KR800001115B1 - Method for removine acethylenic componds - Google Patents

Abstract

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Description

How to remove acetylene compounds

1 is a schematic diagram of a facility for removing acetylene compounds from hydrocarbons.

The present invention relates to a method for removing acetylene compounds from saturated hydrocarbons, olefinic and diene hydrocarbons or mixtures thereof.

More specifically, the present invention relates to propene from a mixture of butadiene, propylene, ethylene present alone, or ethylene present in a mixture with other saturated and / or olefinic hydrocarbons having the same number of carbon atoms, 1 A method for removing butene, dibutene, vinylacetylene, diacetylene and acetylene.

In particular, the present invention relates to (1) propyne, 1 buffin, vinyl acetylene and / or ) A method for removing diacetylene, (2) a method for removing propene from propylene present alone or in a mixture with other saturated hydrocarbons and / or olefinic hydrocarbons having the same number of carbon atoms, ( 3) A method for removing acetylene from ethylene present alone or in ethylene present in a mixture with ethane.

It is already known that these hydrocarbons must be liberated from acetylene compounds in order to make maximum use of saturated hydrocarbons, olefinic hydrocarbons and especially diene hydrocarbons. For example, the content of the acetylene compound in the butadiene monomer should be ≦ 50 ppm, due to the toxic action of acetylene on the polymerization catalyst.

Various methods for removing acetylene compounds have been proposed and are currently used, for example, (a) selective hydrogenation, (b) fractional distillation, and (c) extractive distillation in the presence of a suitable solvent.

If these methods are used alone or in combination with each other, it is possible to remove the acetylene compounds, but in these methods, the operating cost is high and the installation cost is expensive because it requires a special device. According to the present invention, it is possible to completely remove the acetylene compound without using a known technique, and at the same time, a significant economic benefit is obtained.

It is an object of the present invention to selectively convert an acetylene compound in the presence of an acid ion exchange resin containing mercury ions to an alcohol (particularly preferably methanol), or a glycol (particularly preferably monoethylene glycol or diethylene glycol) It is an object of the present invention to provide a method for removing an acetylene compound from the hydrocarbons.

The ether is then removed by a simple and economical subsequent rectification process.

The ion exchange resin used has acid properties as described above and preferably includes sulfonic acid groups (e.g. -SO ₃ H supported on the same resin of polystyrene, divinylbenzene or phenol resins), but includes -COOH groups. Resin can also be used.

Mercury ions may be added to the resin in the form of mercury salts, in particular in the form of mercuric nitrate salts or mercuric acetate salts, and the content of Hg ⁺⁺ ions in the resin may be less than the total cation capacity of the resin.

Hydrocarbons that can be purified according to the invention are paraffinic, olefinic hydrocarbons, and conjugated dienes (particularly butadiene, propylene and ethylene).

The etherification reaction can be carried out over a wide range of temperatures using conventional columns containing ion exchange resins, although a temperature range of -20 ° C to 80 ° C is advantageous, in particular a temperature range of + 20 ° C to 60 ° C. It is advantageous. The reaction pressure is preferably selected so that the hydrocarbons are maintained in the liquid phase at the reaction temperature.

The contact time at this time is in the range of 2-30 minutes.

The reaction is preferably carried out in the presence of a stoichiometric excess of alcohol or glycol with respect to the acetylene compound, and in practice it is convenient to make the alcohol from 1.05 to 2.0 moles with respect to 1 mole of the total acetylene compound.

In addition, the acetylene-based compound reacts with any kind of R-OH-type compound [where R is an alkyl group, acyl group, aryl group, cycloalkyl group] in the presence of the same ion exchange resin containing mercury ions as described above, To produce additional compounds, which were found to be simply removed by distillation, similar to ethers.

The reactions mentioned above are in particular vinylation or etherification reactions. All the reactions described above can be carried out in gas phase or liquid phase without any difference.

The present invention will be further described through the following examples.

Example 1

In 400 cc of an aqueous solution containing 3% by weight of Hg (NO ₃ ) ₂ .H ₂ O, 100 g of a resin in the form of Amberlist 15 containing an acid group in the form of -SO ₃ H was added.

The mixture was stirred for 1 hour and then filtered under vacuum and the resin washed several times with methanol under vacuum.

A portion of the resin treated in this manner was introduced into a 20 cc capacity reactor maintained at 40 ° C. by a constant temperature circuit. 100 cc per hour of butadiene containing methanol, 1,350 ppm by weight of vinyl acetylene, and 1.05% by weight of butene, in an amount of 1.7 moles of alcohol per 1 mole of the total acetylene compound with an operating pressure of 5.0 absolute atmospheres. Pumped into the reactor continuously.

10중량 ppm이었다.The content of the two acetylene compounds measured in the liquid sample taken at the outlet of the reactor

10 ppm by weight.

Example 2

Methanol, 150 ppm by weight vinylacetylene, 200 ppm by weight 2 butyne and 1.2 in an amount capable of bringing the molar number of alcohol to 1.25 moles relative to 1 mole of the total acetylene compound while operating temperature and pressure at 30 ° C. and 4 absolute atmospheres. Butadiene containing wt% butene was pumped continuously to the same reactor as in Example 1 at 200 cc per hour.

10중량 ppm이었다.The content of the three acetylene compounds measured in the liquid chamber at the outlet of the reactor is

10 ppm by weight.

Example 3

100cc / hour of propylene containing methanol and 0.5% by weight of propene in an amount capable of bringing the number of moles of alcohol to 1 mole of acetylene compound to 1.15 moles while operating temperature and pressure at 30 ° C and 10 absolute atmospheres. Pumped continuously to the same reactor as in Example 1.

10중량 ppm이었다.The content of propene measured in the liquid sample taken at the outlet of the reactor

10 ppm by weight.

Example 4

(When carboxylic acid is added to acetylene compound)

With respect to the same reactor as in Example 1 having a resin which was prepared in the same manner as in Example 1 and finally washed with glacial acetic acid, while operating temperature and pressure at 50 ° C and 30 absolute atmospheres, the number of moles of acetic acid per mole of acetylene compound was Propylene containing 0.5% by weight of acetic acid and 0.5% by weight of propylene was continuously pumped at 50 cc per hour.

The content of propine present in the liquid sample taken at the outlet of the reactor was ≦ 10 ppm by weight.

Example 5

The tablet was maintained and a reactor 9 (see Figure 1) with a capacity of 150 cc was used. The reactor 9 is provided with the following conduits.

(a) A conduit for introducing hydrocarbons (1) having a high content of acetylene compounds into the bottom of the reactor as a gas phase.

(b) A conduit for discharging the same hydrocarbons (2) which have been segregated from the top of the reactor as gaseous phase.

(c) Conduits (3) for feeding liquids consisting solely of alcohol or mixtures of alcohols and ethers to the government of the reactor.

(d) Conduits for discharging a liquid stream of alcohol and ether from the bottom of the reactor to the tank (8) by means of a siphon (4).

The final liquid stream is recycled in whole or in part to the reactor 9 via a conduit 3 by a pump 7. The outflowed part 5 is replaced with the same amount of clean alcohol 6.

50 g of the resin (see Example 1) already prepared was fed to the reactor 9 having the structure as described above, and then thoroughly wetted with methanol. [This methanol is finally released through the siphon 4]. It is maintained at 50 ° C by a special constant temperature circuit (the constant temperature liquid is introduced through the conduit 10 and discharged through the conduit 11) and contains 0.1% of propene in the same reactor maintained at an absolute pressure. While the propylene was fed 20g per hour through the conduit (1), the liquid flow discharged 50g per hour from the bottom of the reactor through the conduit (4) was recycled all the way through the conduit (3) to the government of the reactor.

The content of propine present in the gas sample taken at the outlet of the reactor was ≦ 10 ppm by weight.

Claims (1)

Saturated hydrocarbons, olefinic hydrocarbons or diene hydrocarbons, or the like, which consist of etherifying an acetylene compound with an alcohol or glycol in the presence of an acid ion exchange resin containing mercury ions and distilling off the resulting ether. A method of removing an acetylene mixture from the mixture.

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