WO2012128671A1

WO2012128671A1 - Method for producing a sorbent for removing oil and petroleum products from an aqueous surface and from soil

Info

Publication number: WO2012128671A1
Application number: PCT/RU2012/000216
Authority: WO
Inventors: Екатерина Егоровна СИРОТКИНА; Анатолий Владимирович БОРИЛО
Original assignee: Общество С Ограниченной Ответственностью "Аркон Технология"
Priority date: 2011-03-24
Filing date: 2012-03-26
Publication date: 2012-09-27
Also published as: RU2463106C1

Abstract

The method for producing a sorbent for removing oil and petroleum products from an aqueous surface and from soil is carried out by hydrophobization of a fibrous cellulose material with a solution of oxidized ataxic polypropylene. The ataxic polypropylene is oxidized at a temperature of 180°С to 240°С for 4 to 6 hours and dissolved in tetrachloroethylene. The fibrous cellulose material is impregnated with the resultant solution containing 0.4 to 0.5% of oxidized ataxic polypropylene, and excess solution is drained and recycled. The impregnated fibrous cellulose material is dried to a constant weight, with heated air being passed therethrough. The tetrachloroethylene vapours are condensed and returned to the beginning of the process.

Description

A method of producing a sorbent for cleaning water surface and soil from oil and oil products

Technical field

The invention relates to a technology for the production of sorbents for cleaning water surface and soil from oil and oil products during their accidental or emergency spills, as well as for the treatment of oily wastewater.

State of the art

A known method of producing a sorbent of oil products (RU 2071828 C 1, IPC 6 B01J20 / 22, publ. 01/20/1997), including processing the carrier with a solution of active organic substances. Fibrous natural or synthetic material is used as a carrier, and solutions of alkyl carboxylic acids, higher aliphatic alcohols, their esters, polyolefins or paraffins in an organic low-boiling solvent selected from the class of hydrocarbons, halogenated hydrocarbons, ethers, sulfoxides are used as a solution of organic matter. The treatment is carried out at room temperature for 10-60 minutes at a concentration of active organic matter in solution from 0.1 to 1.0% in May, and after processing the sorbent is dried to constant weight at room temperature.

This method does not provide repeated use of the sorbent in the collection of petroleum products, since the active substance applied to the carrier is easily washed off with oil and petroleum products.

A known method of producing a sorbent for water purification from oil products and heavy metals (RU 2132226 C1, IPC 6 B01J20 / 06, B01J20 / 22, publ. 06/27/1999), including processing the fibrous carrier with titanium tetrachloride, followed by hydrolysis with water and drying. As the fibrous carrier use cellulose-containing material. Titanium tetrachloride is used in the form of its 2 - 7% solution in hydrocarbons With ₅ - With ₇ . The process is carried out to the content of titanium dioxide in the sorbent from 5 to 15 May. % In this method, a combustible solvent is used. The process of obtaining the sorbent is complicated, since it is multi-stage. The resulting sorbent does not have buoyancy and, therefore, is not suitable for collecting oil from water surfaces.

Closest to the proposed technical solution is a method of producing a sorbent for collecting oil and oil products from the water surface (RU 2061541 C1, IPC 6 B01J20 / 22, publ. 06/10/1996), which consists in the hydrophobization of fibrous cellulosic material with a solution of oxidized atactic polypropylene in aliphatic hydrocarbons and subsequent drying to constant weight.

The presence of carboxyl groups in oxidized atactic polypropylene allows one to create a strong bond with cellulose due to the formation of a hydrogen bond between the carbonyl groups of the cellulose and the carboxyl groups of the polymer, which ensures high polymer resistance to washing out by oil products and high hydrophobicity of the sorbent. In addition, oxidized atactic polypropylene forms cluster-type compounds with the cellulose surface, which significantly increases the sorption properties of natural fibers. These properties make it possible to ensure multiple use of the sorbent.

In this method of producing the sorbent, the conditions for the production of oxidized atactic polypropylene are not determined, which affect the modifying properties of the oxidized atactic polypropylene and the sorption properties of the sorbent with respect to oil and oil products. In addition, C ₅ - C ₇ aliphatic hydrocarbons, which are classified as fire and explosive organic solvents, are used as a solvent to dissolve atactic polypropylene.

Disclosure of invention

The objective of the invention is to increase production safety, to develop a non-waste technology for producing a hydrophobic fibrous sorbent with a high capacity in relation to oil and oil products, suitable for repeated regeneration while maintaining a high capacity for oil and oil products. The problem is solved due to the fact that in the method of producing a sorbent for cleaning water surface and soil from oil and oil products, as in the prototype, hydrophobization of fibrous cellulosic material with a solution of oxidized atactic polypropylene is carried out, followed by drying to constant weight.

According to the invention, atactic polypropylene is oxidized at a temperature of from 180 ° C to 240 ° C for 4 to 6 hours, dissolved in tetrachlorethylene; a fibrous cellulosic material is impregnated with a 0.4 to 0.5% solution of oxidized atactic polypropylene, excess the solution is drained and returned to recycling. The impregnated fibrous cellulosic material is dried by passing heated air through it. Vapor tetrachlorethylene is condensed and returned to the beginning of the process.

As the fibrous cellulosic material, batting, cotton wool or cotton waste can be used.

In the proposed method, the oxidation of atactic polypropylene is carried out at a temperature of 180 - 240 ° C and non-combustible tetrachlorethylene is used as a solvent for the oxidized atactic polypropylene, which is completely regenerated after drying the sorbent.

This method of producing a sorbent for cleaning water surface and soil from oil and oil products allows to obtain a sorbent with high sorption of oil and oil products in the presence of water, a sufficiently high ability to retain absorbed oil and oil products. Such a sorbent has high buoyancy, is capable of multiple mechanical regeneration (spin up to 20 times) while maintaining high sorption ability, and can also be disposed of by known methods in road construction, burning in furnaces, and biodegradation.

Based on the sorbent, special oil-absorbing products can be made - mats, napkins, booms. The main technological element in the production of these products is our proposed method for producing the sorbent.

This set of sorption-protective products provides nature users with the practical opportunity to quickly and timely respond to both standard and possible emergency situations, arising in the process of extraction, transportation, refining and use of oil and oil products.

The best embodiment of the invention

10 g of atactic polypropylene are heated in a reactor to 240 ° C and air is passed through the polymer melt with stirring for 4-6 hours. Then the air supply is stopped and the reaction mass is cooled to 80 ° C and dissolved in 1900 g of tetrachlorethylene with stirring.

The solution is cooled to room temperature, the resulting solution is poured into 40 g of cotton-based batting, soaked in batting at room temperature for 10-15 minutes, after which the excess solution is drained and returned to recycling, and hot air, heated to 80-100, is passed through the batting. ° C, until complete removal of the solvent. Air with solvent vapor enters the refrigerator, where tetrachlorethylene is condensed, which is reused to prepare a solution of oxidized atactic polypropylene.

The resulting sorbent after cooling to room temperature is examined for the sorption of oil. In a container of 200 cm 3 pour 80 cm 3 of water and 80 cm 3 of oil. 1 g of sorbent is placed on the surface and incubated for 1-3 minutes, the sorbent is taken out, the excess oil is allowed to drain for 1 min. Sorbent with oil is weighed. The weight difference of the sorbent before and after oil sorption determines the weight of the sorbed oil.

After the pressed oil, the sorbent is reused to collect oil.

The results of the influence of the oxidation conditions of atactic polypropylene and its content in a tetrachlorethylene solution on sorption by an oil sorbent are shown in Table 1.

The results of the effect of repeated use of the sorbent (batting is impregnated with a 0.4% solution of oxidized atactic polypropylene at 240 ° C for 4 hours) for collecting oil on its sorption ability are shown in table 2. Table 1

Concentra-

Temperature- Duration- Content Molecule Oxidation Oxygen capacity in the flax flax bone of oxidation, oxidized mass of atactic-atactic- atactic-oxidized polybent, polic poly - propylene g / g propylene, propylene in terachlor

° C% polypropy ethylene,

Lena%

Original - 1.04 26000 -

180 3 1.52 19900 0.4 20.5

180 4 3.34 16000 0.4 22.1

180 5 4.12 12400 0.4 23.0

180 5 4.12 12400 0.3 18.6

180 5 4.12 12400 0.45 23.6

180 5 4.12 12400 0.5 23.4

180 5 4.12 12400 0.6 19.2

180 6 4.32 10600 0.4 22.3

180 8 4.8 6700 0.4 18.9

190 4 3.45 13800 0.4 22.7

190 5 4.2 12400 0.4 23.6

190 6 4.43 9800 0.4 23.8

200 4 3.56 13200 0.4 21, 9

200 5 4.6 1 1200 0.4 24.0

200 6 4.8 9600 0.4 23.8

240 2 2.03 20,000 0.4 19.4

240 4 1.92 10,600 0.4 27.5

240 5 1.81 8300 0.4 28.8

240 5 1, 81 8300 0.3 18.2

240 5 1.81 8300 0.45 28.7

240 5 1, 81 8300 0.5 28.2

240 5 1.81 8300 0.6 20.8

240 6 1, 70 6400 0.4 27.0

240 8 1.73 5400 0.4 18.7 table 2

The number of regeneration cycles

squeezing oil from the sorbent Sorbent capacity, in a centrifuge, g / g number of times

1 27.5

2 26.7

3 26.9

4 26.4

5 26.5

6 26.8

7 26.3

8 26.2

9 25.7

10 25.8

1 1 24.9

12 24.6

13 24.2

14 23.6

15 23.4

16 23.4

17 23.2

18 22.8

19 22.6

20 22.5

21 21, 8

22 21.4

23 20.8

24 20.3

25 19.9 Industrial applicability

The proposed method for producing the sorbent is implemented on standard equipment for chemical production. For the oxidation stage, a stainless steel reactor equipped with a mechanical stirrer and heating to 300 ° C was used. A solution of oxidized atactic polypropylene in tetrachlorethylene was prepared in the same reactor with mechanical stirring after cooling the oxidation product. The impregnation and drying of the fibrous cellulosic material is carried out in separate steel containers. For the recovery of tetrachlorethylene vapors from hot air, standard tube coolers are used, cooled with cold tap water.

Claims

Claim

A method of producing a sorbent for cleaning water surface and soil from oil and oil products by hydrophobization of fibrous cellulosic material with a solution of oxidized atactic polypropylene followed by drying to constant weight, characterized in that atactic polypropylene is oxidized at a temperature of from 180 ° C to 240 ° C for 4 up to 6 hours, dissolve it in tetrachlorethylene, obtained from 0.4 to 0.5% solution of oxidized atactic polypropylene impregnate fibrous cellulosic material, drain the excess solution t and returned to recycling, the impregnated fibrous cellulosic material is dried, passing heated air through it, the tetrachlorethylene vapor is condensed and returned to the beginning of the process.