RU2569153C1 - Integrated waste treatment plant (versions) - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: according to the invention the pant comprises in-series a unit for preliminary treatment of sulphide-alkaline wastes from oil products and or suspended impurities, a unit for treatment from copper ions, which is equipped with a node for mixing sulphide-alkaline wastes and copper-containing wastes with copper-containing flow feed lines, a node for separating suspended insoluble or low-soluble particles having drain for copper sulphide, a unit for treatment from hydrogen sulphide and ammonia equipped with a node for mixing wastes with acidifying reagents and hydrogen sulphide and ammonia stripper with delivery of hot steam to its lower section, a unit for treatment by ozoning and/or biologic treatment of waste water by microbial strain featuring phenol-breaking activity. At vapour output from the stripper there is a chilling condenser and separator designed to return condensate from the separator to the stripper. The plant comprises a bypass line connecting the unit for preliminary treatment directly to the unit for treatment from hydrogen sulphide and ammonia.

EFFECT: improved quality of treatment due to excluded secondary pollution of wastes and atmosphere.

6 cl, 2 dwg, 1 tbl

Description

The invention relates to the field of integrated purification of sulphide-alkaline effluents (SSS) generated at oil refineries and petrochemical enterprises, and effluents containing copper ions, in particular from an installation for the production of acrylic acid.

Sulfide-alkaline effluents are the most polluted effluents, because contain phenols, neutral hydrocarbons, sulfides, ammonia, suspended impurities. The presence of a large number of technological processes at the enterprise, resulting in the formation of effluents that vary significantly in qualitative and quantitative composition, causes a large range of changes in the concentration of pollutants in the total effluent. The typical stock content is sulfides - 100-20000 mg / dm ³ , ammonium nitrogen - 750-5000 mg / dm ³ , phenols - 200-1000 mg / dm ³ , oil products - 200-3000 mg / dm ³ , suspended solids - 100 -350 mg / dm ³ .

The production stream of acrylic acid contains copper ions up to 300 mg / dm ³ , hydrocarbons 200-3000 mg / dm ³ .

Known biochemical purification of phenol-containing compounds using a strain of Pseudomonas aeruginosa XP-25 immobilized on a sorbent (patent for invention RU No. 2270807, IPC C02F3 / 34, published on 02.27.2006). But direct biological treatment of SCW is impossible due to the high concentration of hydrogen sulfide, which is detrimental to the strain of microorganisms.

A known installation for the purification of sulphide-alkaline effluents by carbonization (wastewater treatment of oil refineries / Ya.A. Karelin [et al.]. - M .: Stroyizdat, 1982). The installation includes a column reactor equipped with a mother liquor for supplying carbon dioxide. On the plates of the reactor column, the SSW reacts with carbon dioxide, with the release of hydrogen sulfide, phenol. The disadvantage of this installation is the discharge of blown gases for afterburning in the furnace, which causes secondary pollution of the atmosphere with sulfur oxides. The presence of a significant amount of unreacted carbon dioxide in the blown off gases (80-95% by volume) and a low concentration of hydrogen sulfide (5-15% by volume) preclude the possibility of utilizing hydrogen sulfide in Klaus furnaces.

A known method of neutralizing sulphide-alkaline liquid effluents, including feeding carbon dioxide and an ozone-air mixture into the liquid effluent (patent RU 2326824, IPC C02F 9/14, published June 20, 2008) and initiating a self-similar process of acidification of liquid effluents of the resulting sulfuric acid. The disadvantage of the installation is the secondary pollution of the effluent with sulfuric acid.

There is a method of purifying wastewater from copper ions where activated carbon is added to wastewater, sodium hydroxide is added to a pH of 10.7-12.0, the mixture is heated to 50-55 ° C, held at this temperature for 30 minutes and the precipitate is filtered off (copyright Certificate SU No. 1495308, published on July 23, 1989). The disadvantage of this method is the secondary pollution of the runoff with the reagents used (alkali).

The closest in technical essence is a sulfur-alkaline wastewater treatment plant (utility model patent RU No. 122188, IPC C02F 3/34, published January 10, 2012). The installation includes a series-connected unit for pre-treatment of oil products and suspended impurities; a hydrogen sulfide and ammonia purification unit, a mixing unit for acidifying the SHS and a hydrogen sulfide and ammonia stripping column by supplying water vapor to the bottom of the column; a condenser-cooler and a separator are installed at the vapor output from the column, providing condensation of water vapor with return to the stripping column; a biological wastewater treatment unit using a strain of microorganisms having phenol-destructive activity. The disadvantage of the installation is the lack of a comprehensive purification of effluents from oil products, copper ions, sulfide ions, ammonium nitrogen, phenols.

The technical result of the claimed invention is:

- expanding the arsenal of technical tools for the comprehensive treatment of sulfide-alkaline effluents and effluents of industries containing copper ions from sulfides, ammonia, phenols, copper ions, and neutral hydrocarbons;

- the implementation of the purification while obtaining a gas stream containing at least 60% wt. hydrogen sulfide and suitable as a component of raw materials for plants for the production of elemental sulfur by the Klaus method and the production of solid copper sulfide, which can be processed at the appropriate enterprises;

- the implementation of the treatment of sewage and wastewater from industries containing copper ions, without the formation of secondary pollution of wastewater and the atmosphere.

According to a first embodiment of the invention, the complex wastewater treatment plant includes a series-connected unit for the preliminary purification of sulfide-alkaline effluents from oil products and / or suspended impurities, a copper ion purification unit containing a mixing unit for sulfide-alkaline effluents and copper-containing effluents, which has a copper-containing effluent supply, an assembly separation of suspended insoluble or poorly soluble particles, having a copper sulfide outlet, a unit for cleaning hydrogen sulfide and ammonia, containing a unit for mixing effluents with sub reagents and a stripping column of hydrogen sulfide and ammonia, to the bottom of which water vapor is supplied, and a condenser-cooler and a separator are installed at the outlet of the vapor from the column, condensate from which is returned to the stripping column, an ozonation and / or biological wastewater treatment unit using strain microorganisms having phenol-destructive activity.

In a particular case, the installation includes a bypass line connecting the pre-treatment unit directly to the hydrogen sulfide and ammonia purification unit.

In a particular case, carbon dioxide and / or sulfuric acid is used as acidifying reagents at the unit for mixing effluents with acidifying reagents.

In the drawing of FIG. 1 shows a diagram of the first embodiment of an integrated installation for the purification of sulphide-alkaline effluents and effluents from industries containing copper compounds or ions.

Installation includes:

1 - block pre-treatment of petroleum products and / or suspended impurities;

2 - mixing unit of SHS and copper-containing effluents (purification unit for copper ions);

3 - node separation suspended insoluble or sparingly soluble particles (purification unit from copper ions);

4 - a unit for cleaning hydrogen sulfide and ammonia;

5 - block biological treatment and / or treatment with ozonation;

6 - condenser-refrigerator;

7 - separator;

8 - hydrogen sulfide gas stream;

9 - liquid flow (condensate) at the outlet of the separator;

10 - purified stock;

11 - source copper-containing drain;

12 - copper sulfide;

13 - site mixing runoff with acidifying reagents (in the particular case of carbon dioxide and / or sulfuric acid);

14 - stripping column;

15 - initial sulfide-alkaline runoff;

16 is a bypass line connecting the pre-treatment unit directly to the hydrogen sulfide and ammonia purification unit.

Installation works as follows. Sulfide-alkaline runoff 15 enters the block 1 pre-treatment of oil products and / or suspended impurities. Block 1 may include devices for physicochemical and / or mechanical treatment of oily wastewater, for example flotators, mixers and flocculation chambers for coagulation and flocculation processes, settlers. Block 1 leaves the purified SSS, with an oil content of not more than 50 mg / dm ³ and suspended solids of not more than 25 mg / dm ³ . The presence of petroleum products in the SCW reduces the efficiency of purification from phenol and phenol-containing compounds at block 5 of biological treatment and / or treatment with ozonation. Thus, the presence of block 1 pre-treatment of oil products and / or suspended impurities helps to improve the efficiency of cleaning and achieve the claimed technical result.

After cleaning of oil products, WMS come to the mixing unit 2 of WSS and copper-containing effluents 11. Mixing can be carried out directly in the pipe. Next, at unit 3, suspended insoluble or sparingly soluble particles are separated, and the separated copper sulfide 12 is removed from the installation. Separation of copper sulfide is possible using sedimentation, filtration and other known methods.

In the particular case, the installation additionally contains a bypass line 16 connecting the pre-treatment unit directly to the hydrogen sulfide and ammonia purification unit, bypassing the copper ion purification unit. As a result, a part of the SCH after the pre-treatment unit 1 can be directed via the bypass line directly to the hydrogen sulfide and ammonia purification unit 4.

After node 3, the effluent enters the block 4 for cleaning hydrogen sulfide and ammonia. In the mixing unit 13, the pH of the effluents is lowered by mixing with acidifying reagents, for example with carbon dioxide and / or sulfuric acid.

Next, the effluent flows to the top of the stripping column 14. At the bottom of the column 14, steam is supplied, by means of which stripping of hydrogen sulfide and ammonia is carried out. The overhead vapor from the column 14 is partially condensed in the condenser-cooler 6. Then, in the separator 7, the hydrogen sulfide gas stream 8 is separated from the liquid stream 9 returned to the column 14. Stream 8, containing: hydrogen sulfide - 70.4% wt., Ammonia - 17.5% wt., Water - 12.1% wt., And that meets the requirements for raw materials for the production of elemental sulfur by the Klaus method, can be sent to the installation of sulfur production by the Klaus method.

The stream of stripped effluents from the bottom of column 14 with a sulfide content of not more than 15 mg / dm ³ and ammonium nitrogen not more than 25 mg / dm ^{3 is} directed to ozonation or biological treatment unit 5. The purification from copper, hydrogen sulfide and ammonia ions prevents the death of microorganisms in block 5 or during the subsequent biological treatment of the factory runoff.

At block 5, biological wastewater treatment is carried out using a strain of microorganisms having phenol-destructive activity. Standard equipment for biological cleaning methods is used, for example, reactors with microorganisms immobilized on a sorbent, aerotanks.

Biological treatment can be carried out using the following strains and methods:

- Pseudomonas aeruginosa XP-25 VKPM B-8613 (patents for invention RU No. 2270805, 2270806, 2270807);

- Rhodococcusopacus VKM Ac-2546D (patent for the invention RU No. 2405036);

- Aureobacterium saperdae 6-204 (patent for the invention RU No. 2201446);

- Rsodococcus sp (patent for the invention RU No. 2107665);

- Pseudomonas putida 131 (patent for invention RU No. 2476385).

Biological treatment allows you to ensure the phenol content in the treated effluent 10 is not more than 0.5 mg / DM ³ .

At block 5, it is possible to carry out purification of the runoff by ozonation, which also allows the runoff to be cleaned of phenol and its compounds.

Cleaning at block 5 can be carried out either by ozonation, or by a biological method, or by a joint sequential or parallel treatment of the runoff using the indicated methods.

According to a second embodiment of the invention, the complex wastewater treatment plant comprises a serially connected mixing unit for sulphide-alkaline effluents and copper-containing effluents having inlets of a copper-containing effluent and sulphide-alkaline effluent, a preliminary treatment unit for sulphide-alkaline effluents from oil products and / or suspended impurities, a hydrogen sulfide purification unit and ammonia containing a unit for mixing effluents with acidifying reagents and a stripping column of hydrogen sulfide and ammonia by supplying water vapor to the bottom of the column, and a condenser-cooler and a separator are installed at the vapor outlet from the column, condensate from which is returned to the stripping column, an ozonation and / or biological wastewater treatment unit using a strain of microorganisms having phenol-destructive activity.

In the particular case, the installation additionally contains a bypass line connecting the initial sulphide-alkaline runoff with a pre-treatment unit for oil products and / or suspended impurities.

In a particular case, carbon dioxide and / or sulfuric acid is used as acidifying reagents at the unit for mixing effluents with acidifying reagents.

In the drawing of FIG. 2 shows a diagram of the second embodiment of an integrated installation for the purification of sulphide-alkaline effluents and effluents from industries containing copper compounds or ions.

Installation includes:

1 - block pre-treatment of petroleum products and / or suspended impurities;

2 - mixing unit SCH and copper-containing effluents;

4 - a unit for cleaning hydrogen sulfide and ammonia;

5 - block biological treatment and / or treatment with ozonation;

6 - condenser-refrigerator;

7 - separator;

8 - hydrogen sulfide gas stream;

9 - liquid stream (condensate) returned to the column;

10 - purified stock;

11 - source copper-containing drain;

12 - copper sulfide;

13 - node mixing the drain with an acid stream (in the particular case of carbon dioxide and / or sulfuric acid);

14 - stripping column;

15 - initial sulfide-alkaline runoff;

16 is a bypass line connecting the initial sulphide-alkaline runoff directly to the pre-treatment unit for oil products and / or suspended impurities.

Installation works as follows.

Sulphide-alkaline effluent 15 enters the mixing unit 2 of the SCW and copper-containing effluents 11. Mixing can be carried out directly in the pipe, in the tank or in another way. Next, the effluent goes to block 2 for pre-treatment of oil products and / or suspended impurities, where solid copper sulfide (formed as a result of the reaction) can be separated by settling, filtering, flotation, or otherwise. Functionally, the mixing unit 2 and the preliminary cleaning unit 1 can be implemented in a single apparatus, for example, in a tank, where WMS and copper-containing effluents are mixed, followed by sedimentation in the tank.

In a particular case, there is a bypass line 16 connecting the initial sulphide-alkaline runoff with a pre-treatment unit for oil products and / or suspended impurities, bypassing the mixing unit 2 for mixing water and copper-containing effluents. At the same time, part of the SCW flow can flow to block 1, without flowing into mixing with the copper-containing drain 11 at node 2.

Block 1 leaves the treated effluent with an oil content of not more than 50 mg / dm ³ , suspended solids not more than 25 mg / dm ³ and copper ions not more than 5 mg / dm ³ . The presence of oil products in the effluent reduces the efficiency of purification from phenol and phenol-containing compounds at the stage of biological treatment and / or ozonation treatment (block 5). The purification from copper ions prevents the death of microorganisms in block 5 or during subsequent biological treatment of the factory runoff. Therefore, the presence of the pre-cleaning unit 1 helps to increase the cleaning efficiency and achieve the claimed technical result.

Next, the drain enters the block 4 for cleaning from hydrogen sulfide and ammonia and block 5 biological treatment and / or treatment by ozonation, working, as shown in the first embodiment of the invention.

The composition of the streams according to two embodiments of the invention is presented in the table.

Thus, the installation according to the above options allows complex cleaning of sulfide-alkaline effluents and effluents of plants containing copper compounds or ions from sulfides, ammonia, phenols, neutral hydrocarbons and copper without the formation of secondary pollution of effluents and the atmosphere with the simultaneous production of a gas stream containing more 60% hydrogen sulfide and suitable as a component of raw materials for plants for the production of elemental sulfur by the Klaus method. In addition, the installation allows to obtain copper sulfide, which can be processed at the relevant enterprises.

Claims (6)

1. Installation of complex wastewater treatment, including a series-connected unit for the preliminary purification of sulfide-alkaline effluents from oil products and / or suspended impurities, a purification unit for copper ions, containing a mixing unit for sulfide-alkaline effluents and copper-containing effluents, which has a copper-containing effluent inlet, separation unit suspended insoluble or sparingly soluble particles having a copper sulfide outlet, a hydrogen sulfide and ammonia purification unit, comprising a wastewater mixing unit with acidifying reagents and an outlet column hydrogen sulfide and ammonia, at the bottom of which water vapor is supplied, and at the outlet of the vapor from the column there is a condenser-cooler and a separator, the condensate from which is returned to the stripping column, an ozonation and / or biological wastewater treatment unit using a strain of microorganisms having phenol-destructive activity. 2. Installation according to claim 1, characterized in that it further comprises a bypass line connecting the pre-treatment unit directly to the hydrogen sulfide and ammonia purification unit. 3. Installation according to claim 1, characterized in that carbon dioxide and / or sulfuric acid is used as acidifying reagents at the site for mixing effluents with acidifying agents. 4. Installation of complex wastewater treatment, including a serially connected mixing unit for sulphide-alkaline effluents and copper-containing effluents, having inlets of copper-containing effluents and sulphide-alkaline effluents, a unit for preliminary treatment of sulphide-alkaline effluents from oil products and / or suspended impurities, a unit for cleaning hydrogen sulfide and ammonia containing a unit for mixing effluents with acidifying reagents and a stripping column of hydrogen sulfide and ammonia by supplying water vapor to the bottom of the column, and at the outlet of the vapor from the column s condenser cooler and separator, from which condensate is returned to the stripper unit ozonation purification and / or biological treatment of wastewater by microorganisms strain having fenolrazrushayuschuyu activity. 5. Installation according to claim 4, characterized in that it further comprises a bypass line connecting the initial sulphide-alkaline effluent directly to the unit for pre-treatment of effluents from oil products and / or suspended impurities. 6. Installation according to claim 4, characterized in that carbon dioxide and / or sulfuric acid is used as acidifying reagents at the site for mixing effluents with acidifying reagents.

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