

24

,

0.2

0.2

48, f7

0.05

96.6

500

0.2

0.2

48.47

0.05

0.15

96.4

1000

0.2

0.2

48.47

0.05

0.2

96.4

f

Over 99 Over 99 Over 99

The content of MTVE, wt.%. 38.1

Dimsras and sodimers, wt.% 0.05

Butenyl ethers. wt.%

Conversion is invented. % Yield of butadiene,%

0.2

96.6

99

PRI me R 4 (comparative). The source material of example 3 at the same temperature and spatial velocity is fed into two reactors connected in series with the flow from top to bottom.

In the first stage of the experiment, the results are similar to those in Example 3, but after a while there is a gradual increase in pressure drop and a slight decrease in conversion. The following values are fixed:

24

0.3

0.3

38

0, 1

0 .2

96, 4

99

0.1

500

0.4 0.5 37.9

0.2

96.1

99

2000

1.5 1.8 36

0.05

0.2

91.3

93

PRI me R 5 (comparative, without butadiene). Methanol was added to the olefin fraction containing 35% by weight of isobutene and 0.2% by weight of butadiene to obtain a mixture with an isobutene / methanol molar ratio of 0.85. The mixture is passed at a speed of 14 l / h at 50 ° C through two series-connected reactors in the direction of flow from top to bottom. From 0

the absence of butadiene did not increase pressure drop or decrease conversion. The following values are fixed:

Time h245002000

1st pressure drop

reactor 0.30.30.3

Pressure drop in the 2nd

reactor0.3

MTBE. wt.% 43,142.943

Dimers and Joint

dimers. wt.% 0.30.30.3

Isobutene Conversion96,896,696.6

5

As can be seen from the above examples, carried out according to the proposed method, isobutylene conversion and pressure remain unchanged.

Claims (1)

0 Claims Method for the preparation of methyl tert-butyl ether by methanol treatment of the olefin fraction GJ. containing butadiene, in the presence of a macroporous sulfonic exchange resin in the H-form as a catalyst at 50-55 ° C, when reactants are fed from the bottom up to the reactor or reactors, characterized in that, in order to reduce the pressure drop and stabilize the degree of conversion, 0 use olefin fraction C4. containing from 10 to 70% butadiene, and the process is carried out when the feed is supplied with a linear velocity of 0.5-2 cm / s as an upward flow under conditions of expansion of the layer.