SK279394B6 - Agent for removing free liquid hydrocarbons and compounds thereof - Google Patents

Abstract

An agent contains basic elements of black which are produced during the process of gasification of oil and tar materials at a temperature ranging from 1,300 to 2,300 K. The basic particles' porous structure is formed by free agglomeration of the primary particles or secondary agglomerates having an aggregation force determined according to a granule strength, but not higher than 5 N upon a formed particle with a specific surface, determined by nitrogen adsorption, in a range from 700 to 1,250 m2/g and with a specific pore volume in a range from 2.0 to 4.5 cm3/g. Addition of non-polar organic substances, e.g. highmolecular alkanes, results in non-wettability of the surface of black's basic particles. The agent is suitable for removing liquid hydrocarbons and its compounds, optionally hydrocarbon derivatives out of the polluted surfaces, e.g. exteriors and interiors of technological devices or surfaces of running or dead waters.

Description

Technical field

The invention relates to the field of processing, storage and transport of petroleum products, namely, agents for removing free hydrocarbons and their derivatives from contaminated surface areas.

The free hydrocarbon removal agent is a special carbon black prepared from aqueous suspensions of carbon black microparticles by pelletizing with hydrocarbon solvents and formed into spherical granules, optionally prepared in the form of dust. Special carbon black is a product of partial oxidation of petroleum or tar raw materials.

The invention relates to an agent for removing free hydrocarbons and mixtures thereof, or hydrocarbon derivatives thereof from contaminated surfaces, which may be solidified or non-solidified surface earth surfaces, internal or external surfaces of process equipment, surface water surfaces and the like.

BACKGROUND OF THE INVENTION

Crude oil and petroleum products processing plants, tar and semi-finished products processing plants, petrochemical plants, mineral oil refineries, fuel depots and pumping stations, situations where non-compliance with technological processes occurs regulations or a variety of other causes leakage of liquid hydrocarbons and subsequent contamination of surface areas. In some cases, e.g. For repairs of technological equipment, it is necessary to completely remove the liquid hydrocarbon residues from the system before repairing. It is also necessary to remove hydrocarbons when leaking into watercourses to prevent environmental accidents.

At present, free liquid hydrocarbons are removed from contaminated surface areas by the use of special absorbents based on polyethylene foam, cellulose fibers and the like, or by using inorganic sorbent materials based on silicates. A disadvantage of the sorbent materials used hitherto is their low sorptive capacity, difficult regeneration, requiring mostly special regeneration furnaces, or in the case of regeneration of a sorbent saturated with hydrocarbons, a special deposition must be available.

SUMMARY OF THE INVENTION

These drawbacks are overcome by an agent for removing liquid hydrocarbons and their derivatives from contaminated surface areas.

A reagent to remove free liquid hydrocarbons and mixtures thereof, as well as hydrocarbon derivatives from contaminated surfaces, such as paved or unpaved terrestrial surfaces, internal or external surfaces of process equipment, surfaces of standing or flowing, eventually moving water levels and other unspecified surfaces, based on the carbon black according to the invention, it is characterized in that it is formed from basic carbon black particles formed in the gasification process of petroleum or tar raw materials at temperatures of 1300 to 2300 ° K, which are shaped into granules with a diameter of

0.1 to 5 mm, or left in the form of dust, their porous structure is formed by free agglomeration of primary particles or secondary agglomerates with mechanical cohesion, determined on the basis of granular strength, not exceeding 5 N per shaped particle having a specific surface area, determined by adsorption nitrogen in the range of 700 to 1250 n / g, with a specific pore volume in the range of 2.0 to 4.5 cm 3 / g; % of high molecular weight alkanes in an amount not exceeding 20% by weight, preferably in the range of 10 to 15% by weight, calculated on the weight of the carbon black.

Determination of specific surface area is performed according to ASTM D 3037 B by nitrogen adsorption. The method is based on determining the amount of gas required to form a simple layer of gas molecules, i.e., a molecular layer on a sample. Testing is carried out using nitrogen gas at liquid nitrogen temperature.

The determination of the specific pore volume is carried out e.g. high pressure mercury porosimeter CARLO ERBA 225. The method uses the phenomenon of capillary depression. Mercury penetrates the pores of the test substances under the influence of higher pressures. This pressure is related to the pore radius and the volume of the mercury injected then corresponds to the volume of the filled pores.

The relationship between the pore radius and the pressure at which mercury pores are filled is expressed by the WASHBURN equation

2acosa r = ---------->

P where r - the effective pore radius, σ - the surface tension of mercury, and - the contact (wetting) angle Hg with the solid, P - the total pressure at which Hg enters the pores.

The evaluation is performed in the form of integral or differential distribution.

The consumption of free liquid hydrocarbon mixture removal agent is in the range of 0.1 to 1 kg of carbon black granules per 1 kg of hydrocarbons.

The agent according to the invention has the following advantages - especially carbon black, granular or left in the form of dust, when in contact with free liquid hydrocarbons adsorb these substances on their surface and form a separate non-sticky layer of sorbent particles with pores filled with liquid hydrocarbons removed. The efficiency of the liquid surface hydrocarbon removal process depends on the contact time of the sorbent and the adsorbent. Due to the extraordinary ability of the reagent to bind hydrocarbons on its surface, complete sorption of the hydrocarbons occurs in virtually 10 minutes. This sorbent material is able to adsorb to itself five to six times its weight. This ability is due to the porous structure formed in the carbon black formation process, which can be increased by the adsorptive during the sorption process.

Deactivated sorbent, i. j. special soot with pores filled with hydrocarbons to be removed, unlike the sorption materials used hitherto and without the need for additional fuel, is burnt. The incineration utilizes not only the energy value of the absorbed hydrocarbons, but also the energy content of the actual sorbent - soot, which is essentially pure carbon. The sorbent is burned in solid fuel furnaces. In addition, the deactivated sorbent can be mixed in the furnace

Or waste oils and prepare a suspension of special soot in the oil or generally hydrocarbon fractions and burn the resulting suspension in a liquid fuel burner.

In the manner described, any free hydrocarbons or mixtures thereof or their derivatives can be advantageously removed from the contaminated surface areas, which is particularly desirable in the case of environmental accidents.

The invention is illustrated by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

An oil spill of 10.5 m2 and a layer thickness of approx. 1 mm was detected on the surface of standing water. The contamination corresponded to an oil concentration of 830 g per 1 water level. The oil slick was sprinkled with 3 kg of sorbent, with quantitative oil sorption. Carbon black granules of 0.5 to 2 mm in size with a mechanical particle strength of 0.8 N per particle, a specific surface area of 964 m @ 2 / g and a specific pore volume of 4.1 cm @ 2 / g were used as the sorption agent. These carbon blacks were obtained in the partial oxidation of the heavy petroleum fraction at 1665 ° K and 3.2 MPa.

The deactivated sorbent was removed from the water level and the residual oil concentration at the water level was found to be 0.004 g / m 2, corresponding to a purification process efficiency of greater than 99.999%. The sorbent consumption was 0.344 kg per 1 kg of oil.

Example 2

There was a breakdown in the oil industry economy of the engineering company, during which about 200 liters of oil had escaped to the spring. The nominal wall for catching the hydrocarbon stain was built approximately 1500 m below the leak site. In front of the wall, 35 kg of the sorbent specified in Example 1 was successively poured onto the water surface, allowing practically quantitative removal of the oil layer from the jar. After removal of the sorbent from the water surface, the efficiency of the purification process was checked. Surface water samples were taken from the space in front of the wall so that the height of the surface layer removed did not exceed 5 mm. The oil content of the sampled samples did not exceed 0.25 ppm.

Example 3

Technological adjustments and regular technical revision were necessary on the light fuel oil tank. The device was emptied and the inexhaustible liquid residue was removed from the device with the sorption agent of the invention. Carbon black from the gasification of the black oil was used as the sorbent. The technological conditions of the gasification process were: temperature 1630 ° K and pressure 3.4 MPa. The basic carbon black particles having a specific surface area of 1,063 m 2 / g and a specific pore volume of 4.35 cm @ -1 were formed into spherical granules having a size of 0.8 to 1.3 mm. The mechanical strength of the carbon black granules did not exceed 1.27 N per particle.

The liquid layer was overlaid with 10 kg of reagent and after 15 minutes of sorption, the inactivated sorbent was mechanically removed from the apparatus. The bottom of the container was smooth and glossy, indicating a high efficiency of the reagent used. The hydrocarbon content of the collected reagent was 4.67 kg per kg of sorbent.

Example 4

When pumping diesel fuel, it was blown to the floor of the concrete gripper. The amount leaked was estimated to be 50 L. The hydrocarbon spot formed was immediately sprinkled with 10 kg of the sorbent specified in Example 3. Within 5 minutes the diesel fuel was quantitatively sorbed into the pores of the sorbent and after a further 5 minutes a layer of deactivated sorbent was possible. remove it from the floor. The removed sorbent, saturated with hydrocarbons, was non-sticky. The hydrocarbon content of the deactivated sorbent was 4.26 kg per 1 kg of sorbent.

Example 5

In the event of a motor vehicle failure, engine oil leaked in the amount of approx. 1500 g on the clay surface of the yard. The resulting oil stain was immediately overlaid with 300 g of the sorbent, the specification of which is given in Example 1. Within two minutes, the oil was quantitatively sorbed into the pores of the sorbent. The sorbent was quickly removed and the clay surface was contaminated by hydrocarbon infiltration into the soil. Using the sorbent, 1448 g of oil was collected which was not sufficient to soak into the clay surface.

Example 6

On the surface of standing water two oil spots of approx. 1 m2 and a layer thickness of approx. 0.5 mm were modeled. Both stains were sprinkled with a sorption agent, resulting in quantitative oil sorption. 0.5 to 1.5 mm carbon black granules having a mechanical particle strength of 2.3 N per particle, a specific surface area of 1,024 m 2 / g and a specific pore volume of 4.2 cm 2 / g, with an addition of 10% weight. These carbon blacks were obtained in the partial oxidation of the heavy petroleum fraction at a temperature of 1680 ° K and a pressure of 3.35 MPa. The same carbon black was added as a comparative sorption agent without the addition of 10 wt. hydrocarbons. One spot was covered with 200 g of the specified sorbent, and the other spot was covered with 200 g of the comparative sorbent. In both cases, there was virtually quantitative oil sorption. The residual oil concentration at the water level after removal of the sorbent was 0.005 g / m 2. The sorbent was left on the water surface for 24 hours in both cases. In the case of soot with the addition of hydrocarbons as a non-wetting agent, virtually all of the sorbent remained at the water level (more than 99.999%), with the comparative agent falling below about 10% of the sorbent.

Industrial usability

The agent of the invention may be used to remove free liquid hydrocarbons that are spread on standing or flowing water levels, or spilled on paved or unpaved open areas, or to remove free hydrocarbon residues from process equipment.

Claims (1)

PATENT CLAIMS Reagent for the removal of free liquid hydrocarbons and mixtures thereof, and possibly hydrocarbon derivatives, from contaminated surfaces, such as paved or unpaved terrestrial surfaces, internal or external surfaces of process equipment, surfaces of standing or flowing or otherwise moving water levels and other unspecified surfaces, based on carbon black, characterized in that it consists of basic carbon black particles resulting from the gasification process of petroleum or tar feedstocks at temperatures of 1300 to 2300 ° K, which are shaped into granules with a diameter of 0,1 to 5 mm or kept in the form of their porous structure is formed by free agglomeration of primary particles or secondary agglomerates with mechanical cohesion, determined on the basis of granular strength not exceeding 5 N per shaped particle, with a specific surface area determined by adsorption of nitrogen in the between 700 and 1250 m ² / g, with a specific pore volume in the range of 2.0 to 4.5 cm 3 / g; % of high molecular weight alkanes, in an amount not exceeding 20% by weight, preferably in the range of 10 to 15% by weight, calculated on the weight of the carbon black.