WO1998009724A1

WO1998009724A1 - A crude oil (oil products) adsorbent and the method of producing it

Info

Publication number: WO1998009724A1
Application number: PCT/IB1996/000905
Authority: WO
Inventors: Zinaida T. Dimitrieva
Original assignee: Destiny Oil Anstalt
Priority date: 1996-09-09
Filing date: 1996-09-09
Publication date: 1998-03-12
Also published as: AU6751996A

Abstract

The cleaning of surface water and soil from flammable and toxic liquids, the collection of crude oil (petroleum products) aimed at reducing loss and the pollution of the environment during emergency situations, and also the absorption (trapping) of gaseous waste from the petrochemical industry. The crude oil (petroleum products) adsorbent and the method of producing it (consisting of an organic surfactant and a porous material/carrier) is distinguished by the fact that as a surfactant it contains substances from the classes of the higher alkylcarbonic acids, the alkyl ethers of alkylcarbonic acids, the higher aliphatic alcohols and their simple ethers polyolefins, paraffins, applied (introduced) by a special method onto the branched surface of the fibrous or powdered polymeric materials/carriers with a defined structure.

Description

A Crude oil (Oil Products) Adsorbent and the Method of producing it

Field of Technology

The invention relates to the efficient collection of crude oil (oil products) from the surface of water on the basis of the complex application of high-capacity adsorbents intended to eliminate emergency spillages of flammable and toxic liquids.

The invention can with the greatest success ensure ecological safety during the production, transporting, processing, and storing of crude oil (oil products) and can reduce the loss of them in emergency conditions.

The invention can also be used with great success during the absorption (trapping) of gaseous waste (emissions into the atmosphere) from chemical plants and oil refineries.

Backround Art

In connection with the growth in the production, refining and transporting of crude oil and the use of crude oil products, the areas of polluted water and soil are increasing. It is known that 1 I. of oil pollutes 1 ,000,000 of water.

The drawbacks of the known adsorbent materials and the methods for collecting the film of oil from the surface of water consists above all in their low capacity to absorb hydrocarbons. The use of oil emulsifiers, for example, containing 30 mass % of a compound of [RCO(R')_aO] - [0(R')_bH]_{m 1} (the X-group of a polyhydric alcohol, R-alkyl, C₈.₂₂, R'- ethylene propylene oxide group, m = 3-6, a+b = 10-50), 16 mass % monooleate adsorbent, 16 mass % of sodium dioctyl- sulfosuccinate and 38 mass % of the monobutylene ether of ethylene glycol (Patent JP 59-110925, cl. C09K 3/32, B01 F 17/00) of emulsifiers on the basis of ethyl-, octyl-, lauryl- alcohols, castor oil, ethylene oxide (Patent PL 145458 cl. B01 F17/38) does not resolve the problem of cleaning the oil from the surface of the water because the collection of the liquid oil emulsion from the surface of the water is a technically extremely complex problem.

The use of oil coagulants consisting of carboxy-methylated yeasts, the salts of a multivalent metal (aluminium sulphate, aluminium chloride, ferrous chloride) and a fatty acid C₈-C₂₂ (Patent US 417265, cl. 252/316 and Patent JP 52-19440, cl. B01 J13/00, BO1 D17/02) also does not ensure an effective collection of the oil film from the surface of water.

Adsorbents on the basis of wood shavings, wood flour, hemp, clays, ash, viscoses, synthetic fibre, processed silicon or petroleum oil, the monalkyl ethers of polyethylene glycol have an adsorbent capacity for liquid hydrocarbons of only 1.5 - 3.0 kg / kg (Patent JP 61 -284, cl. C09K3/32; 56-100884, cl. C09K3/32; N54-15279, N54-30154 cl. 01 D15/00; Patent DE 3416357, cl. C09K 3/39; Patents RU 1323536, cl. 02F 1/29., E02B 15/04; 1060755, cl. E02B 15/04).

Granulated mineral wool and tyre chippings which have been proposed as adsorbents for crude oil on the surface of water are even less effective (Patent FR 2457345, cl. E02B 15/04; Patent GB 1384217, cl. E02B 15 / 04; Patent RU 1305128, cl. E02B 15 / 04.

Keramzit modified with iron absorbs crude oil from the surface of water in a quantity of only 0.45g for 1g of adsorbent (Patent RU 1062340, cl. E02B 15 / 04).

Using the product of pyrolysis of the solid sludge of domestic sewage as an oil adsorbent increases its adsorption capacity by comparison with known adsorbents to only 4.5 kg / kg. However, this small increase in capacity does not justify the heavy expenditure on producing the adsorbent by the solid sludge pyrolysis method requiring a temperature of 600° - 800° for 2-4 hours (Patent

RU 939636, cl. E02B 15 / 04).

The use of modified [aerosil] and polyvinyl chloride in powder form increases the collection of oil from the surface of the water to 11.5 - 15g for 1g of adsorbent (Patent RU 834085, cl. C09K 3/32; 1214595, cl. E02B 15 / 04). However, these adsorbents quickly sink.

With the purpose of increasing the time that the adsorbents remain on the surface of the water and cutting down the expenditure rate, the following have been proposed: a modified [aerosil] and multi-component compositions based on the non-organic salts of multivalent metals, soda, anion-bearing organic compounds (e.g. a peat-alkali reagent, latex, polyamine oxidation paraffin), applied to volcanic ash or pine turnings (Patents RU 834085, cl. C09K 3/32; 8932245, cl. E02B 15 / 04). These adsorbents are not discriminating with regard to hydrocarbon liquids. In connection with the large content of the hydrophilic mass (metal salts, soda) they adsorb sea water along with the adsorption of the oil.

Fibrous wood pulp produced during sulphate and sulphite processing does not surpass the above-mentioned adsorbents in the adsorption of crude oil and hydrocarbons (Patents US 4753917, cl. B01J 20 /22; 4925343, cl. E02B 15/00).

An adsorbent based on basalt fibre (85-98 mass %), dimethyl dichlorsilane, polyorganic silicon hydride liquids or paraffins and ozocerite in a quantity of 2-15 mass % has a capacity for hydrocarbons of 2 to 110g per 1 g of adsorbent (Patent RU 1930319, cl. C02F 1/40). However, this adsorbent, despite its high capacity for adsorption, has a number of major drawbacks. In the process of manufacturing it gives off toxic, gaseous hydrogen chloride. Moreover, the method for producing the given adsorbent by means of the interaction of organic silicon hydride liquids, paraffin, wax with a basalt fibre having a complex chemical composition, is achieved by heating the reactive mass to 160° - 200° which makes the technology energy consuming, expensive in terms of material, equipment, and ecologically stressed. The non-reproducibility of its adsorption capacity for crude oil is clearly governed by the difficulty of producing the adsorbent. For instance, under similar production conditions, adsorbents based on 98g and 85g of a basalt fibre and 2.0g and 15g of dimethyl dichlorsilane have a crude oil-bearing capacity of: 52g and 110g per 1 g of adsorbent respectively.

Under the same conditions an adsorbent based on 90g of basalt fibre and 10g of dimethyl dichlorsilane absorbs only 8g of crude oil per 1g of adsorbent. The non-reproducibility of the capacity can be explained by the acidity of the adsorbent; its pH is equal to 5.7 - 6.3, as a result of which, the adsorbent obviously absorbs sea water together with the oil, and that exaggerates it capacity in an unnatural way.

An adsorbing material is known which contains peat as its basis (carrier), and the salts of aliphatic amines with the long organic chain C₈-C₁₆ and the following ratio of components as its mass % :

Peat -95.0 - 99.95

Amine salt 0.05 - 5.0

(Patent RU 704903, cl. C02B 9 / 02). The adsorption capacity for oil of the known material equals 13 - 15.5g / g without taking account of the mass of the peat - if the mass of the peat is taken into account the capacity of the adsorbent will be less.. Moreover, on account of the strong polarity of the adsorbent "peat+R-NH₃" and the strong affinity of the tertiary amino group to water, it absorbs water together with the crude oil in the form of a aqueous emulsion. Therefore, the capacity of the adsorbent for crude oil is far less than for oil.

The major drawbacks of this known adsorbent include the high cost and the energy consuming technology for producing the adsorbent. Due to the low solubility of the aliphatic amines in water at a normal temperature they are exposed to the peat during the heating of the aqueous solution to 80 - 90°. After this, to remove the water from the adsorbent, heating again, and possibly a vacuum, are required. Moreover, due to the low tendency towards surface branching or the low capacity of the peat for the active (adsorbing) agent, the maximum content of aliphatic a ine in the peat is only equal to 5 mass %. This means that the known material does not have the potential for increasing its adsorption capacity - the basic parameter of the adsorbent. Moreover, an adsorbent in powder form based on peat sinks in water. Peats by their structure, and by the place of their origin, differ markedly from one another. The general drawback of the known inventions is the fact that in their descriptions the absorption capacity is shown without regard for the parameters of the specific experiment, e.g. the thickness of the layer of the crude oil (hydrocarbon) being absorbed, the density of the water, the time taken for the adsorption. For this, reason a comparison of adsorbents by their absorption criteria is extremely difficult.

Disclosure of Invention

The task which the invention aims to solve is the identification of an adsorbent and a method (technology) for producing it which will allow the adsorption capacity of the adsorbent for crude oil (petroleum product) to be increased, the frequency of its use to be expanded, the expenditure of the surfactant to be reduced, and in the final analysis, the life of the adsorbent to be extended.

A technical result is being achieved by the fact that the adsorbent for crude oil (petroleum products), based on an organic surfactant (the higher alkylamines) and a carrier / material (peat), in accordance with the invention, contains as a surfactant fractions of: the higher (fatty) alkylcarbonic acids, RCOOH (C₉ - C₂₇), the alkyl ethers of alkylcarbonic acids RCOOR' (R' = C,-C_1S; R = C₈ - C₂₇), the higher aliphatic alcohols ROH (R = C₁₅ - C₃₀), their simple ethers, ROR (R = C₈ - C₁₇), and also polyolefins, paraffins and their mixtures, and as a porous material / carrier - fibrous, and natural and synthetic polymers in powder form, specifically: cotton and wood pulp viscose, polyvinyl acetate, polyether, polyacrylo-nitrile, polyvinyl chloride, polypropylene, polyethylene.

Aiming towards increasing the selectivness of the adsorbent for crude oils, fuels, and oils, - in accordance with the invention, the following are used as a surfactant: mixtures of the fractions of alkylcarbonic acids, aliphatic alcohols, their simple and complex ethers in specific mass ratios.

Aiming towards increasing the hydrophobic nature of the adsorbent and its affinity to hydrocarbons, - in accordance with the invention, the surfactant, based on carbonic acids and alcohols, contains additionally a hydrophobic compound from the classes of polyolefins, paraffins and higher ethers.

It is preferable to use in the composition of the surfactant mixtures of the fractions of the higher (high-molecular) alkylcarbonic acids jointly with the hydrophobic compounds in any of their mass ratios. The amount of surfactant in the make-up of the adsorbent, in accordance with the invention, is equal from 0.1 to 7.0 mass %; the preferred concentration of surfactant in the adsorbent is 1.5 - 3.8 mass %.

For increasing the capacity of the adsorbent and the speed it absorbs the crude oil (petroleum products) from solid and liquid surfaces it is preferable to use a non-fabric, fibrous material / carrier with a density of 40-70 kg / m\ and polymers in powder form with a polydispersity of particles of 5-200 μm.

Aiming for a uniform application of the surfactant onto the surface of the porous material / carrier, in accordance with the invention, this process is effected (carried out) in the medium of an organic solvent without heating. After processing the material with the surfactant solution, the adsorbent is dried, also without the application of heat.

For regulating the technical and the capacitive characteristics of adsorbent for the crude oil (petroleum product), depending on the nature and the structure of the components, the length of time that the material / carrier remains in contact with the surfactant solution is varied between 10-360 minutes, whilst the concentration of the surfactant in the industrial solution is altered from 0.1 to 2.0 mass %.

The application (introduction) of the surfactant onto the surface of the material / carrier, in accordance with the invention, takes place in the medium of hydrocarbons with a low boiling point (pentane - heptane, petroleum ether, a fraction of light hydrocarbons), halohydrocarbons, chloroform, carbon tetrachloride, esters, sulfoxides. It is preferable to produce the adsorbent in the medium of halohydrocarbons and chloroform.

The adsorption characteristics, depending on the make-up of the adsorbents, (according to the invention) are defined during the absorption of the layers (films) of crude oil (petroleum products) with a thickness of 0.3 - 3.0 mm from the surface of water, i.e. when the surface interaction between the crude oil and the water is at its most powerful, and destruction of this interaction might occur if the interaction between the adsorbent and the crude oil were any more vigorous than the interaction between the crude oil and the water.

The thick layers (films) of crude oil (petroleum products) are absorbed from the surface of water preferably using adsorbents based on fibrous materials, whereas the monomolecular (iridescent) films of hydrocarbons are absorbed by polymers in powder form.

The adsorbent with set properties (in accordance with the invention) is prepared in accordance with industrial rules and in accordance with the following procedure. A sample of the material / carrier with a specific mass [mj is immersed on metallic gauze netting into an air-tight vessel containing the surfactant solution with a defined starting concentration. Depending on its nature and structure, the sample is kept in the surfactant solution for 10-360 minutes at normal temperature. The material processed in this way is transferred from the reactor of impregnation together with the gauze netting into a drying chamber equipped with low-level ventilation or a blower. Dried to a constant weight, the adsorbent sample is weighed (m) and the content of the surfactant in it is defined

(C_surt , mass %):

(C_surf = (m-m₀ )/m] • 100 (1)

The evaporated solvent after the drying of the adsorbent is condensed in a trap and returned to the carrier impregnation reactor. A filter is fitted at the trap exit to absorb any remains of the solvent. The surfactant solution remaining in the reactor is used to impregnate another sample of the carrier, and the volume and concentration of the surfactant in it is brought up to the required starting values. Depending on the nature of the chosen components, the starting concentration of the solution and surfactant, and the length of impregnation (length of contact) an adsorbent with a prescribed capacity is obtained (table 1 ).

Defining the concentration of the surfactant in the solution after impregnation of the carrier.

For making an analysis out of the reactor, an aliquot quantity of the solution υ_a is taken, with a density d, and it is placed into a retort with a mass m_{1 f} the solvent is evaporated to a constant weight (m₂), and the concentration of the surfactant is calculated (mass %):

C-_suri= [(m₂-m,) /v_a d] * 100 (2)

The quantity of solvent which has to be added to the reactor of impregnation in order to achieve the required starting concentration of surfactant (C_surf) (if C_1sur1 > C_surt) the solution is calculated from formula (3):

υ₂ = [(C_1surt - C_surt) / C_surf] (vo -υ_a) (3) where v- = the volume of the surfactant solution which remains after impregnation, ml;

υ₂ = the volume of solvent which it is necessary to add to the reactor of impregnation , ml;

υ_a = the aliquot amount of surfactant solution taken for analysis, ml.;

Cι_surι = the concentration of surfactant solution which remains after the impregnation of the sample of the adsorbent, mass %;

C_surf = the concentration of the required starting solution of the surfactant in order to produce a new sample of the adsorbent, mass %.

The quantity of surfactant which has to be added to the reactor of impregnation for obtaining the required starting concentration of surfactant (if C_1sur( < C_surt) in the solution is defined by formula (4):

m_a = [(C_surf - C_1surf) / 100] • [ (_υι -υ_a ) d] (4)

where m_a = the mass of the surfactant required to achieve the starting solution of surfactant, g;

C_surf = the starting concentration of surfactant for impregnating the carrier, mass

%;

C_1sur1 = the concentration of surfactant solution remaining in the reactor after impregnation of the sample, mass %;

υ, = the volume of surfactant solution remaining after impregnation of the sample, ml; υ_a = the aliquot amount of surfactant solution taken for analysis, ml.;

d = the density of the surfactant solution after impregnation of the sample, g / cm³.

Table 1. Selection of industrial parameters for the process to produce an adsorbent based on the viscoses and fractions of RCOOH (C₉-C_1β:C₁₇- C₂₀:C₂₁-C_Z7=2:3:5) with C_8Urf (mass %) and capacity E(g/g) set by the concentration of surfactant in the carrier.

Imp- Concentration of the starting surfactant solution for impregnating the carrier, reg- mass % nat- ion time/ hour

0.1 0.2 0.3 0.35 0.5 1.0 surf E Csurf E surf E C_Surf E Csurf E surf E

1/6 1.09 34.2 1.62 36.2 3.06 44.1 3.72 48.7 7.97 38.4 16.31 32.9

1/3 1.15 35.1 1.73 36.9 3.5 47.1 3.84 49.9 9.64 35.1 16.20 33.4

1/2 1.17 35.5 1.82 38.1 3.81 48.9 4.46 47.6 9.09 34.9 15.73 34.8

2/3 1.19 36.3 1.88 38.7 3.84 49.5 4.88 46.3 9.09 34.5 16.20 32.7

5/6 1.17 35.1 1.86 38.9 4.46 37.3 5.26 45.2 9.09 35.2 16.30 33.0

1 1.20 34.4 1.86 39.4 5.11 46.6 4.67 45.9 9.60 35.0 15.73 35.2

4 - - 1.88 39.7 - - 4.71 46.2 - - - -

6 - - 2.09 40.6 - - 4.71 46.1 - - - -

15 - - 1.89 38.5 - - 4.71 46.0 - - - -

The results of table 1 show that, according to the invention, the technology for producing porous adsorbents excludes heating and complicated industrial equipment - it is not energy consuming. Besides this, the technology, assisted by such parameters as the starting concentration and the composition of the surfactant, the length of the process, the nature of the material / carrier, allows the process of applying the surfactant to be controlled on the branched surface of the carrier, and to produce adsorbents with prescribed adsorption properties. With a low content of the active agent in the structure of the material, the adsorbents are characterised by a high capacity: up to 45-50kg of crude oil per 1 kg of adsorbent. The technology ensures the complete hydrophobic nature of the adsorbent. The technology which has been developed can be effectively repeated in the process to manufacture large quantities of the adsorbents. The adsorbents do not absorb water. The surfactants do not dissolve in water. The adsorbents are regenerated by the simple effect of squeezing out or by centrifugal force. After regeneration the adsorbents can be used many times over for absorbing crude oil (petroleum products) from the surface of water.

Table 2.

Capacity of an adsorbent (based on nitron and the surfactant mixture) - (see

Example 4) - depending on the frequency of regeneration and use during the adsorption of crude oil from the surface of water

Number of times adsorbent Duration of centrifugal Capacity of the adsorbent used separation, mins. for crude oil, g /g

1 3 39.71

2 3 39.22

3 3 39.10

4 3 38.18

5 3 38.61

6 4 37.43

7 4 37.04

8 4 35.29

9 5 36.64

10 5 34.11

11 5 33.78

12 5 34.15

13 6 32.25

14 6 32.40

15 6 30.61 Modes for Carrying Out the Invention

Example 1. An 11.0 I., 0.3% solution of a fraction of alkylcarbonic acids, C₁₇-C₂₅ in chloroform, is loaded into the reactor where impregnation is to take place. 1 kg of cotton fibre material in the form of matting is mounted on metallic (plastic) gauze netting and immersed in this solution. The sample is kept in the solution for 30 minutes at normal temperature. The processed (impregnated) material on the gauze netting is transferred to a drying chamber in which the solvent is evaporated without heating until a constant weight of matting is reached. An adsorbent is produced with a surfactant content of 3.8 mass % and an adsorption capacity of 48.9kg of crude oil per 1 kg of adsorbent during a single collection (adsorption) of crude oil from the surface of water. The hydrophobic nature of the adsorbent amounts to 99.78%.

Example 2. 20g of cotton fibre material in the form of matting is loaded into a impregnation reactor and a 1 I. , 0.1 % solution of mixed alcohols, ROH (R= C₁₅- C₂₃) in petroleum ether is added. The material is kept in the solution for 50 minutes without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of active agent of 1.17 mass % and an adsorption capacity (single time) for crude oil from the surface of water of 35.1 g /g. The hydrophobic nature of the adsorbent is 98%.

Example 3. 30g of cotton fibre material in the form of matting is loaded into a impregnation reactor and a 1.4 I., 0.3% solution of mixed ethers, RCOOR' (R= C₁₆-C₂₃, R' = C₁₂-C₁₃ ) in hexane is added. The material is kept in the solution for 60 minutes without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of surfactant of 5.11 mass % and a single-time adsorption capacity for crude oil from the surface of water of 43.6 g /g. The hydrophobic nature of the adsorbent is 99.7%.

Example 4. 20g of polyacrylonitrile fibrous material (nitron) in the form of matting is loaded into a impregnation reactor and a 0.7 I. , 0.2% benzene solution consisting of a mixture of atactic polypropylene and a fraction of RCOOH (R= C^-C^) in a mass ratio of 1 :1 is added. The material is kept in the solution for 4 hours without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of surfactant of 1.6 mass % and a single-time adsorption capacity for crude oil from the surface of water of 39.7 g /g. The hydrophobic nature of the adsorbent is 99.5%. Table 2 shows the results of the change in the capacity of the adsorbent depending on the number of times it is used to collect crude oil from the surface of water, and the frequency of its regeneration. After using for 15 times, the capacity of the adsorbent for attracting crude oil diminishes by 21 %.

Example 5. 20g of nitron in the form of matting is loaded into a impregnation reactor and a 0.7 I., 0.8% solution of paraffin in a mixture with a fraction of RCOOH acids (C₁₅-C₂₇) with a mass ratio of 3:1 respectively in chloroform is added. The material is kept in the solution for 6 hours without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of surfactant of 4.71 mass % and the following single-time adsorption capacity from the surface of water for: crude oil - 46.1 g / g; and diesel fuel - 32 g / g. The hydrophobic nature of the adsorbent is 100%.

Example 6. 80g of polyester fibrous material (lavsan) in the form of matting is loaded into a impregnation reactor and a 3.8 I., 0.2% solution of the ethers of fatty acids, RCOOR' (R= C₈-C₂₁, R' = CV-C,, ) in petroleum ether is added. The material is kept in the solution for 1/6 hours (10 mins.) without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting.

An adsorbent is produced with a content of surfactant of 3.7 mass % and a single-time adsorption capacity for crude oil from the surface of water of 29 g /g.

The hydrophobic nature of the adsorbent is 100%.

Example 7. 50g of nitron in the form of matting is loaded into a impregnation reactor and a 1.7 I. , 0.1 % solution of fatty acids, RCOOH (R= C₁₀-C₂₅) in carbon tetrachloride is added. The material is kept in the solution for 2/3 hours (40 mins.) without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of surfactant of 1.19 mass % and a single-time adsorption capacity for crude oil from the surface of water of 36.3 g /g, and for diesel fuel - of 31 g /g. The hydrophobic nature of the adsorbent is 98.9%.

Example 8. 20g of polypropylene fibrous material in the form of matting is loaded into a impregnation reactor and a 1.3 I. , 0.29% solution of polyisoprene in chloroform is added. The material is kept in the solution for 1 hour without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of surfactant of 2.2 mass % and a single-time adsorption capacity for crude oil from the surface of water of 30 g /g, and for oil - of 27.2 g / g. The hydrophobic nature of the adsorbent is 100%.

Example 9. 100g of polypropylene fibrous material in the form of matting is loaded into a impregnation reactor and a 2.1 I. , 2.0% solution of a fraction of alkyl carbonic acids C₁₀-C2_Z5 in pentane is added. The sample is kept in the solution for 1 hour without heating. The impregnated material is transferred on the gauze netting into a drying chamber where the solvent is evaporated without heating to a constant weight of matting. An adsorbent is produced with a content of surfactant of 15.7 mass % and a single-time adsorption capacity for crude oil from the surface of water of 35.2 g /g.

Example 10. 300 ml of chloroform is loaded into an impregnation reactor and a 1.44 g (0.32 mass %) mixture of fractions of alkyl carbonic acids C₉-C₁₆: C₁₇-C2₂₁ : C₂₂-C2₂₇ = 2:3:5 is dissolved in it. Cotton or nitron matting is loaded into this solution with a mass of 5 g, a thickness of 2 cm, and is kept in the solution for 50- 60 minutes without heating. After processing the matting, it is dried without heating to a constant weight. An adsorbent is produced with a content of surfactant of 3.8 mass % and a single-time adsorption capacity for crude oil from the surface of water of 48.6 g /g.

Example 11. 500 ml of chloroform is loaded into an impregnation reactor and a 10.67 g (1.4 mass %) mixture of fractions of alkyl carbonic acids C₉-C₁₆: C_l7-C2₂₁ ■ C₂₂-C2₂₇ = 2:3:5 is dissolved in it. 3.01 g (0.4 mass %) of paraffin is added to this solution and it is agitated until the components have completely dissolved. Nitron matting with a thickness of 0.5 cm. and a mass of 10 g is loaded into this starting solution, and it is impregnated with the surfactant solution for 50-60 minutes without heating. After processing the matting, it is dried without heating to a constant weight. An adsorbent is produced with a content of surfactant of 3.8 mass % and a single-time adsorption capacity for crude oil from the surface of water of 49.3 g /g. Table 3 shows examples of producing adsorbents with a prescribed overall content of surfactant (3.8 mass %) in an adsorbent based on nitron (cotton) and a mixture of fractions of alkylcarbonic acids with the addition to them of hydrophobic compounds in the starting solution for the impregnation of the carrier.

Example 12. Crude oil (diesel fuel) with a layer thickness (film) of 1-2 mm is poured onto the surface of water. 5.1 g of isotactic polypropylene powder with a particle size of 25-150 μm is spray coated onto the crude oil (hydrocarbon) film. After 35-40 minutes the swelled adsorbent is collected mechanically from the surface of the water. The crude oil (diesel fuel) is squeezed out of the adsorbent by means of centrifugal force. The single-time capacity of the adsorbent amounts to 1.2 (0.9) g / g. The process for adsorbing the crude oil (diesel fuel) by the use of a regenerated adsorbent is repeated 27 times. The overall capacity of the adsorbent based on isotactic polypropylene amounts to 27.4 (18.8)g of crude oil per 1g of the polymer.

Example 13. Crude oil (diesel fuel) with a layer thickness (film) of 1 -2 mm. is poured onto the surface of water. 7.6g of polypropylene powder (containing in its structure 15 mass % of atactic poly-propylene) with a particle size of 50-180 _μm is spray coated onto the crude oil (hydrocarbon) film. After 45 minutes the swelled adsorbent is collected mechanically from the surface of the water. The crude oil (diesel fuel) is squeezed out of the adsorbent by means of centrifugal force. The single-time capacity of the adsorbent amounts to 2.3 (1.5) g / g. The process for the adsorption / desorption of the crude oil (diesel fuel) from the surface of water is repeated 20 times. The overall capacity of the adsorbent amounts to 36 (23.8) g /g.

Example 14. Crude oil is poured onto the surface of water in such a way that an iridescent (monomolecular) film is formed. 5.7g of polypropylene powder (containing in its structure 15 mass % of atactic polypropylene) with a particle size of 50-180 μm is spray coated onto the crude oil (hydrocarbon) film. After 30- 35 minutes the iridescent film is adsorbed by the adsorbent until the water becomes completely transparent. The process of adsorbing the iridescent film is repeated until the adsorbent is completely saturated with the crude oil. The single-time capacity of the adsorbent during the collection of the iridescent film from the surface of water amounts to 4.5 g / g. Table 3. The single-time capacity (E) of the adsorbents depending on the concentration of the surfactant components in the impregnation solution. The overall concentration of surfactant in the adsorbent is 3.8 mass %. The mass of the adsorbent is 2.0g. The thickness of the matting is 0.5 cm. The layer of crude oil on the water is 1 mm.

Composition of surfactant is a mixture of

No fractions of Cotton carrier Nitron carrier RCOOH (MF) C₉-C₁₆: C₁₇- C2₂₁ : C₂₂-C2₂₇ = 2:3:5 and hydrophobic compound

Content of E of the Content of E of the surfactant adsorbent for surfactant adsorbent for components in crude oil, g /g components in crude oil, g /g the carrier the carrier impregnation impregnation solution, mass solution, mass % %

MF 0.32 48.6 1.60 39.8

MF 0.26 1.50 Paraffin 0.06 49.3 0.09 36.6

MF 0.25 1.40 Paraffin 0.08 52.2 0.12 37.3

MF 0.24 1.20 Paraffin 0.10 53.0 0.35 39.4

MF 0.23 1.00 Paraffin 0.12 50.4 0.40 40.1

MF 0.22 0.90 Paraffin 0.14 46.7 0.47 40.0

MF 0.21 0.80

Paraffin 0.15 40.5 0.55 38.7

MF 0.32 0.75

Paraffin 0.03 52.8 0.65 38.3

MF 0.25 1.40 Polyisoprene 0.08 47.4 0.12 37.5 0 MF 0.25 1.40 Polybutadiene 0.08 40.0 1.12 33.8

Claims

1. The adsorbent of the crude oil (petroleum products) and the method of producing it (consisting of a surfactant and a porous material-carrier) is distinguished by the fact that as a surfactant it contains agents from the classes of higher alkyl carbonic acids, the alkyl ethers of alkyl carbonic acids, the higher aliphatic alcohols and their simple ethers, polyolefins, and paraffins applied (introduced) in a special way onto the branched surface of fibrous or powdery polymeric materials-carriers of a defined structure.

2. The crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that as a surfactant it contains mixtures of alkylcarbonic acids of the formula RCOOH of the following fractions C₉-C₁₆: C₁₇-C₂₀ •' C₂₁-C₂₇ with mass ratios from 0.2:1 :1 - 0.5:1 :3 - 0.5:2:3 to 1 :1 :1 - 1 :3:5 - 2:3:5 - 2:3:7 respectively.

3. The oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that as a surfactant it contains mixtures of the aliphatic ethers of akyl carbonic acids of the formula RCOOR' (R' = C C₁₅) of the following fractions: R = C₈-C₁₆, R = C₁₇-C₂₀₎ R = C₂₁-C₂₇ with mass ratios from 0.2:1 :1 - 0.5:1 :3 - 0.5:2:3 to 1 :1 :1 - 1 :3:5 - 2:3:5 - 2:3:7 respectively. -

4. The crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that as a surfactant it contains paraffins, aliphatic alcohols, ROH (R = C₁₅-C₃₀ ), polypropylene of an atactic structure, polyisoprene, polyisobutylene, polybutadiene or their mixtures in any mass ratio.

5. The crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that as a surfactant it contains, together with, and simultaneously, mixtures of the fractions of the alkyl carbonic acids in paragraph 2, and mixtures of the fractions of the aliphatic ethers of the alkyl carbonic acids in paragraph 3 in their mass ratio - RCOOH:RCOOR' = 10:1 - 1 :10

6 The crude oil (petroleum products) adsorbent in paragraphs 2 and 3 is distinguished by the fact that, additionally to the surfactant, it contains a hydrophobic component (H) in a mass ratio - surfactant:H = 5:1 - 1 :5.

7. The crude oil (petroleum products) adsorbent in paragraph 6 is distinguished by the fact that the following are used as a hydrophobic component (H): paraffin, aliphatic alcohol (ROH, R = C₁₅-C₃₀ ), dialkyl ether (ROR, R = C₈-C₁₇ ), atactic polypropylene, polyisoprene, polyisobutylene, polybutadiene.

8. The crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that it contains a surfactant and a material-carrier with the following ratio of components, mass %:

surfactant - 0.1 - 7.0 carrier - 93 - 99.9.

9. The crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that as a carrier it contains a non-fabric material in the form of matting, a boom, cassettes of natural and synthetic fibres with a density of 40-70kg / m³ and with fibres secured by the needle-punching method.

10. The crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that as a carrier it contains the powders of synthetic polymers with a polydispersity of particles of 5-200 _μm.

11. The method for producing the crude oil (petroleum products) adsorbent in paragraph 1 is distinguished by the fact that the surfactant is applied to the surface of the material-carrier in the medium of an organic solvent and with contact between the surfactant solution and carrier for 10-360 minutes without heating and with a surfactant concentration in the solution of 0.1 - 2.0 mass %.

After processing, the adsorbent is dried to a constant weight at normal temperature.

12. The method for producing the crude oil (petroleum products) adsorbent in paragraph 11 is distinguished by the fact that as an organic solvent hydrocarbons with a low boiling point, halohydrocarbons, chloroform, carbon tetrachloride, ethers and sulfoxides are used.