SU355867A1 - - Google Patents

Description

The invention relates to the field of chemical processing of coal.

There is a method of hydrogenation of coal by ed. St. No. 257484, which involves the hydrogenation of coal at a hydrogen pressure of 50-150 at and a temperature of 400-450 ° C in the presence of petroleum products, active catalysts and additives (anthracene, anthraquinone, anthracene oil), which initiate the transformation of the organic mass into liquid products. However, with this method, anthracene and anthraquinone are relatively expensive and are used in small quantities by the coke industry.

In order to reduce the cost of the process, it is proposed to hydrogenate the coal and petroleum product in the presence of 0.5-15% lignin, which is a many-sided waste from the hydrolysis industry. The presence in the structure of lignin of a large number of reactive groups (benzene, phenolic, hydroxyl, etc.), as well as orthochinoid or quinone methidic structures, determines its reactivity.

Lignite or hard coal with a low degree of metamorphism (long flame, gas) containing about 0.5% sulfur and 5-10% ash, for example the coals of the Kansk-Achinek and Kuznetsk basins, is subjected to hydrogenation.

Fractions with m.p. bale are used as a pasta former. above 240 ° C sulfur or high-sulfur oil, for example, deposits of Western Siberia and Bashkiria. The catalyst (compounds of molybdenum, ferric iron and two) impregnates the crushed coal at the rate of 0.1-1% of the metal per organic mass of coal. For high-moisture brown coal (25-30%), the catalyst is added in the form of a powder of salts or other compounds, followed by drying the mixture to a residual moisture content of more than 1.5-2%.

A mixture consisting of 40–50% coal, 60–50% oil and 0.5–15% hydrolytic lignin (calculated on the organic paste mass) is hydrogenated. The use of an oil product rich in hydrogen and containing a significant amount of hydrocarbons with six-membered hydrocarbon cycles, which are partially dehydrogenated in the process, allows the process to be carried out at a low hydrogen pressure, since it decomposes when heated in hydrogenation

the organic mass of the coal is the active atomic hydrogen released from the oil product. Accordingly, the cost of hydrogen gas from the outside does not exceed 1.5–2%, which is 2–3 times less than in mild hydrogenation conditions in the presence of an oil product, which is hydrogen, and allows gas formation to be reduced by 2–3 times. The addition of 0.5-15% lignin to the reaction mixture allows increasing the degree of conversion of the organic mass of coal from 70% to 85-90% with a simultaneous increase in the yield of liquid products to 85-90%. Co-processing of low-sulfur coal and sulfur or high-sulfur oil in the presence of lignin also solves another problem - the problem of production of low-sulfur boiler fuel. At joint processing, dilution of high-sulfur petroleum products with low-sulfur liquid liquids of the organic coal mass occurs, as well as partial hydrogenolysis of sulfur compounds of the raw material. High-boiling (mazut) fractions of hydrogenates (48-50%) contain up to 1.0% sulfur and can be used as boiler fuel for power plants and for other purposes. Liquid products of hydrogenation, along with high-boiling fractions, contain a significant (45-50%) number of fractions with m.p. up to 300 ° C enriched with phenols, nitrogen bases, aromatic hydrocarbons. The latter are the raw material for the production of chemical products. For the processing of distillate fractions into commercial products, methods of hydrotreating, hydrodealkylation, extraction with selective solvents are used. As a result of the joint processing of coal and petroleum products in the presence of lignin, high-quality products can be obtained:

Table 1 boiler fuel with a sulfur content of 0.7-0.9%, gasoline A-86, diesel fuel with a cetane number of 49-53, phenols containing 60% of deficient cresols, ammonia, hydrogen sulfide, hydrocarbon gases Ci-Ci, Preliminary economic calculations show that during the hydrogenation of black and brown coal mixed with a fraction of m. bale. above 240 ° C of arlan (Tyumen) oil and lignin, compared with the known method, the cost of production remains virtually unchanged, but the capital costs are reduced when co-hydrogenating coal with oil and lignin and the main production is reduced by 25-30% and transportation of raw materials - by 10-13%. Example 1. Carrying out the hydrogenation of various coal samples (see Table I), using the residues after distillation at atmospheric pressure of the fractions with so-called bale as paste-forming agents. up to 240 ° С Arlan oil with the following characteristic: Fractional composition,% boils: up to 300 ° С up to 450 ° С higher than 450 ° С Elemental composition,%: carbon hydrogen sulfur nitrogen Asphaltenes content.

Characteristic of the inhibiting additive

Table 2 lignin is given in table. 2

The ratio of coal: oil in the paste 30: 70-50: 50, the amount of lignin is 0.5-15%. The duration of hydrogenation at 400-425 ° C is 2 hours, the hydrogen pressure is 50-150 at. To prepare the catalysts, the carrier is impregnated with aqueous solutions of salts.

When heated, gas coal from Kuzbass mixed with a fraction of m. Bale. above 240 ° C of arlan oil with a coal: oil ratio of 40: 60 in the range of 400-425 ° C without hydrogen, the conversion of the organic carbon mass (WMD) into liquid products does not actually occur. Under hydrogen pressure, about 100 atm (without catalyst), about 20% of WMD is converted into liquid products. When a catalyst is added, containing its molybdenum and iron, the degree of conversion increases to 70–75% (more precisely, 72–73%). The addition of 0.5-15% lignin to the reaction mixture results in an "increase in the depth of conversion of OMU" and by 10-15%, which, under optimal conditions, is 85-90%. Without additives, a similar depth of OMD conversion is achieved at a pressure of 200 at.

The yield of liquid products in the calculation of the coal-oil mixture, depending on the residence time of the mixture in the reaction zone, is 80-90%, gas 6-10%. The rest is unconverted WMD and ash ... Consumption of hydrogen 1 -1.5%.

After separating the solids, the liquid hydrogenate obtained at 425 ° C has the following characteristic:

Fractional composition%, boils up to 180 ° C1,2

180-240 ° С12.6

240-300 ° C22.1

above 300 ° С64,1.

Elementary composition,%: carbon87,76

hydrogen 10.38

sulfur1.0

nitrogen 0.78.

Hydrogenated fractions with m. Bale. above 300 ° C, they contain 0.8-1.0% sulfur, have a calorific value of 8.5 kcal / kg, a pour point below 0 ° C and are high-quality boiler fuel. For incineration, the total product before the separation of the solid phase can also be used, since the content of the mineral part and the unconverted WMD does not exceed 20%. When hydrogenating a mixture of coal and petroleum products (40: 60) in the presence of lignin, averaging data for a pressure of 100 at and a temperature of 425 ° C can be used to balance, in%:

Motor Fuel Components 25

Low sulfur fuel oil75

Gaz10

Hydrogen consumption

reactions1

subject matter

The method of hydrogenation of coal auth. St.

No. 257484, characterized in that, with

the purpose of reducing the cost of the process, as an initiating additive in the mixture is introduced 0.5-

15% lignin.