RU2320427C2 - Method for utilizing of oil sludge and rice hull - Google Patents

Abstract

FIELD: ecology, in particular, utilization and processing of solid and liquid wastes.

SUBSTANCE: method involves mixing oil sludge and rice hull with maximum concentration of rice hull in oil sludge. Method allows semi-finished product to be obtained, said product may be used upon processing as low-grade fuel and as high-activity additives in construction material industry, and it may be also used as hydrophobic coating in road building industry.

EFFECT: improved quality of semi-finished products and wider range of application.

5 cl, 5 tbl, 2 ex

Description

The invention relates to the field of ecology, namely to the simultaneous use of: in the oil refining industry, in particular for the disposal of oil waste in oil refineries and in places of oil production; in the field of agricultural processing, in particular for the disposal of waste in the form of husks of rice husks; in the fuel industry, in particular for the disposal of substandard coal dust wastes from filters for purifying atmospheric emissions from boiler houses and thermal power plants, for subsequent production of low-calorific fuel by briquetting; in the building materials industry, in particular for the primary disposal of waste in the form of substandard cement dust from filters for cleaning emissions from cement plants, for the subsequent production of prefabricated briquettes for the manufacture of hydrophobic road (airfield, hydraulic) slabs; the secondary use of the semi-finished product obtained by briquetting with coal dust for the manufacture of a highly active additive in the form of amorphous silica for a binder (for example, cement, lime, gypsum), and in road construction, in particular for the use of bitumen additives for the manufacture of road coverings (airfields, hydraulic facilities).

The problems of oil sludge utilization and processing, which are solved by various methods, in particular [1], [2], [3], [4], [5], [6], are aimed at bringing commodity fractions of oil products, in particular bitumen, to conditioning [ 7].

The tasks of utilization and processing of agricultural waste in the form of husk (husk) of rice waste [8] are aimed either at destroying them by burning, or at removing them from useful production by dumping, or at redistributing them, in particular, to obtain amorphous silica high purity, for example, suggest [9] to use water and sulfuric (or hydrochloric) acid.

There is a known [10] method for the treatment of oil sludge, in which a coagulant is added to it and, after the formation of flakes, crushed wood or cellulose is added to dehydrate the oil sludge.

Various sorbents [11] are also known, for example, ODM-1F [11 4] for the elimination of spills of crude oil and petroleum products.

In addition, there is the problem of recycling agricultural waste in the form of husk (husk) of rice waste, which is especially important for the rice-producing Krasnodar Territory. The fact is that the ultra-light (γ = 12-26 kg / m ³ ) husk must be removed from the elevators to landfills, where it spontaneously ignites during caking (the effect of peat bogs), which automatically leads to environmental fines and waste transport and penal expenses of rice processing end enterprises.

Known [12] is a method of utilizing husk of rice husk by obtaining from it a highly active additive for astringent roasting husks at 600 ° C.

At the same time, significant material and energy costs are required for a separate husk firing process on specialized equipment with controlled multi-stage temperature conditions.

At the same time, ash from the burning of husks is an indispensable supplier of high-purity amorphous silica [9] for the production of high-quality binders, for example, cements [13].

The essence of the claimed invention lies in the fact that the husk of rice husk is mixed with oil sludge in the amount of the maximum concentration of sorbent (husk) in oil sludge [claim 1].

At the same time, a good sorbent - husk of rice husk ensures the utilization of agricultural waste and at the same time the disposal of oil waste at oil refineries and oil production sites by briquetting the resulting semi-finished product with substandard coal dust (waste from the third - the fuel industry). Next, the briquettes are used as low-calorie fuel (husk calorific value is 3300-3600 kcal / kg) for the fuel industry’s own needs, and ash is used as a highly active additive in the third field - the building materials industry, [claim 2] and in the fourth - areas of road (airdrome) construction as a hydrophobic coating (slabs) for roads (aerodromes) and hydraulic structures (including briquetting of the resulting semi-finished product with substandard cement dust (waste) ementnyh plants)) [Claim 3].

It is possible to directly use semifinished product 1 as a stabilizing and hydrophobic additive in bitumen [claim 4 of the invention], a hydrophobic additive for the manufacture of road plates, hydraulic coatings, wood concrete [claim 5] by pressing (instead of briquetting). The addition of husks to bitumen also leads to an additional positive super-effect - an increase in its flash point above 250 ° C and its minimum self-ignition temperature above 370 ° C - according to GOST 12.1.044.

The advantages of the claimed method is that:

a) does not require separation from oil sludge mass of mechanical impurities;

b) separation of oil sludge into the phases “oil product” and “water” is not required;

c) there is no need for demulsifiers in case of sludge sedimentation with separation into oil product and water phases;

d) special equipment is not required, waste selection and redistribution of semi-finished products is carried out at existing plants without stopping them and without changing existing technologies and equipment;

e) there is no need for tolling raw materials for the production of additional materials, components, etc.

Laboratory and industrial tests [14] confirm the effectiveness of the claimed method, but also identify problems, in particular, in the removal of sulfur from high-sulfur oil sludge and, for example, in high motor costs, since the construction and operation of product pipelines requires large capital costs and the investment of the project must be carried out in an agreed manner actions of various industries.

Example 1

In table 1, table 2, table 3 shows the results of full-scale industrial tests [14].

Characteristics of the original husk of rice husk.
Table 1 No. P / P INDICATOR NAME Units CHANGE PUSH VARIETY "Start" Krasnodar 424 Party 1 Party 2 one Silica content
in the original product % 18.11 18.06 2 Exit
amorphous silica % 86,42 86.31 3 Losses
initial mass % 78.76 79.42 four Ash content % 21.24 20.58

Replacing a mineral additive with an ash of an organic component obtained, for example, by burning husk of rice husk, allows one to obtain a highly active hydraulic additive mainly due to amorphous silica, which has been proved by [Moad N. AL-Khalaf and Hana A. Yousift “Use of rise husk ash in concrete, page 243 "The International Journal of Cement Composites and Lightweigt Concrete, Volume 6, Number 4, Njvember 1984, pp / 241-248] by diffraction analysis in the temperature range 450-700 ° C. with a two-hour burning time of the organic component.

Pod has the highest porosity ["Rice and its quality." Ed. Dr. tech. sciences E.P. Kozmina Monograph of the American Association of Grain Chemists. M .: Kolos, 1976, p.303], which turns it into an indispensable sorbent due to the property of separate sorption of the phases “water” and “oil product”, i.e. there is a natural (under the influence of natural forces) phase separation in space according to the difference in their specific gravities.

In the conditions of the Krasnodar Territory with five rice plants and a daily average waste production of 304 tons / day of husk, the real disposal is carried out by transporting the waste to landfills with immediate land filling to prevent wind entrainment of husks due to its low bulk density. In this case, husk spontaneous combustion occurs (peat fire effect) with subsequent extinguishing of these fires and reimbursement of environmental fines for harmful emissions into the atmosphere, which is more profitable for rice plants than utilization of husk waste (by burning in absent specialized furnaces) due to high waste fuel consumption .

Due to the high abrasiveness due to the limiting (in organic) content of silica in the husk of rice husk, for example, in France and in Spain, legislation [“Rice and its quality”, p. 288 - see above] prohibits the use of husk waste as feed and feed additives for animals.

At the same time, the proportion of unpromising for further purification of oil sludge in places of oil production and refining is steadily increasing.

Comparative characteristics of the original sludge and the claimed method.
table 2 No.
P / P INDICATOR Units CHANGE EXODUS.
NEFTESHlam STATED METHOD Semi-finished product 1 Prefabricated 2 Prefabricated 3 Note one Relative density at 20 ° С g / cm ³ 0.984 1,165 1,232 0.211 2 Water content wt. 30.00 8.00 2.44 - 3 Conventional viscosity at 20 ° С at 80 ° С units
units 1,62
1.35 -
- - - four Flash point
in an open crucible ° C 126 260 - - 5 The content of the fur. impurities wt. 0.18 1,67 1.72 0.06 6 Ash content % 0.35 0.84 88.00 100.00 7 Coking wt. 13,2 - - - 8 Sulfur content wt. 2.0 2.0 2.0 0.8 In road construction, the sulfur content is reduced due to an emulsifier, for example, type EMU-4

Table 3
Comparative characterization of binders No.
P / P Units CHANGE INITIAL STATED METHOD NOTE one kg / cm ² 506 582 Standard cube 2 kg / cm ² 12 74 150 × 150 mm

In this case, the husk is an adsorbent (water absorption by the surface of the husk body) and absorbent (absorption of oil products by the entire surface of the husk body) at the same time, i.e. the water-oil product phases are separated naturally, and the degree of sorption of the semi-finished product 1 is initially determined visually by its color, and then (after drying by natural evaporation of water) is laboratory, and briquetting by pressing with cement dust is carried out with the predominance of water in the semi-finished product 1, and Briquetting by pressing with coal dust is carried out with the predominance of oil in the semi-finished product 1.

Example 2

Laboratory data are the basis for selecting the composition of the optimal ratios of multicomponent mixtures during further industrial testing. The firing was carried out in an electric muffle furnace for one hour, fuel ash was obtained from real waste from the Krasnodar CHPP. Standard samples were tested when adding substandard cement dust (for the formation of cubes and beams) from air filters to purify emissions from the cement plant into the atmosphere of a cement plant:

a) Rzh. - cubes 150 × 150 mm;

b) Rizg. - beams 40 × 40 × 160 mm;

c) The age of the samples is 28 days.

The silica content depends on the variety of ripened husks of rice and ranges from 22.75% ("Astrakhan precocious") to 10.4% ("Shklovsky mutant"). Taken (averaged over silica content) and the most common in the waste rice-processing enterprises of the Krasnodar Territory, the Start variety.

Tab. 4 the content of silicon dioxide (silica) to dry matter.

Tab. four The content of silicon dioxide (silica)
to dry matter No.
p / p Raw material Value The claimed method Standard sample Fuel ash Units ism Fuel ash Husk ash Firing temperature (° C) Prefabricated ash 3 Ratio:
husk: sludge: coal cement dust Rzh, kg / cm ³ Rizg, kg / cm ³ one Donetsk coal skinny % 43 85.88 450 twenty 1: 4: 0.04 31.15 4.24 2 Donetsk anthracite % 49 86.89 500 10 1: 4: 0.03 35.06 5.55 3 Coal near Moscow % 43 87.19 550 four 1: 4: 0.02 43.96 4.89 four Estonian slate % 34 86.02 600 2 1: 4: 0.01 40.60 5.41 5 Sour fly ash % 40 85.71 700 0 1: 4: 0,00 40.10 6.50

Comparative characteristics of materials at different ratios of components in the semi-finished product 3.
Table 5a No.
p / p Materials Units rev. Indicators (prefabricated 2 = husk: oil sludge: coal dust) - with briquetting Source 1: 4: 0 1: 6: 0.5 1: 10: 3 one 2 3 four 5 6 7 one Cement M 500 kg / cm ³ 506 584 528 483 2 Concrete M 100 kg / cm ³ 102 144 122 84 3 Concrete M 150 kg / cm ³ 158 162 138 138 four Concrete M 200 kg / cm ³ 214 216 198 186

Table 5b
(continued) No.
p / p Materials Units rev. Indicators (prefabricated 2 = husk: oil sludge: cement dust) - without briquetting Source 1: 4: 0 1: 6: 0.5 1: 10: 3 8 9 10 eleven 12 13 fourteen one Road plates MPa / cm ³ 25.0 30,2 26.8 24.4 2 Road plates MPa / cm ³ 22.0 28,4 23.6 21.6 3 Asphalt concrete MPa / cm ³ 20,0 24.5 21.1 18.2 four Arbolite MPa / cm ³ 1.42 2.86 2.24 1.48 Table 5c
(continued) No.
p / p Materials Units rev. Indicators (prefabricated 1 = husk: oil sludge) without briquetting Source 1: 4: 0 1: 6: 0.5 1: 10: 3 fifteen 16 17 eighteen 19 twenty 21 one Bitumen BND 200/300 mm 254 211 242 263 2 Bitumen BND 130/200 mm 186 134 178 188 3 Bitumen BND 90/130 mm 115 95 116 128 four Arbolite kg / cm ³ 14.2 30,4 26.6 25.7

For bitumen - units. ISM - depth of penetration of the needle 0.1 mm at 25 ° C, for all samples of bitumen (columns 19, 20,21) - water resistance with prolonged water saturation above 0.92 (hydrophobicity).

For arbolit - units. ism is the compressive strength at the age of 28 days, for all arbolite samples (columns 19, 20, 21) - water resistance with prolonged water saturation above 0.95 (hydrophobicity). Water saturation for bitumen (% by volume) was determined by samples molded from cuttings and cores of the finished road surface, for wood concrete - by finished products.

BIBLIOGRAPHY

PATENT

1. A.S. SU 668884, application 2563315 / 29-26 from 12.29.77, publ. 06/25/79, bull. Number 23.

2. A.S. SU 947091, application 2962073 / 23-26 from 07.17.80, publ. 07/30/82, bull. Number 28.

3. Patent RU 2098361 C1, application 95118795/25 from 1995.10.31, publ. 1997.12.10.

4. Patent RU 2116265 C1, application 96106660/25 from 1996.04.03, publ. 1998.07.27.

5. Patent RU 2148035 C1, application 99100534/12 of 1999.01.06, publ. 04/04/27.

6. Patent RU 2176660 C1, information about the application reg. No. 2000111586/04.

6.a) A.S. SU 1773886, application 4797790 \ 33 from 01/15/90, publ. 11/07/92, bull. Number 41.

7. BITUMEN

7.1. GOST 22245-90. Viscous petroleum bitumen.

7.2. GOST 6617-76. Bitumen oil construction.

7.3. GOST 31015-2002. MIXES ASPHALT CONCRETE AND ASPHALT CONCRETE.

7.4. Cementing materials BITREK.

7.5. Scientific-practical conference "On measures to improve the quality of the coating of highways of the North-West".

8. HUSBAND

8.1. Spill response for crude oil and petroleum products - ODM-1F sorbent.

8.2. COLLECTION OF INVESTMENT PROJECTS AND DEVELOPMENTS:

"Establishment of production for the production of amorphous silicon dioxide (silica)."

8.3. Project: "Development of a technology for producing and studying the properties of hydraulic binders based on local raw materials and production wastes."

8.4. Oil sorbents for surface waters.

9. Collection of investment projects and developments: "Obtaining amorphous silica from waste from rice production."

10. Japanese application No. 59-19760, С02F 11/14, op. 1984 year

11. SORBENTS

12. UK Patent Application, GB 2147286 A, INT CL ⁴ C04B 18/24; C04B 18/04, Published 9 May 1985, priority data 30 Sept. 1983, Australia.

13. A.S. SU 1773886 A1, application 4797790/33 from 01/15/90, publ. 11/07/92, bull. Number 41.

14. Act No. 01/17 of 09.15.06, the test of the claimed method.

Claims (5)

1. The method of disposal of oil sludge and husk of rice husk, which includes mixing waste products, characterized in that, for environmental safety and further useful redistribution of the semi-finished product, the husk of rice husk is used as agricultural waste by mixing it with oil slurry in the maximum concentration sorbent (husks) in the oil sludge. 2. The method according to claim 1, characterized in that as a further useful redistribution of the semi-finished product, it is briquetted with coal (cement) dust to obtain low-calorific fuel, followed by the use of ash from burning briquettes to obtain amorphous silica, which is then used as an additive for production high-quality binders, such as cements. 3. The method according to claim 1, characterized in that as a further useful redistribution of the semi-finished product, it is used after applying pressure to it, for example, an asphalt paver roller, a press in the manufacture of plates with concomitant heat treatment, as a hydrophobic coating, for example, for roads, for airfields, for hydraulic structures, etc. 4. The method according to claim 1, characterized in that the semi-finished product is used as a stabilizing additive in bitumen during the construction and repair of hydrophobic road and airfield coatings, city streets and squares. 5. The method according to claim 1, characterized in that the semi-finished product is used as a hydrophobic component in an amount of from 1 to 25% by weight of the filler, when producing arbolite by pressing from cement and filler in the form of husk of rice husk.