CS214013B1 - Method of pyrolysis of middle crude oil fractions - Google Patents

Abstract

The purpose of the invention is to modify the process of pyrolysis So that the middle oil fraction and the temperature boiling at 100 to 400 ° C are pyrolyzed in the presence water vapor and sulfur additives make the temperature range was increased 600 to 1000 ° C. It progresses aa so that the raw material compounds are added prior to pyrolysis sulfur in an amount of 0.001 to 1.5% by weight, wherein inorganic compounds are sulfur, hydrogen sulfide, carbon disulfide, sulfur dioxide, sulphides, sulfur, metal thiosulphates I. and II. groups of periodic tabs, ammonium and organic bases. From organic substances these were compounds of the merkatans, sulfides, sulfoxides, disulfides, xanthates, thiophene, thiophenols and aromatic and aliphatic derivatives, phosphorus compounds and ethers or alkenylthiophosphoric acids or Ο, Ο-dialkyldithiophosphoric acids or their inorganic and organic esters and esters. The invention can be used in petrochemical production.

Description

The invention relates to a process for the pyrolysis of medium petroleum fractions having a boiling point of 100 to 400 ° C in the presence of water vapor and spring-increasing sulfur-containing additives in the temperature range of 600 to 1000 ° C.

Currently they have. pyrolysis processes for olefin production dominantly poatavenie in petrochemistry. Pyrolysis of hydrocarbons with oil and natural gas is the basic source of not only ethylene, propylene and butadiene, but also low molecular weight aromatic hydrocarbons. Under the conditions of a significant increase in ethylene production, the issue of extending the raw material base from light fractions - ethane to gasoline to petroleum distillates boiling above 150 ° C to the oil itself is of great importance. The use of intermediate fractions as a feedstock for pyrolysis has several disadvantages compared to lighter injections. The main drawback is the relatively lower yield of ethylene that aa moves around

2.2% by weight. Pyrolysis of higher petroleum fractions results in significantly more liquid fractions and coke than pyrolysis of gasoline. Therefore, an increased effort has been devoted to increasing conversion in the pyrolysis of medium and higher petroleum fractions to the detriment of liquid products and the suppression of coke formation. Pyrolysis oils are currently mainly used for energy purposes only. · Solving the problems indicated would lead to a significant improvement in economic indicators.

The above-mentioned drawbacks are eliminated by the pyrolysis of medium petroleum fractions boiling in the range of 100 to 400 ° C in the presence of water vapor and sulfur additives, increasing the conversion in the temperature range of 600 to 1000 ° C, which consists in adding to the feedstock before pyrolysis sulfur compounds, in an amount of 0.001 to 1.5% by weight. Among the inorganic compounds, it is elemental sulfur, hydrogen sulfide, carbon monoxide, sulfur dioxide, sulfides, sulfides, metal thiosulfates of the first and second groups of the periodic table, ammonium or organic nitrogen bases. Among the organic sulfur compounds, these were compounds of the mercaptan, sulfide, sulfoxide, diaulfide, xanthate, thiophene, thiophenol type and their aromatic and aliphatic derivatives, the derivatives having 1 to 32 carbon atoms. Furthermore, they may be phosphorus and sulfur compounds of the alkenylthiophosphonic acid or Ο, Ο-dialkyldithiophosphoric acid type or their inorganic and organic salts or esters, in particular the metal salts of the first and second groups of the periodic table, the alkyls having 1 to 16 carbon atoms.

By impregnating olefinic sulfur and sulfur compounds, the medium petroleum distillates are largely recovered into olefinic products, mainly ethylene, due to the increase in conversion to gaseous products at the expense of liquid pyrolysis products. In addition, by impregnating elemental sulfur and sulfur compounds, the conversion of the hydrocarbons to the pyrocarbon is prevented so that it does not deposit in the form of coke on the inner surface of the pyrolysis apparatus.

The subject matter of the invention is apparent from the examples, without being limited to the examples.

Example 1

The experiments were carried out in stainless steel flow-through tubular reactors at a temperature range of 600 to 1000 ° C. The pressure ranged from 0.05 to 0.5 MPa, preferably from 0.1 to 0.21IPa, and the residence time was less than 1 and the reaction was carried out in the presence without an inert diluent.

Water inert vapor in an amount of 20 to 150% by weight of hydrocarbon spray was used as the inert diluent. Petroleum fractions having a boiling point of from 100 to 400 ° C were pyrolyzed, focusing on petroleum and gas oils. The manner of dosing the additives into the pyrolysis system was determined by their nature. Sulfur compounds, which are normally gaseous, were fed directly into the reactor. Water-soluble compounds were dosed in the form of aqueous solutions and hydrocarbon-soluble additives were added to the starting material. The sulfur compounds were dosed in an amount of from 0.001 to 1.5% by weight per hydrocarbon feed.

Example 2

The process of Example 1 was carried out by pyrolysis of gas oil in the absence and presence of elemental sulfur and dibenzyl sulfide. He used gas oil for pyrolysis ea with the following properties: start of distillation

234 ° C 360 ® end of distillate density at 20 ° C molecular weight aromatic content sulfur content

850.2 kg / ® ³²⁶⁹

24.5% by weight 0.89% by weight

The experiments were carried out by pyrolysis of gas oil at 770 ° C, with a residence time of 0.54 s in the absence of water vapor.

Table 1 Influence of sulfur compounds on extracts and composition of reaction products by pyrolysis of gas oil at 770 ° C, holding you 0.54 and in the absence of water vapor

additive without sulfur DBS ¹ Additive amount,% h®. - 0.1 0.5 Product yield, 56 h®. pyrokvapaliny 27.79 14.23 19.41 pyrogas 64.26 83.22 72.14 coke 2.93 2.45 2.46 methane 14,07 18.21 16.98 ethene 5.36 7.81 6.64 E you fief 23,00 31.61 27.54 propyl 16.62 13.68 11.76 1,3-butadié® 3.30 4.17 3.37 The residue in pyroplyn 1.91 7.74 5.85

x DBS - dibenzylsulfide

Example 3

Way! In Example 1, a gas oil was pyrolyzed in the presence and absence of 0.05 and 0.1 wt% elemental sulfur and in the presence of water vapor. The gas oil of the composition as described in Example 2 was used for pyrolysis. The results are shown in Table 2.

214 013

Table 2 Influence of the additive on the yields and composition of pyrolysis products in pyrolysis of gas oil at 800 ° C and water-to-feed ratio 0.8

additive without sulfur sulfur Quantity of additive,% hnu - 0.05 0.1 Dwell time, p 0.22 0.24 0.18 Pyrop gas yield,% hnu 54.65 65,66 67,86 curling 11.25 12.67 12.58 hundredth 2.68 3.47 3.95 ethylene 22.64 29.54 28.17 Propylaia 9.67 10.62 11.48 1,3-butadián 2.87 3.39 4.59 residue in pyroplyn -------------- 5.54 5.97 7.09

SUBJECT MATTER

Claims (1)

A process for the pyrolysis of medium petroleum fractions having a boiling point of 100 to 400 ° C in the presence of water vapor and sulfur additives increasing the conversion in the temperature range of 600 to 1000 ° C, characterized in that 0.001 to 1.5% by weight are added to the feedstock before pyrolysis. elemental sulfur, hydrogen sulfide, carbon disulfide, sulfur dioxide, sulfide; sulphates, metal thiosulphates of the first and second groups of the periodic table, ammonium or organic nitrogen bases, sulfur compounds of the mercaptan, sulfide, aulfoxide type, diaulfides, thiophane and their aromatic and aliphatic derivatives, the derivatives containing 1 to 32 carbon atoms; and phosphorus of the alkenylthiophosphonic acid type or of β, θ'-dialkyldithiophosphoric acids or their inorganic and organic salts or esters, in particular the salts of the metals of the first and second groups of the periodic table, the alkyls containing 1 to 16 carbon atoms;