RU2106898C1 - Method of removing petroleum products, surfactants, and organic pollutants from waste waters - Google Patents

Abstract

FIELD: environmental protection. SUBSTANCE: invention is intended to be used when constructing treatment plants in oil production and oil processing industries as well as when eliminating consequences of incidents accompanied by strong pollution of water reservoirs. Waste water treatment is performed by way of successively filtering it through layers of basalt fiber (5-50 wt %) and powdered adsorbent - high-activity aluminum oxide (50-95 wt %) prepared by electric explosion of aluminum wire. EFFECT: enhanced treatment efficiency. 2 tbl, 9 ex

Description

 The invention relates to methods for purifying heavily contaminated water from oil products and surfactants, as well as other organic and inorganic pollution, and can be used to create treatment facilities at oil fields, oil refineries and pipeline transport, enterprises supplying oil products, as well as to eliminate the consequences of accidents involving severe pollution of the water basin.

 A variety of methods are known for purifying industrial wastewater from organic and inorganic contaminants, based on adsorption technologies using natural and synthetic adsorbents, as well as adsorbents obtained by processing waste from various industries. The most effective adsorbents, in particular activated carbons and ion-exchange resins, in conditions of severe water pollution by oil products, as a rule, quickly lose their working capacity and are used only for post-treatment, in combination with other adsorbents, for example, in a method and device for cleaning water from oil products in emergency situations (Austrian Pat. N 391124B, class C 02 F 1/18, published. 08.28.90) provides for the placement of an activated carbon filter after the preliminary treatment steps for water contaminated with oil products.

 Known methods for the purification of oily wastewater based on the joint use of activated carbons with heat-treated schungite (Aut. St. N 1453901, class C 02 F 1/28, published. 21.08.86), or in conjunction with an additional prefilter layer of fibrous material (Pat UK N 8810741.2, class B 01 D 46/00; published 08.11.89), which can be, for example, a layer of hydrothermally treated polyacrylonitrile fiber (Ed. St. USSR N 1650601, class C 02 F 1 / 28, published May 23, 91). In the general case, compositions of powdered materials allow combining the advantages and reducing the disadvantages of individual components (Filtering with the use of compositions of excipients / Leichkis I. M. // Chemical technology - 1990. -N 5.-S.52-57).

 Known methods for wastewater treatment from suspended and emulsified oil products using various synthetic and natural porous and fibrous adsorbents, for example, the use of filtering from oleophilic foam (Aut. St. USSR N 1662625, class B 01 D 39/00, published. 07.27.91 , BI N 26), filtering through asbestos-containing material (Aut. St. USSR N 1451099, C 02 F 1/28, published. 12.02.87), the use of activated cellulose (US Pat. USA N 306564, CL B 01 D 13 / 00; French Patent Application No. 2657076, class C 02 F 1/42, N 9000760, published July 19, 91), basalt fiber (Aut. St. N 1803388, class C 02 F 1/26, published March 23, 93; Auth. St. USSR N 1030319, class C 02 F 1/40, published 23.07.83).

 It is known to use activated alumina as an adsorbent for purifying water from organic and inorganic impurities, for example, in a combination of a peptized and activated mixture of carbon and powdered alumina (US Pat. No. 4,923,843, class B 01 J 20/08, published 08.05. 90).

 The indicated methods and devices are either bulky and multi-stage, or do not provide a sufficient degree of purification and quickly lose their effectiveness under conditions of highly contaminated (up to 1 - 2 g / l) water products of oil, which is typical for emergencies and normal water supply conditions in oil-producing regions of Russia. In addition, they, as a rule, do not provide a comprehensive purification of oil-contaminated water from surfactants, metals and other harmful substances.

 Closest to the claimed technical solution is a method of treating oil wastewater based on the use of filter material from four layers of basalt fiber (Filter for water purification from oil / O. Tutakov, N. Gavrilyuk, V. I. Bozhko, Shust E.A. // Industrial construction and engineering structures. - 1991.- N 4-С.34). The first and second layer consist of a knitting-piston material of stapled basaltic thin and superthin fibers. The third layer consists of needle-punched basalt material, and the fourth - of basalt tow fabric. The third and fourth layers perform the function of the frame, providing mechanical strength of the filter material.

 The use of fine-fiber basalt fiber as a filter charge is justified by its good sorption ability to oil and oil products, high corrosion and chemical resistance, allowing multiple hydrothermal and chemical regeneration of filters without noticeable loss of efficiency.

 However, the proposed technical solution is ineffective for deep wastewater treatment from emulsified oil products, especially at their high initial concentration, and does not provide a comprehensive treatment of water from oil products and other impurities, and the degree of purification is not high enough.

 The aim of the invention is to increase the degree of wastewater treatment from petroleum products and other organic and inorganic pollution.

This goal is achieved by treating wastewater contaminated with oil products by passing it through layers of materials: basalt fiber in the form of a fine fiber canvas, alternating with layers of highly dispersed highly active alumina powder obtained by hydrothermal treatment of ultrafine aluminum obtained by electric explosion of aluminum conductors when the ratio of components, wt.%:
Highly Active Alumina - 95 - 50
Fine fiber basalt canvas - 5 - 50
Distinctive features of the proposed technical solution are the use in the filtering process of a combination of at least 3 alternating layers of powder and fibrous adsorbents, the outer layers are made of fine basalt canvas and the inner layers are of highly active fine alumina. Another distinguishing feature is the use of ultrafine aluminum obtained by the method of electric explosion of conductors to produce highly active aluminum oxide as a starting material (Burtsev V.A., Kalinin N.V., Luchinsky A.V. Electric explosion of conductors and its use in electrophysical installations. - M .: Energoatomizdat, 1990.- 288 p.).

 Example 1 (prototype). Wastewater containing 50 mg / l of petroleum products and 5 mg / l of anionic surfactants (AAS) is passed through 4 layers of basalt fiber, of which two layers are composed of piercing mats, and the other two layers are of thin-fiber basalt canvas, each layer 25 mm high . The ratio of the mass of the passed water and the mass of the adsorbent 25: 1. The content of oil products in the filtrate after a single pass was 13.9 mg / l, APA - 2.9 mg / l.

 Example 2. Wastewater containing 50 mg / l of petroleum products and 5 mg / l of anionic surfactant is passed sequentially through three layers of adsorbents: first through a layer of fine fiber basalt fiber, then through a layer of alumina, and then again through a layer of basalt fiber. The ratio of the components 95: 5 wt.%. The height of the oxide adsorbent layer is 25 mm. The ratio of the mass of the passed water and the mass of the adsorbent 25: 1. The content of oil products in the filtrate after a single pass was 1.4 mg / l, APAW - 0.8 mg / l.

 Example 3. Wastewater containing 50 mg / l of oil products and 5 mg / l of anionic surfactants is passed sequentially through three layers of adsorbents: basalt fiber - alumina - basalt fiber. The ratio of the layers 85: 15 wt. % The height of the oxide adsorbent layer is 25 mm. The ratio of the mass of the passed water and the mass of the adsorbent is 25: 1. The content of oil products in the filtrate after a single pass was 1.3 mg / l, APA - 0.7 mg / l.

 Example 4. Wastewater containing 50 mg / l of petroleum products and 5 mg / l of anionic surfactants is passed sequentially through three layers of adsorbents: first through a layer of fine fiber basalt fiber, then through a layer of alumina, and then again through a layer of basalt fiber. The ratio of the layers 50:50 wt.%. The height of the oxide adsorbent layer is 25 mm. The ratio of the mass of the passed water and the mass of the adsorbent is 25: 1. The content of oil products in the filtrate after a single pass was 3.3 mg / l, APA - 2.9 mg / l.

 Example 5. Wastewater containing 50 mg / l of petroleum products and 5 mg / l of anionic surfactants is passed sequentially through five layers of adsorbents: basalt fiber - alumina - basalt fiber - alumina - basalt fiber. The ratio of the layers 85:15 wt.%. The height of the oxide adsorbent layer is 25 mm. The ratio of the mass of skipped water and the mass of adsorbent 25: 1. The content of petroleum products in the filtrate after a single pass was 0.5 mg / l, APA - 0.6 mg / l.

Example 6. Through 5 layers of adsorbents: basalt fiber - alumina - basalt fiber - alumina - basalt fiber with a component ratio of 85: 15 wt.% Pass water contaminated with 1,2,7,8-tetrachlorodibenzodioxin - 3500 • 10 ^-12 mg / l (280 MAC) and 2,3,7,8-tetrachlorodibenzodioxin - 5600 • 10 ^-12 mg / l (280 MAC) in an amount of 1 liter. No polychlorinated dibenzodioxins (PCDDs) were detected in the filtrate. The degree of purification is 100%.

 Example 7. Through 5 layers of adsorbents in example 5, water contaminated with 0.0056 mg / l of 3-chlorophenol and 0.0007 mg / l of 2,4,6-tetrachlorophenol (approximately 1 MAC) is passed. The content of 3-chlorophenol in the filtrate is 0.00068 mg / l, and 2,4,6-trichlorophenol is 0.00019 mg / l. The degree of purification was 88 and 72%, respectively.

 Example 8. Through 5 layers of adsorbent in example 5, water contaminated with organochlorine pesticides is passed: hexachlorocyclohexane (HCH) - 0.1047 mg / l (5.2 MAC) and 2,2,2-trichloro-1,1-bis-n -chlorophenyl) ethane (DDT) - 0.0242 mg / l (1 MPC). The content of HCCH in the filtrate is 0.0147 mg / L, DDT - 0.0048 mg / L. The degree of purification was 85 and 80%, respectively.

 Example 9. Through 5 layers of adsorbent in example 5, water contaminated with 5 mg / l propazine (5 MAC) is passed. The propazine content in the filtrate was 0.9 mg / L. The degree of purification is 82%.

 The effect of the ratio between alumina and basalt fiber on the degree of water purification from oil products and surfactants when passing sequentially through three layers of adsorbents, first through a layer of basalt fiber, then through highly active alumina, then through basalt fiber, are given in tables 1 and 2. The initial concentration petroleum products of 50 mg / l, APS - 5 mg / l. (Purification factor is the ratio of the initial concentration of pollution to its concentration in purified water).

 The data in tables 1 and 2 show that alternating layers of fine-fiber basalt fiber and oxide adsorbent provide the maximum degree of purification with a ratio of alumina to basalt fiber of 85:15 wt. %

 Thus, the proposed method allows you to clean wastewater containing not only petroleum products, but also surfactants, while the degree of purification is several times greater than that of the prototype.

Claims (3)

 1. The method of purification of highly contaminated wastewater from oil products, surfactants and organic pollutants, including filtering them through basalt fiber, characterized in that the filtering is carried out through alternating layers of fine fiber canvas from basalt fiber and highly active aluminum oxide, while the outer layers are made of basalt fiber.  2. The method according to p. 1, characterized in that the use of alumina, which is the product of oxidation in an aqueous medium of ultrafine aluminum powder obtained by the method of electric explosion of aluminum wire. 3. The method according to claim 1, characterized in that the filtering is carried out through layers of materials taken in the following ratio, wt.%:
Alumina - 50 - 95
Basalt fiber - 5 - 50

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