RU2402589C2 - Method for production of road bitumen - Google Patents

Abstract

FIELD: construction.

SUBSTANCE: invention relates to method for production of bitumen by oxidation of carbon-containing mix oxidation by air oxygen in presence of catalyst, at the same time carbon-containing mix is represented by brown coal and dissolvent - oil product, which is previously exposed to thermal dissolution in presence of catalyst, such as ferric oxide, promoted with oxides of alternating valency metals at the ratio of coal: oil residue: catalyst 1:3:0.01 accordingly, temperature of 300-350°C, pressure of 2-5 atm., soaking time of 30 minutes with further separation of light fractions up to 350°C, and oxidation of high-temperature distillation residue with above specified catalyst at the temperature of 160°C for 2.5-3 hours to produce bitumen.

EFFECT: expansion of raw materials base for production of road bitumen with improved biocide properties.

2 cl, 4 tbl

Description

The invention relates to methods for producing road bitumen from products of thermal liquefaction of brown coal and oil residues and can be used in the petrochemical, coal and road industries.

A known method of producing road bitumen from oil shale (AS No. 1268599) in the presence of an additive - still residue of the production of phenols by the cumene method. The following fractions are used as solvent:

a) obtained during the processing of oil shale and boiling in the range of 200-320 ° C in a ratio of 1: 0.3-0.7;

b) obtained also during the processing of oil shale and boiling off at 200-320 ° C in a ratio of 1: 0.2-0.8.

The disadvantage of this method is that the high boiling ash extract is classified as bitumen, but the main indicators characterizing it as bitumen are not indicated.

A known method of producing bitumen (A.S. No. 1260384) by oxidizing hydrocarbon feed with atmospheric oxygen, where a semi-tar oil or mixture thereof with coal tar is used as hydrocarbon feed, and sulfuric acid oxidizing agent is used, which is used as acid tar for the production of sulfate additives, acidic oil distillate refining tar or spent sulfuric acid sulfuric acid alkylation.

The disadvantage of this technology for the production of bitumen is the use of acidic components, in particular spent sulfuric acid, sulfuric acid alkylation, which will very quickly destroy organic bitumen derivatives, such as resins, asphaltenes and paraffin-naphthenes, which are the main components of bitumen. Therefore, such bitumen is rapidly destroyed and the quality of the pavement based on them will be low.

There is also a method of producing road bitumen based on products of cracking of lignin and coal tar, which are used in a ratio of 1: 1 (AS No. 355867).

The disadvantage of this technology is that it is necessary to carry out cracking of lignin, separation of a series of undesirable components from the resulting product. Next, semi-coking or coking of coal should be carried out in order to obtain coal tar.

The resulting bitumen is evaluated only in three parameters. By-products of the processes of cracking of lignin and coal, which are obtained in a sufficiently large amount, must be disposed of, which, of course, affects the implementation of this technology.

There is also a method of producing bitumen by oxidation of oil residues, in particular tar, in the presence of a catalyst containing solid chlorides - waste from titanium-magnesium production, open-hearth slag and / or aluminum slag (AS No. 2098178, 1995).

The disadvantage of this method is the need for the presence of these wastes of metallurgical industries, the composition of which is unstable, which will affect the quality of the resulting bitumen.

Closest to the invention is a method for producing bitumen by oxidation of oil residues in the presence of a catalyst, which is used as shale and / or coal, or a mixture of zeolite and shale, or a mixture of zeolite and coal in the form of dust in the amount of 5-60 wt.% From the feedstock (patent RU No. 2221003). Both natural zeolites and artificial ones are used. Used zeolite also contains spent zeolite-containing catalysts for oil refining processes.

The disadvantage of this method is that the catalytic properties of coal, shale and the used zeolites in any modification are very small and, in addition, are not selective, because they do not allow the extraction of the missing components of bitumen from coal, such as asphaltenes and phenols. Phenols possess biocidal properties, protecting it from the effects of microorganisms, which generally increases the durability of bitumen materials (Patent RU No. 2208024). The role of coal in the prototype is limited only to finely divided filler. Spent zeolite-containing catalysts can introduce unwanted components into bitumen, making it environmentally hazardous.

To eliminate these drawbacks, a method for producing bitumen by catalytic oxidation of a bottom residue of thermal dissolution of coal obtained after distillation of light products to a temperature of 350 ° C is proposed.

For thermal dissolution of coal, a solvent was used - an oil product, which was used as fuel oil or oil residue with a boiling point above 300 ° C or a mixture thereof. Thermal dissolution was carried out in the presence of a catalyst, which is iron oxide promoted with variable valence metal oxides with a ratio of coal: oil residue: catalyst 1: 3: 0.01 at a temperature of 300-350 ° C, pressure 2-5 atm, holding time 30 minutes. The bottom residue was oxidized in the presence of the above catalyst at a temperature of 160 ° C for 2.5-3 hours at atmospheric pressure.

The method is as follows.

Finely dispersed coal dust ≤0.1 m and a catalyst representing iron oxide promoted by oxides of metals of variable valence are added to fuel oil or oil residue with a boiling point above 350 ° C or their mixture.

The resulting paste is placed in an autoclave and heated at a temperature of 300-350 ° C and pressure up to 5 atm, for 30 minutes, to extract the necessary components from coal, in particular phenolic compounds and asphaltenes.

Next, light fractions are distilled off from the obtained product. The obtained high-boiling residue is fed into a dispersant and subjected to oxidation at temperatures up to 200 ° C at atmospheric pressure.

The method is illustrated by the following examples.

Example 1

As solvents used fuel oil-100, with the following characteristic:

No. Name of indicator Norm one Viscosity at 80 ° С, no more 96.5 2 Viscosity at 100 ° С, no more 46.6 3 Ash content,% no more 0.14 four Mass fraction of mechanical impurities,% no more 1,0 5 Mass fraction of water,% no more 1,0 6 The content of water soluble acids and alkalis Lack of 7 Mass fraction of sulfur,% no more 1,0 8 Flash point in an open crucible, ° С, not lower 110 9 Density at 20 ° С, kg / m ³ Not standardized 10 Pour point, ° C, not higher 25

Coal is brown, with the following characteristic: A ^d - 4.6; V ^daf - 15.8; C ^daf 72.1; H ^daf - 5.9; (S + O + N) ^daf - 25.3.

The coal is pre-crushed to a fraction of 0.1 mm, mixed with fuel oil in a ratio of 1: 3, the catalyst is added to the resulting paste in an amount of 0.01 g per kg of paste, which is then placed in an autoclave and kept at a temperature of 300-350 ° C for 30 minutes. The catalyst is introduced into the system at the stage of dispersing coal. Light fractions are distilled from the resulting mixture to 350 ° C. The remaining high-boiling residue with the catalyst is placed in a dispersant, through which air is passed and oxidized for 2.5-3 hours at a temperature of 160 ° C. The result is bitumen grade BND 40/60.

Example 2

The preparation of the paste is carried out according to example 1. As a solvent, use a fraction boiling in the range of 200-350 ° C, with the following characteristic:

- density at 20 ° C, kg / m ³ - 860.

Group composition, wt.%:

- asphaltenes - 3.4;

- oil - 78.0;

- resin - 21.6.

The experience in obtaining bitumen is carried out as in example 1. As a result, bitumen grade BND 60/90 is obtained.

Example 3

The preparation of the paste is carried out according to example 1. As a solvent, use a fraction boiling in the range of 200-350 ° C and fuel oil in a ratio of 1: 1. The experience in obtaining bitumen is carried out according to example 1. As a result, bitumen grade BND 90/130 was obtained.

The experimental results are presented in tables.

At the initial stage of the work, the optimum coal-solvent ratio was established in experiments on the thermal dissolution of coal. The data are presented in table No. 1.

Table 1 The influence of the ratio of coal: solvent on the group composition of the high-boiling residue No. p / p Coal: Solvent Ratio The group composition of the high-boiling residue, wt.% asphaltenes pitches oils carbenes, carbides one 1: 1 fifteen 22 61 2 2 1: 2 12 twenty 66 2 3 1: 3 10 12 75 3 four 1: 4 8 10 80 2 5 1: 5 5 9 83 3

As follows from the studies, with an increase in the amount of solvent, there is a decrease in asphaltenes and resins with a simultaneous increase in oils. The optimal value is a ratio of 1: 3, because this is the closest value to derivatives of bitumen products: asphaltenes - 10.2%; resins - 19.4% and oils 70.4%.

table 2 The results of thermal dissolution of coal with various solvents (temperature - 300 ° C, pressure - 5 atm, coal: solvent ratio - 1: 3) No. p / p Solvent Fractional composition, wt.% The group composition of the product after the autoclave, wt.% Up to 200 ° C Up to 350 ° C asphaltenes oils pitches one Fuel oil * 10,2 18.9 6.1 74.0 19.9 2 Fr. 200-350 ° C ^** 8.2 22.6 4.8 72.0 23,2 3 Fuel oil + fr. 200-350 ° C (1: 1) ^*** 10.6 35.8 7.7 62,4 29.9 * - solubility of coal - 26%; ** - solubility of coal - 21.7%; *** - solubility of coal - 28%.

From the results of the table it follows that when using a high boiling fraction and a mixture of fuel oil and a high boiling fraction 1: 1 as solvents, the resulting group composition of the product is close to bitumen compositions.

The following table presents the results obtained after vacuum distillation and subsequent production of bitumen according to the procedure described in example 1.

Table 3 The results of a group analysis of products of thermal dissolution of coal No. p / p The group composition of the high-boiling residue ^* , wt.% The group composition of bitumen, wt.% Kish asphaltenes oils pitches asphaltenes oils pitches one 8.2 64.0 27.8 16.3 56.2 27.5 79 2 7.8 68.6 23.6 8.5 60.3 31,2 51 3 8.7 47.6 43.7 18.3 42,2 39.5 46 * Group composition after vacuum distillation of the thermal dissolution product.

As follows from the data given in table 3, after oxidation of the high-boiling residue obtained by vacuum distillation of the thermal dissolution product of coal to 350 ° С, a residue is formed that corresponds to the group composition and softening temperature according to the chisel bitumen.

Physico-chemical characteristics of the obtained bitumen are shown in table 4.

Table 4 Physico-chemical characteristics of the obtained bitumen Name of indicator Norm in accordance with GOST BND 40/60 / example 1 Norm in accordance with GOST BND 60/90 / example 2 Norm in accordance with GOST BND 90/130 / example 3 1. The depth of penetration of the needle, 0.1 mm, with:
- 25 ° C 40-60 / 54 61-90 / 72 91-130 / 94 - 0 ° С 13/15 20/22 28/30 2. The softening temperature of the ring and ball, ° C, not lower 51/54 47/53 43/47 3. Elongation, cm, at: - 25 ° С 45/53 55/58 65/66 - 0 ° С - 3.5 / 3.6 4.0 / 4.2 4. Fragility temperature, ° С, not higher -12 / -10 -15 / -12 -17 / -17 5. Flash point, ° С, not lower 230/250 230/260 230/250 6. Change in softening temperature after heating, ° C 5 / 4.6 5 / 4.7 5 / 4,2

The physicochemical values of bitumen given in table 4, obtained according to examples 1-3, meet the requirements of GOST 22245-90.

Claims (2)

1. A method of producing bitumen by air oxygenation of a mixture of carbon-containing raw materials in the presence of a catalyst, characterized in that brown coal and a solvent are used as a mixture of carbon-containing raw materials, which are subjected to preliminary thermal dissolution in the presence of a catalyst, which is iron oxide promoted by oxides of metals of variable valency with the ratio of coal: oil residue: catalyst 1: 3: 0.01, respectively, temperature 300-350 ° C, pressure 2-5 atm, holding time 30 m N followed by stripping to 350 ° C, and high temperature oxidation of the distillation residue with the above catalyst at a temperature of 160 ° C for 2.5-3 hours to give the bitumen. 2. The method according to claim 1, characterized in that fuel oil is used as a petroleum product, or an oil residue with a boiling point above 300 ° C, or a mixture thereof.