CS248576B1 - A method for producing ethylene initiator polymer solvents - Google Patents

Abstract

Method for producing a solvent for initiators of ethylene polymerization with a boiling point of 120 to 210 °C from a raffinate from the extraction of aromatics, or from a petroleum fraction from the primary distillation of crude oil after removal of sulfur and nitrogen compounds on a catalyst containing cobalt-molybdenum or nickel compounds with reaction with hydrogen and subsequent deaxomatization with hydrogen in the presence of a catalyst containing metals of group VIII of the periodic table of elements, or their combination. The product obtained has a maximum aromatic hydrocarbon content of 0.01 wt. %, a maximum sulfur content of 0.001 wt. % and a maximum content of unsaturated compounds expressed by the bromine number of 0.150 g Br per 100 g of sample.

Description

248 578

The present invention relates to a process for the production of ethylene initiator polymer solvents in the production of polyethylene from petroleum fractions, first-alkane fractions! contaminated with sulphite, aromatic nitrogen and olefinic carbonates ·

In the production of high-pressure polyethylene, polymerization initiators are used in the polymerization of ethylene such as di-tertiarybutylperoxide, tertiarybutylper-2-ethylhexanoate, tertiary butyl perbenzoate and tertiary butylperpivalate dissolved in a solvent consisting of isoparaffinic hydrocarbons. , 01% by weight of aromatics, 0.001% by weight of sulfur compounds, calculated as sulfur total, unsaturated compounds expressed in mg Br per 100 g of sample 150, nitrogen compounds below 0.001% by weight hurts esate (with the initiators used and did not decompose them). ethylene polymerization agents are produced by the isoforming of isobutene in the presence of acidic macroporous ion

I Changers · The mixture after oldgomerization is then hydrogenated. Distillation An insulating material consisting of a lysobutylene trimer with a yield of 38% for isobutene butene ·

The disadvantage of this process is that it requires pure isobutene, a precious macroporous ion exchange resin and gives low yields of 35-38%.

BACKGROUND OF THE INVENTION The present invention relates to a process for the production of a solvent for ethylene polymerization initiators using a mixture of alkanic hydrocarbons having a boiling point of 120 to 210 from a raffinate extracting aromatic hydrocarbons, or a fractions from direct distillation of crude oil. compounds with a reaction with hydrogen at a pressure of 0.2 to 4.0 MPa and a temperature of 180 to 360 ° C in the presence of a catalyst comprising cobalt and molybdenum or nickel compounds or compounds thereof. The volume velocity is 0.4 to 1.4% by volume per catalyst volume per hour. Nitrogen compounds can be removed by binding to acidic macroporous sulfonated ion exchange copolymers of styrene and divinylbenzene. 248 376

The raw material is further subjected to dearomathalation with hydrogen at a pressure of 1.5 to 3.5 MPa, with hydrogen in 50 to 200% by weight of the theoretical excess at 170 to 350 ° C in the presence of a catalyst which contains metals VIII of the perhydric group the system of elements, or their bile, and the volume velocity is 0.5 to 1.5 volumes of feedstock per catalyst volume per hour »The product obtained has a maximum content of aromatics of 0.01% by weight, max. , max content of crude protein 0.005 wt%, max content of unsaturated compounds expressed as bromine number 0.15 g Br per 100 g of sample.

In this way, it is possible by simple and technically unpretentious preparation of the solvents which can be replaced by the so-called "solvent" consisting of the isopraphins of the C 2 - C 1 -alkyl group. Example 1. From a gasoline fraction of 80 to 175 ° C after extraction! the aromatic-raffinate is distilled off with hydrocarbons having a boiling point of up to 130 ° C on a 30 TP column and a reflux ratio of 5. A distillation residue is obtained with a desiccation range of 130-175 ° C, containing 0.1% % of N-methylpyrrolidone, 8% by weight of aromatics and unsaturated compounds expressed by bromine number 4.5 g Br per 100 g of sample. The crude is injected at 350 ml / well into a reactor containing 300 ml of cobalt-molybdenum catalyst through a preheater where it is heated to 280 ° C. Hydrogen is fed into the reactor at a pressure of 3 MPa of 100 l / h. After exiting the reactor, the feedstock is injected a second reactor containing 300 ml of platinum catalyst heated to 260 ° C. Feeding hydrogen to the reactor at 220 l / wt has a pressure of 3.5 MPa ·

After leaving the reactor, the feedstock is cooled and analyzed for the content of N-methylpyrrolidone aromatics and unsaturated compounds.

Solvent composition by number 1 j

distillation range 130-175 ° C n-methylpyroidone 0.0005%% aromatics play 0.0095% bromine bromine 0.003g Br · per 100g sample Example 2. 248 576

The gasoline fraction, after removal of the aromatic raffinate, is distilled in accordance with the conditions of Example 1 and passed through a Wofa-tit OK-80 macroporous 300 ml / 300 ml ion exchanger for one hour at 20 DEG C. and then dearomatized in a platinum catalyst reactor at 300 ° C and a partial pressure of 2.7 MPa. The raw material feed is 200 ml / h * d ·

This results in solvent no. 2 of the following parameters: rain & n range 131-175 ° CN-methylpyrrolidone 0.0002% hmaromates. 0.009% hmbrom number 0.003 g Br per 100 g sample ECiHUUa.

The kerosene fraction with a precipitation range of 135 to 200 ° C with a content of 0.077 X Hm of sulfur, 9.2% by weight of aromatics and a bromine number of 0, (8 g Br per 100 g of sample is injected through a preheater into a 250 ° C-heated rack filled with 300 500 kPa of 200 l / l of hydrogen are fed to the reactor. The reactor outlet is injected into the second reactor at 200 ml / h, filled with 300 ml of platinum catalyst and kneaded. to 240 DEG C. Hydrogen at a pressure of 3 bar at 150 l / w is added to the reactor. This gives solvent No. 3 with the following parameters < RTI ID = 0.0 > 4 < / RTI > total 0.0006 wt% bromine number 0.005 g Br per 100 g sample Example 4 »248 576

The kerosene fraction β of the composition shown in Example 3 was sprayed through a pre-heater at 400 ml / hepk into a reactor not filled with 300 ml cobalt-molybdenum catalyst at 300 ° C and a hydrogen pressure of 2.6 MPa at 100 l / hr. 400 ml / htd to a second reactor with 300 ml of platinum catalyst * The temperature in the reactor is 310 ° C and a hydrogen pressure of 3.2 MPa o The amount of hydrogen supplied is 200 l / h · 1 to obtain solvent number 4 of the following parameters by distillation range 142 - 200 ° Caromates 0.0095% by weight Sulfur total 0.0005% hmbrom number 0.006 g Br ha 100 g of sample i Stability of peroxides and polymerization tests have been tested in solvents prepared according to 1 to 4 Table 1 * Peroxide Peroxide Concentration,% wt hr · Spread * C, Isoparanate Spread No. 1 Ί · Spread * 2 Spread 3 Spread * 4 0 0.96 0.94 0, 96 1.05 0.93 24 0.95 0.93 0.94 1.05 0.93 48 4 »0.93 0.94 1.02 0.93

Polymer i start test negat * negat * negat * negat * negat *

Claims (1)

SUMMARY OF THE INVENTION 248 S76 A process for the preparation of a solvent for ethylene polymerization initiators characterized in that a mixture of alkanic hydrocarbons having a boiling point of from about 120 to about 210 ° C of a raffinate extraction of aromatic hydrocarbons, or from a petroleum fraction of direct distillation of rpoy, is deprotected with a water or hydrogen-containing gas at a pressure of 0.2 to 4.0 MPa and tapioteISO to 3 (0 ° C in the presence of a catalyst comprising cobalt and molybdenum bile, or nickel and / or its compounds, abrasion rate 0) , 4 to 1.4 vol. Of feedstock per catalyst volume per hour, or by removing nitrogen compounds by binding with acidic macroporous ion exchangers of the sulfonated copolymers of styrene and divinylbenzene followed by dearomatization of the feedstock with hydrogen or hydrogen containing gas at pressure 1.5 to 3.5 MPa, with a 50 to 200% excess of the theoretical amount and at a temperature of 170 to 350 ° C in the presence of a metal-containing catalyst (VII i) of the periodic constituent group, or a compound thereof, and a volume rate of 0.5 to 1.5 volumes of catalyst volume per hour,