SU1458372A1 - Method of destructive processing of oil shale - Google Patents

Abstract

The invention relates to the destructive processing of combustible shale 1 The invention relates to the field of thermochemical processing of solid multi-ash fuels, in particular combustible shale, with the release of gaseous, liquid (resin) and solid products from them, which can be used in the chemical industry as gaseous fuel and solid products for the production of cement clinker. The purpose of the invention is to increase the yield and quality of the products obtained by obtaining from them liquid, gaseous and solid products used as fuel, in the chemical industry, in the production of cement clinker. The goal is to increase the yield and quality of the products obtained, reducing the environmental pollution. Oil shale is crushed to a particle size of 0.03-0.08 mm, granulated with the addition of a liquid binder (waste water or petroleum halide) to obtain granules 5-20 mm, dried to 150-250 0, treated with heated shale resin or hydrocarbon fraction with boiling temperature is 360-430 ° C and then subjected to semi-coking at 450- 650 ° C with separation of gaseous products, tar and solid residue. Additionally, before granulating, the crushed slate is mixed with lime, clay in a mass ratio of 1: (O, 9-1.0). 2 hp f-ly, 2 tab. reduction of environmental pollution. Example 1. Baltic shale (kerogen 36%, mineral substance 54%, moisture 10%) with a calorific value (dry weight) of 2910 kcal / kg is ground in a ball mill to 0.08 mm (passes through a sieve 98.0%). Similarly, crushed limestone and clay to 0.05-0.08 mm and mixed with slate. The mixture is granulated at 30 ° C in a disk (L 4 SP 00 100

Description

IBOM granulator with the addition of waste iodine to a moisture content of 12.0%. Then, the granules are dried in the flow of the raw gases from the combustion products of Natural Gas at 220 ° C for 10 microns to a moisture content of 2% in the granules. Before loading into the reactor, the pellets are treated (irrigated) through nozzles of shale resin heated to 300 ° C, which is the product of semi-coking of pellets. The amount of resin (fraction boiling over at 360 ° C) added to the granules is 5.0% by weight of the granules. Pasting of granules of 7–8 mm in size is carried out in an electrically heated tube reactor (load 1.5 kg | for the experiment). The residence time of granules IB in the reactor with a temperature rise from 220 to 550 ° C is 10 minutes, at 550 ° C 15 minutes. During the heating of the semi-coking of the granules, their layer is pumped with nitrogen, pre-heated granules are added with vacuum distilled distillation of oil, boiled away, within 360-430 s in an amount of 10% by weight of the granules.

P m and me p 5. The conditions are similar to that shown in example 1, but the size of the granules is chosen in the range of 9-14 mm, the temperature of drying heat

10 and semi-coking equal to, respectively, 250, 250-650 and 650 ° C, the residence time of the pellets in the reactor at the indicated. temperatures of 10, 10 and 25 minutes, respectively.

15 When granulating as

binder materials are applied to oil slimes, subjected to preliminary centrifugation and having the following composition,%; organic matter

20 66.0; water 30} mineral impurities 4.0, the addition of sludge is 20% by weight of the granules.

Example 6. The conditions of the ana: are logical given in example 1, but are {up to 400-600 C. respectively. About 25 granules are chosen to be 9-14 mm, the native mixture (mixture) before the pelletizing temperature of drying, heating and semi-coking, respectively. Equal 250;

Gan contains, wt%; slate 50; known to 45; clay 5.

The vapors and gases cool and collect common laboratory instruments. Example 2. The experiment was carried out in the reactor of example 1, but the size of the granules was 5-6 mm, the temperature of drying, heating and semi-coking was 150; 150-450 and 450 ° C, drying time, heating and semi-coking for 10 minutes, the addition of resin to the granules is 3.0% of their mass.

Example 3. All conditions are similar to those shown in Example D, but the granules are made without the addition of mineral components, the granule size is 9-14 mm, the temperature of drying, heating and semi-coking is 250, 250-650 and 650 ° C, respectively, the residence time of the granules at the indicated temperatures of 10.0, 10.0 and 25 minutes, respectively; the amount of resin added to the granules is 10 jO% of their mass.

Example 4. The conditions for conducting experiments are similar to those described in example 1, but using granules with a size of 15-25 mm without clay, those

40

250-650 and 650 ° С, the residence time of the granules in the reactor at the specified temperature is 10.10, respectively

25 min As a binder, wastewater from an oil refining plant before their purification, having the following composition,%, is used: water 9 8, 5; mineral impurities 0.5; organic matter 1.0. The amount of added water is 15.0% by weight of the granules.

Example 7. All the conditions for the preparation, drying and semi-coking of the granules are similar to those under 1-1. 1.

Slate is used; the heat of combustion is 3480 kcal / kg, the kerogen content is 39.2%, and the ash is 43.2%. In contrast to Example 1, sucking the charge as follows,%: slate 40; known to 50; clay 10,

Example 8. All the conditions for the preparation, drying, semi-coking of the granules are similar to those of Example 1, but the amount of resin is 10%.

The following mixture was used: 1%: slate 60.0; known to 30;

45

50

The following mixture was used: 1%: slate 60.0; known to 30;

Drying, heating and semicoast temperature, respectively, 250, 250-650 clay 10.

and 650 ° Se contact time (time is pre-Example 9. All conditions are similar to those of Example I, but take

pellets at the indicated temperatures) respectively 15.20,35 minutes.

shale 790 g, limestone 635 g. OtK granules are added with vacuum distilled distillation of crude oil, boiled away, within 360-430 s in an amount of 10% by weight of the granules.

P m and me p 5. The conditions are similar to that shown in example 1, but the size of the granules is chosen in the range of 9-14 mm, the temperature of drying heat

and semi-coking equals 250, 250-650 and 650 ° С, respectively, the time of pelleting of the pellets in the reactor at the indicated -. temperatures of 10, 10 and 25 minutes, respectively.

When granulating as

binder materials are applied to oil slimes, subjected to preliminary centrifugation and having the following composition,%; organic matter

66.0; water 30} mineral impurities 4.0, the addition of sludge is 20% by weight of the granules.

Example 6. Conditions ana: are logical given in example 1, but once

0

250-650 and 650 ° C, the residence time of the granules in the reactor at the specified temperature is 10.10, respectively

25 min As a binder, wastewater from an oil refining plant before their purification, having the following composition,%, is used: water 9 8, 5; mineral impurities 0.5; organic matter 1.0. The amount of added water is 15.0% by weight of the granules.

Example 7. All the conditions for the preparation, drying and semi-coking of the granules are similar to those under 1-1. 1.

Slate is used; the heat of combustion is 3480 kcal / kg, the kerogen content is 39.2%, and the ash is 43.2%. In contrast to Example 1, sucking the charge as follows,%: slate 40; known to 50; clay 10,

Example 8. All the conditions for the preparation, drying, semi-coking of the granules are similar to those of Example 1, but the amount of resin is 10%.

The following mixture was used: 1%: slate 60.0; known to 30;

five

0

tava, clay 10.

shale 790 g, limestone 635 g. The ratio of the mass of shale to the mass of limestone and clay is 1: 0.9.

Example 10. All conditions are similar to those of Example 1, except for the size of the particles after grinding shale, limestone and clay, and the size of the granules entering for drying and semi-coking. In this example, the screening of the crushed starting components is carried out through a sieve with a mesh size of 0.03 mm (98% sampling). The size of the granules with this 18-20 mm

Example 11. All conditions are similar to those of the example: 4, except for the size of the particles going to the granulation, and the size of the granules entering the drying and semi-coking. Particulate shale, limestone and clay particles passing through a 0.03 mm sieve (98%) are fed to the granulation. The size of granules is 18-20 mm.

In tab. 1 shows the modes of the proposed method (in examples 1-6) and known, the composition and characteristics of the products obtained. In tab. 2 shows the modes, yield and composition of the products obtained, depending on the size of shale particles and shale granules.

As follows from the table. 1 and 2 of data, during the processing of granules, uniform in shape and similar in size, the required residence time in the reactor. Considerably less than during processing of pieces of different size. In addition, a layer of crushed shale, turned into pellets, more uniformly across the cross section is purged with gas and has a much lower flow resistance. At the same time, dust entrainment and, consequently, losses (and environmental pollution are insignificant. When granulating, petrochemical and oil refining wastes are used. Grinding of shale particles less than 0.03 mm is impractical, as it is associated with excessive energy consumption, with a particle size of more than 0.08 mm granules do not form or their size and mechanical strength are unacceptable for further drying and semi-coking.

The limits of granule sizes are 5-20 mm. Pellets less than 5.0 mm do not satisfy the requirements for their mechanical

five

abrasion and crushing strength. Granules larger than 20 mm are obtained as a result of granulation for too long a time (3–4 times longer than the time of obtaining granules with a size of 10-15 mm). The time of their semi-coking is 40-50 minutes (granules 30 mm). The time of semi-coking and drying of the granules 5-20 mm is 5.0-15.0 minutes. Accordingly, the reactor productivity (for the same mass of granules) with a granule size of 5–20 mm is 8.0–2.5 times more than for a 30 mm granule. Processing the granules prior to semi-coking with a heated shale resin to a hydrocarbon fraction with a boiling point of 360-430 ° C provides an increase in the yield of gas and resin in the proposed method in comparison with the known: the difference in output is 4.8-8.8%.

The limits of the boiling point of carbon5 hydrogen mixtures used for the treatment (irrigation) of granules are determined by the fact that the fractions at a lower temperature are of higher value. The residue residue at temperatures above 430 ° C is usually immaterial in semi-coking shale resins. Therefore, irrigation of the pellets with these hydrocarbon blends allows them to be converted into coke, light liquid products and high calorific gas. This makes it possible to increase the yield of liquid products boiling away at a temperature below 360 ° C. At the same time increases

0

kip -,

five

the carbon content in the semi-coke granules to the value that ensures the transformation of these granules into cement clinker.

Thus, when using the proposed method, the output of the SMOLE is increased at the same heat of its combustion (22.0-23.6% instead of 14.8–18.2% by a known method), the yield of the gas increases with the same heat of combustion (6, 7–9.0% instead of 5.0–6.0%), the quality of the resin, gas and solid residue increases: dust content in the resin and gas is 0.3% instead of 4.3–25.0% by a known method. In this case, the solid residue according to the proposed method, i.e. semi-coke has a chemical composition that meets the requirements for cement clinker, while the composition of the solid residue is

eight

the known method does not provide its application. In addition, dust discharge to the atmosphere and grains of solid residue in the dump, pollution of the environment (0.5-1.0% by weight of grail instead of 76.8-79.2% according to a known method) are sharply reduced.

environment, crushed to a particle size of 0.03-0.08. mm slate is granulated with the addition of a liquid binder to a granule size of 5-20 mm and before semi-coking, the dried granules are treated with a heated slate resin or hydrocarbon fraction with a boiling point of 360 Formula 10 1030 C.

2. The method according to p. 1, otlicha1. The method of destructive processing is done so that in front of the oil shale granules, which include grinding the shale by grinding, and drying to-150-250 ° C, they are crosslinked with limestone and clay in mass and semi-coking at 450 -650 sec with a high 15soles ratio l: tP, 9-1.0). the division of gaseous products, cm3. A method according to claim 1, characterized by a solid residue, characterized in that as a quality and with the fact that, for the purpose of binder additive in the granulation of yield and quality, waste water or oil products are used, reduce slurry 20.

eight

Size of granules (particles), mm

Drying temperature, С Temperature of heating 7-8 5-6 9-14 15-20 9-U 9-14 0.2-10.0 0.2-10 220 150 250 250 250 250 150 150 150

va s

from

before

Pulping temperature, С

The time of the process, NIN

drying warming semi-coking total

Additive binder, wt.%, By weight of dry slate

220 150 250 250 250 250 150 550 450 650 650 650 650 650 480

550 450 650 650 650 650 480

5.0 3.0 10.0 10.0 20.0 15.0 Table 1

150 530

530

Output of semi-coking granules (calculated on dry slate, without additives), t

Total

including: resin

gaseous products

solid residue

losses

heap

The content of organic matter in products from organic matter granules, wt.%

Total

including;

 in liquid products

in gaseous products

in solid residue in yateri dump

The dust content in the products by weight of the granules, wt.%:

Total

including:

in liquid products

in gas

in solid residue

100100100100 00100100100

23,623,022,822,022,722,718,2U, 8

7,86,78,99,07,98,35,06,0

68,069,867,568,068,567,00 .60.50.8, .00.9I.O-.

100 100 100 100 100 100 100 100

71.0 70.5 70.0 69.5 70.1 70.0 57.1

21.8 21.2 22.0 22.5 21.9 21.9 13.7 6.6 7.7 7.2 7.0 7.1 7.1 0, 6 0.6 0.8 1.0 0 , 9 1

I 29.2 "J.

58.1 17; 7

24.2

0.5 0.6 0.5 0.5 0.6 0.5 4.3-21.5 5.0-25.0

0.10.10.10.10.10.13.13-16.8 5.0-25.0

0.20.20.20.20.20.20.9-4.7

0.20.30.20.20.3 a.2, 0 57.1

1.9 13.7, 1 I 29.2 "J.

in dump

Total loss from the source, wt.% Of the charge

including masp% g

organic matter

Mineral Substance

Heat of combustion, kcal / kg

gas tar

, --- 66,869,10

0,600,500,801,000,901,0076,8079,20

0,200,150,300,400,350,4010,0010,10

"

0,400,350,500,600,550,6066,8069,10

9800985098509850985098509800 800

99009900990099009900990098009800

Particle size after zmelch, mm

The size of the granules, mm raw after drying

after semi-coking

Yield, wt.% Resin

gaseous solid residue

losses

0.08 0.03

0.08 0.03

7.0-8.0 7.0-8.0 15-25 18-20 7.0-8.0 7.0-8.0 15-25 18-20

7.0-8.0 7.0-8.0 15-25 18-20

0.08 0.03

13

145837214

Continuation of table 2

Claims (4)

Claim 1. The method of destructive processing of oil shale, including grinding shale, drying to 150-250 ° C and semi-coking at 450-650 ° C with the release of gaseous products, resin and solid residue, different. the fact that, in order to increase the yield and quality of the products released, reduce pollution 8 environment, crushed to a particle size of 0.03-0.08. mm slate granulated with the addition of liquid binder to svya _with grain size 5-20 mm □ and before semi-coking, the dried granules are treated with a heated shale resin or hydrocarbon fraction with a boiling point of 360 ° C 430 ° C. 2. The method of pop. 1, characterized in that before granulation, the crushed shale is mixed with limestone, clay in oil 15 ow ratio 1: (0.9-1.0). 3. The method of pop. 1, characterized in that in the granulation use wastewater or oil 20 sludge. Indicators Table 1 The proposed method Known method Examples Soft PL'PP / Hard mode 1 2 3 4 5 6 Granule size (hour- type), mm 7-8 5-6 9-j4 15-20 9-14 9-14 0.2-10.0 0.2-10 Drying temperature ° C 220 150 250 250 250 250 150 150 Warm-up temperature, ° C from 220 150 250 250 250 250 150 150 BEFORE 550 450 650 650 650 650 480 530 Semi-coking temperature, C 550 450 650 650 650 650 480 530 Process time "* sa min drying 10.0 10 ¹⁰ fifteen 10 10 fifteen fifteen warming up 10.0 10 10 20 . 10 18 22 semi-coking 15.0 10 25 ³⁵ ‘25 25 J Total 35.0 thirty 45 70 45 45 33 37 Additive binder, wt.%, By weight of dry shale E 1458372 10 Continuation of the table. 1 Indicators The proposed method Known method Examples Soft mode Hard mode * 1 2 3 4 5 6 The output of the products of semi-coking pellets (calculated on dry shale, bee additives), X Total 100 100 100 100 100 100 100 100 including: pitches 23.6 23.0 22.8 22.0 22.7 22.7 18.2 14.8 gaseous products 7.8 6.7 8.9 9.0 7.9 8.3 5,0 6.0 solid residue 68.0 69.8 67.5 68.0 68.5 67.0 - - losses 0.6 0.5 0.8 1,0 0.9 1,0 ' 76.8 79.2 dump - - “ * The content of organic matter in the product max from the organic matter of the granules, wt.% Total 100 100 100 100 100 100 100 100 including: in liquid products 71.0 70.5 70.0 69.5 70.1 70.0 57.1 58.1 in gaseous products 21.8 21,2 22.0 22.5 21.9 21.9 13.7 17 ’, 7 in solid residue 6.6 7.7 7.2 7.0 7.1 7.1 - - in the dump - - - - - 29, g] 24.2 Losses 0.6 0.6 0.8 1,0 0.9 1,0 • The dust content in products by weight of granules, wt.%: Total 0.5 0.6 ‘0.5 0.5 0.6 0.5 4.3-21.5 5.0-25.0 including: in liquid products 0.1 0.1 0.1 0.1 0.1 ο, ι 3.4-16.8 5.0-25.0 in gas 0.2 0.2 0.2 0.2 0.2 0.2 0.9-4.7 in solid residue 0.2 oh s 0.2 0.2 0.3 0.2 - - Continuation of table 1 Indicators The proposed method Known method Examples. Soft mode Hard mode 1 2 3 4 5 6 in the dump - - - - - "· 66.8 • 69.10. The total loss from the original granules, wt.% From the mixture 0.60 0.50 0.80 1.00 0.90 1.00 76.80 79,20 including wt.% ί organic matter 0.20 0.15 0.30 0.40 0.35 0.40 10.00 10.10 Mineral Substances 0.40 0.35 ·· 0.50 0.60 0.55 0.60 66.80 69.10 Calorific value, kcal / kg > pitches 9800 9850 9850 9850 9850 9850 9800 ? 800 gas 9900 9900 9900 9900 9900 9900 9800 9800 table 2 Indicators Particle size after and grinding, mm Granule size, mm wet after drying after semi-coking The yield of products, wt.% Resin gaseous solid residue loss Examples “- 4 eleven 1 0.08 0,03 0.08 0,03 7.0-8.0 7.0-8.0 15-25 18-20 7.0-8.0 7.0-8.0 15-25 18-20 7.0-8.0 7.0-8.0 15-25 18-20 23.6 24.0 22.0 23.0 7.8 8.0 9.0 9.0 68.0 67.0 68.0 67.0 0.6 1,0 10 1,0 Continuation of Table 2 Indicators Examples 1 10 4 eleven Drying process conditions: 1 temperature, C 220 220 250 250 contact time, min 10.0 10.0 15.0 15.0 semi-coking: 0_ temperature, C 550 550 650 650 contact time, min 15.0 15.0 35.0 35.0 The content of organic matter, wt.% in liquid products 71.0 71.0 69.5 70.0 in gaseous products 21.8 21.5 22.5 22.0 in semicoke 6.6 6.5 7.0 7.0 losses 0.6 1,0 1,0 1,0 The composition of the granules of the solid residue, wt.% CaCOj 78.5 78.0 78.0 78.5 Si0 ₂ 11.5 12.0 12.0 11.0 A1 _g 0 ₃ 2.0 2.0 1,5 1,5 Fe ₂ 0 _} 1.6 1,5 1,0 1,0 coke 4.4 4,5 5.5 5,0 other components 1,0 1,0 1,0 1,5 moisture 1.0 1,0 1,5 1.5 * on slate and added resin.