RU2064959C1 - Method of processing high-molecular residues of petroleum processing - Google Patents

Abstract

FIELD: petroleum chemistry. SUBSTANCE: petroleum asphaltenes were mixed with technical sulfuric acid and vat residues of recovered dimethyldioxane from rectification stage at isoprene synthesis by dimethyldioxane decomposition at 180-200 C for 120-180 min. Mixing is carried out at ratio, wt.-%: petroleum asphaltenes 78-82; vat residues 10-12, and technical sulfuric acid - the rest. EFFECT: improved method of processing. 3 tbl

Description

 The invention relates to the chemical and petrochemical industries, in particular, to methods for processing high molecular weight residues of oil refining, namely: oil asphaltenes.

High molecular weight oil refining residues are used as raw materials for bituminous materials used in paving construction. However, for their more qualified use, their chemical processing is required. So, there is a method of processing asphalt deasphalting tar tar with propane [1], which involves mixing it with technical sulfuric acid and bottoms of isoprene production obtained in the production of isoprene by the formaldehyde method at the stage of rectification of return dimethyldioxane for 30-90 minutes when heated to 90-110 ^o C (prototype). The ASMOL processing product has semiconductor properties.

The known method, however, is ineffective for processing more condensed high molecular weight oil compounds than asphalt, which consists of asphaltenes only 40-60%
The aim of the proposed technical solution is to increase the efficiency of the method for processing asphalt concrete, which consists entirely of high molecular weight polycyclic substances with a branched conjugation system.

This goal is achieved by the fact that petroleum asphaltenes are mixed with technical sulfuric acid and bottoms of isoprene production by the formaldehyde method at the rectification stage of return dimethyldioxane for 120-180 minutes when heated to 180-200 ^o C in the following ratio of components, wt.

oil asphaltenes 78-82
technical sulfuric acid 8-12
bottoms of isoprene production by the formaldehyde method at the stage of rectification of return dimethyldioxane 10-12
When processing asphaltenes according to the proposed method, a hard-brittle product of black-brown color is formed with a higher degree of condensation of the substance than by the prototype. The product, conditionally called asphaltene, turned out to be a modifier of secondary polyethylene (VPE) and a heat insulator in its properties.

 The method is carried out by the following sequence of operations.

The balance amount of bottoms of isoprene production is pumped into the reactor-mixer, then oil asphaltenes are poured and technical sulfuric acid is pumped. The reaction mixture is heated for 120-180 minutes at a temperature of 180-200 ^o C. The resulting product is cooled to a temperature of 80-100 ^o With and fall asleep in a container.

 For experimental substantiation of the method, a series of experiments was conducted with a different ratio of components and at different temperatures and duration of mixing.

Asphaltenes are obtained from dehydrated reservoir oil by precipitation with saturated hydrocarbons. Their characteristics are as follows:
density, g / cm ³ 1.05
molecular weight 1500
Conradson coking ability, wt. 60
solubility in benzene, wt. one hundred
concentration of paramagnetic 3 centers, sp / cm 1,5 • 10 ¹⁹
the temperature of the beginning of decomposition, deg. S 210
Characteristics of used bottoms from isoprene production:
density at 20 ^o C, g / cm 0,920-1,00
kinetic viscosity at 20 ^o C 15-20
the content of dimethyldioxanes, wt. 1-8
the content of isoprene trimer dimers, wt. 10-20
fractional composition:
the beginning of the boil, ^o Since 197
distillation 10% 262
50% 313
90% 360
end of boiling, ^o C 380
Example. The balance amounts of asphaltenes, industrial sulfuric acid and bottoms of isoprene production in a weight ratio of 82: 8: 10, respectively (Example 9, Table 1) are loaded into a stirred reactor and stirred for 120 minutes at 180 ^° C. The resulting product is cooled to 80 ^o With and unload in a container. Asphaltene has a melting onset temperature of 182 ^{° C.} , a softening temperature of 192 ^{° C.} , a decomposition onset temperature of 210 ^° C. The mass loss of the product upon heating was 1.5%
The results of other experiments on the processing of oil asphaltenes are presented in table. one.

 As can be seen from the table. 1, an increase in the concentration of sulfuric acid above the upper declared limit results in an inhomogeneous granular mass with the inclusion of a liquid. The lack of sulfuric acid, as well as the lack of asphaltene, leads to a semi-solid product, because sulfuric acid is not only a sulfonating agent, but also a catalyst for the condensation of unsaturated and aromatic compounds in the composition of resins and asphaltenes.

Heating above 200 ^o With leads to thermal degradation of raw materials and products. A decrease in temperature <180 ^o C and a reduction in process time <120 minutes leads to a semi-solid inhomogeneous mass.

 The properties of the products obtained by the proposed method and the prototype method are presented in table 2.

 From table 2 it can be seen that the product of the processing of asphaltenes by the proposed method in comparison with the prototype has a higher molecular weight and higher softening and coking properties. Unlike the prototype, the processed product is an electrical insulator and, just like the prototype, is a thermal insulator.

 It was experimentally established that asphaltene is a modifier of secondary polyethylene: it improves the tensile strength and elongation of the VPE film, and the mechanical properties of the asphaltene-modified film do not deteriorate with an increase in the exposure time (Table 3).

 Given the scarcity of polymer modifiers purchased abroad, the value of the found properties of asphaltene should be recognized.

 Thus, the proposed technical solution allows the processing of oil asphaltenes to obtain a useful product with the properties of a secondary polyethylene modifier and a thermoelectric insulator. The technical solution is industrially applicable, as industrial waste and available equipment are used.

Claims (1)

 A method of processing high molecular weight oil refining residues by mixing them with technical sulfuric acid and bottoms from the rectification stage of the return dimethyldioxane of the isoprene production process by decomposition of dimethyldioxane by heating for a certain time, characterized in that oil asphaltenes are used as raw material, mixing is carried out in the following ratio of components, wt . Oil asphaltenes 78 82
VAT residues 10 12
Technical sulfuric acid Else
and heating is carried out at 180 to 200 ^o C for 120 to 180 minutes

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