The method of purification of oligomers of propylene

 

(57) Abstract:

The invention relates to petrochemistry, namely the production of oligomers of propylene by oligomerization of propylene in phosphoroclastic catalysts and the method of purification of oligomers of propylene. The method is carried out by processing oligomerizate aqueous alkaline solution and subsequent washing with water containing copolymers of propylene oxide and ethylene on the basis of polyhydric alcohols or amines with an average molecular weight of 300-10000.E. or mixtures thereof. When this mass ratio of propylene oxide:ethylene oxide block copolymers support equal 20-80:80-20 wt.% The proposed method allows to reduce the time of separation of hydrocarbon aqueous phase and significantly reduce the content in the propylene oligomers nitrophosphate salts of neutralization. 1 C.p. f-crystals, 1 table.

The invention relates to petrochemistry, namely the production of oligomers of propylene by oligomerization of propylene in phosphoroclastic catalysts.

A known method of purification and neutralization of oligomers of propylene obtained in the oligomerization of propylene in postinoculation catalyst, in which the oligomers are passed through the layer of adsorbent granules is3(Patent Poland No. 263025, IPC 08 J, publ. 15.09.1988).

The disadvantage of this method is the need for complex multi-stage regeneration of the adsorbent and the increase in the content of the oligomers of mechanical impurities formed during adsorption.

The closest in technical essence is a method of purification of oligomers of propylene (A. C. of the USSR №1549942, IPC C 07 C 7/148, publ. 15.03.90). The process of purification of oligomers of propylene obtained by the oligomerization of propylene in the presence of solid postinoculation catalyst, lead processing oligomers 20-40% NaOH solution, which is injected into a stream of oligomers. Then the oligomers bubbled through an aqueous solution of NaOH 30-40% concentration with a bulk velocity of 10-50 h-1. These conditions provide target oligomerizate the content of phosphoric acid to 0.007 wt.%, mechanical impurities up to 0.01 wt.%, moisture - to 0.008 wt.%.

The disadvantage of this method is the high content of phosphoric acid oligomers, which causes corrosion of metal salts of neutralization, leading to clogging of the distillation equipment, and moisture.

The objective of the invention is to increase the degree of extraction of oligomers nutrifaster salts not is received by oligomerization of propylene in phosphoroclastic catalysts, includes treatment with an aqueous solution of alkali and washing, the washing is conducted with water containing copolymers of propylene oxide and ethylene on the basis of polyhydric alcohols or amines with an average molecular weight from 3000-10000.E. or mixtures thereof.

The mass ratio of propylene oxide: ethylene oxide in the copolymers withstand equal 20-80:80-20 wt.%.

The difference of the proposed method from the closest is the washing of the oligomers of water, to which add the copolymers of propylene oxide and ethylene on the basis of polyhydric alcohols or amines with an average molecular weight from 3000-10000.E. or a mixture thereof, the content of propylene oxide and ethylene copolymers withstand equal 20-80 and 80-20 wt.%, respectively.

As block copolymers using block copolymers of propylene oxide and ethylene based on polyhydric alcohols, such as glycerol, diethylene glycol, dipropyleneglycol, or amines, for example monoethanolamine, Ethylenediamine, triethanolamine, with varying degrees of oxypropylation and oksietilirovannye, when this mass ratio oxypropylene and oxyethylene groups is 20-80:80-20 wt.%, or a mixture of these copolymers.

The water after washing the oligomers of propylene containing copolymers of propylene oxide and ethylene, can be directed to the recycling stage water washing oligomers of propylene.

The implementation of the method of purification of oligomers are illustrated in the following examples.

Example 1

Oligomerized obtained by oligomerization of propylene in postinoculation the catalyst bubbled through an aqueous solution of caustic soda and sent to a water washing salts from the neutralization of phosphoric acid with alkali. In wash water pre-type block copolymers of propylene oxide and ethylene oxide based on monoethanolamine with an average molecular weight of 3000.E. with a content of 80 wt.% oxypropylene and 20 wt.% oxyethylene groups in the amount of 100 g per 1 ton of oligomerizate.

Block copolymers of propylene oxide and ethylene obtained as follows.

In the rector volume of 1.0 l load starting system containing 14.2 g of monoethanolamine and 1.4 g of potassium hydroxide, serves the inert gas is nitrogen and twice purge the reactor with nitrogen. Then include a stirrer, heating of the reactor and adjusting the temperature of the reaction mass up to 100C, then start feeding propylene oxide. The reaction oxypropyl the 545,8, The reaction mass was incubated for 1 hour at a temperature of 115S, then start feeding the ethylene oxide. The process of oksietilirovannye carried out analogously to process oxypropylation at a temperature of 115-120C and a pressure of 5.0-6.0 kg/cm2. The total flow of ethylene oxide is 140, the Reaction mass was incubated for 1 hour at a temperature of 115-120C, gradually reducing the pressure in the reactor to 1.0 kg/cm2. The result is 700 g blockcopolymer of propylene oxide and ethylene based on monoethanolamine.

Washing oligomerizate carried out at a temperature of 65-70C, then determine the time separation of hydrocarbon and water phases. In laundered oligomerizate determine the content nutrifaster salts in terms of sodium ions (salts of neutralization).

The results of the experiment are shown in the table.

Example 2

The method is carried out as described in example 1, but add water block copolymers of propylene oxide and ethylene oxide based on monoethanolamine, having an average molecular weight of 10000.E., obtained as described in example 1.

The results of the experiment are shown in the table.

Example 3

The method is carried out as described in molecular weight of 4000.E. with a content of 40 wt.% oxypropylene and 60 wt.% oxyethylene groups obtained similar to that described in example 1.

The results of the experiment are shown in the table.

Example 4

The method is carried out as described in example 3, but add water block copolymers of propylene oxide and ethylene oxide to glycerin with an average molecular weight of 8000.E., obtained as described in example 1.

The results of the experiment are shown in the table.

Example 5

The method is carried out as described in example 1, but add water block copolymers of propylene oxide and ethylene oxide based on ethylene diamine with an average molecular weight of 5000.E. containing 20 wt.% oxypropylene and 80 wt.% oxyethylene groups obtained similar to that described in example 1.

The results of the experiment are shown in the table.

Example 6

The method is carried out as described in example 5, but add water block copolymers of propylene oxide and ethylene oxide based on ethylene diamine with an average molecular weight of 10,000.E. with a content of 30 wt.% oxypropylene and 70 wt.% oxyethylene groups obtained similar to that described in example 1.

Re in example 6, but in the water add block copolymers of propylene oxide and ethylene oxide based on ethylene diamine, obtained as described in example 1 in an amount of 10 g per 1 ton of oligomerizate.

The results of the experiment are shown in the table.

Example 8

The method is carried out as described in example 6, but in the water add block copolymers of propylene oxide and ethylene oxide based on ethylene diamine, obtained as described in example 1, in the amount of 50 g per 1 ton of oligomerizate.

The results of the experiment are shown in the table.

Example 9

The method is carried out as described in example 6, but in the water add block copolymers of propylene oxide and ethylene oxide based on ethylene diamine, obtained as described in example 1, in the amount of 250 g per 1 ton of oligomerizate.

The results of the experiment are shown in the table.

Example 10

The method is carried out as described in example 1, but in the water, add a mixture of blockcopolymer of propylene oxide and ethylene on the basis of glycerol with an average molecular weight of 7000.E. with a content of 40 wt.% oxypropylene and 60 wt.% oxyethylene groups obtained similar to that described in example 1, and blockcopolymer OK oxypropylene and 70 wt.% oxyethylene groups, obtained in the same manner as in example 1, in the amount of 100 g per 1 ton of oligomerizate.

The results of the experiment are shown in the table.

Example 11

The method is carried out as described in example 6, but at wash oligomerizate use recycle water after washing oligomerizate containing block copolymers of propylene oxide and ethylene oxide based on ethylene diamine with an average molecular weight of 10,000.E. with a content of 30 wt.% oxypropylene and 70 wt.% oxyethylene groups obtained similar to that described in example 1. The results of the experiment are shown in the table.

As can be seen from the presented examples, the proposed method allows to reduce the time of separation of hydrocarbon and water phases, and significantly reduce the content in the propylene oligomers nutrifaster salts.

1. The method of purification of oligomers of propylene obtained by oligomerization of propylene in phosphoroclastic catalysts, including treatment with an aqueous solution of alkali and washing, characterized in that the washing is carried out with water containing block copolymers of propylene oxide and ethylene on the basis of polyhydric alcohols or amines with an average molecular weight of 3, the ratio of propylene oxide:ethylene oxide block copolymers withstand equal 20-80:80-20 wt.%.

 

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