CN105439312A - Coking wastewater reuse device and treatment technology - Google Patents

Coking wastewater reuse device and treatment technology Download PDF

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Publication number
CN105439312A
CN105439312A CN201410508142.9A CN201410508142A CN105439312A CN 105439312 A CN105439312 A CN 105439312A CN 201410508142 A CN201410508142 A CN 201410508142A CN 105439312 A CN105439312 A CN 105439312A
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China
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described
tank
waste water
cross
heterogeneous catalyst
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CN201410508142.9A
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Chinese (zh)
Inventor
殷武
王虎
罗红妍
白永玲
章真杰
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上海宝钢化工有限公司
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Priority to CN201410508142.9A priority Critical patent/CN105439312A/en
Publication of CN105439312A publication Critical patent/CN105439312A/en

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Abstract

The invention provides a coking wastewater reuse device, which comprises a raw water tank, a first reaction tank, a first flocculation tank, a first settlement tank, a cross flow heterogeneous catalysis apparatus and a first middle water tank that are connected in order. The catalysis apparatus is internally provided with reaction columns filled with a catalyst. The outlet of the first middle water tank is connected to a second flocculation precipitation apparatus, an ultrafiltration apparatus and a reverse osmosis apparatus. The invention also provides a technology for coking wastewater reuse treatment with the device. The device and the technology can effectively perform depth treatment reuse directed to coking wastewater, also have the characteristics of short treatment process, stable treatment effect, low production and operation cost, convenient operation and stable water production rate, can effectively treat hardly degradable biochemical wastewater, make the effluent water accord with the requirements of reuse standard, reduce the influence of pollutants to the environment, and improve the economic benefits.

Description

A kind of coking waste water reuse device and treatment process

Technical field

The present invention relates to waste water treating and reutilizing field, the novel process of specifically reuse after a kind of Treatment of Coking Effluent.

Background technology

Coking chemical waste water is a kind of high COD, high phenol value, high ammonia nitrogen, highly-saline difficult degradation industrial organic waste water.There is many difficulties in Treatment of Coking Effluent always.Country is more and more higher for the environmental requirement of coking industry, in October, 2012 implement " more original for coking industry discharge of wastewater limit value " Iron And Steel Industry pollution discharge standard " (GB13456-92) and " integrated wastewater discharge standard " (GB8978-1996) increase substantially by coking industry pollutant emission standard GB16171-2012.Domestic in the majority to Treatment of Coking Effluent research and probe, it is little that practical stability runs, and effective process of its coking chemical waste water hardly degraded organic substance is difficult point and the emphasis of restriction reuse always.

The research and development of domestic coking waste water reuse process disposal technology are little.More existing patent documentations are mainly depended merely on embrane method and are filtered solution reuse, but because it does not well solve the impact stifled on film dirt of the hardly degraded organic substances such as phenyl ring, heterocycle, condensed ring, reuse operating performance is not good, and have pretreated system before its some films also all because pretreating effect is unstable, COD is high causes the problems such as membrane lifetime shortening not solve very well, so wherein actual motion case is little.The more ripe waste water recycling process of current use is mainly by the biochemical water depth treatment process of " catalytic oxidation+electricity flocculation+electro-flotation+ultrafiltration+reverse osmosis ".By adopting electro-catalytic oxidation technology and electric flocculation-air floating technology etc. as preprocessing means, then in conjunction with ultrafiltration and reverse osmosis technology advanced treatment and reuse coking chemical waste water.The problems such as it is longer that this method exists treating processes, and floor space is large, and life of equipment is failed to understand, processing cost is high.

Summary of the invention

Therefore, the technical problem to be solved in the present invention is to provide the coking waste water reuse device that a kind for the treatment of effect is stablized, production run cost is lower, operation operation is easy.Another technical problem that the present invention will solve is, provides and utilizes this device to carry out the technique of coking waste water reuse process.

Technical scheme of the present invention is, a kind of coking waste water reuse device, comprise the former tank, the first reactive tank, the first flocculation tank, the first subsider and the first intermediate water tank that connect successively, it is characterized in that: between described first subsider and the first intermediate water tank, be provided with cross-flow heterogeneous catalyst device, described cross-flow heterogeneous catalyst device comprises the first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit that connect successively; Be respectively arranged with reaction column in described first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit, in described reaction column, be filled with catalyzer;

The outlet of described first intermediate water tank is connected with the entrance of the second reactive tank, second reactive tank is connected successively with the second flocculation tank, the second subsider, the second intermediate water tank, the outlet of described second intermediate water tank is connected with the entrance of more medium filter by respective pump assembly, the outlet of more medium filter is connected with the entrance of ultrafiltration system, the outlet of described ultrafiltration system is connected with the entrance of ultrafiltration water tank, and the outlet of ultrafiltration water tank is connected with first-stage reverse osmosis system, two-stage reverse osmosis system and reuse water tank successively.

Wherein, the outlet of described second intermediate water tank is connected with the entrance of described ultrafiltration system.

Wherein, hyperfiltration membrane assembly is provided with in described ultrafiltration system.

Present invention also offers a kind of coking waste water reuse treatment process, comprise the following steps:

Pre-treatment: extract biochemical secondary clarifier effluent and enter former tank and carry out water quality and quantity homogenizing, enter one-level flocculation deposition apparatus again and carry out flocculation sediment, supernatant liquor after precipitation enters cross-flow heterogeneous catalyst device, the catalyzer added in hydrogen peroxide and described cross-flow heterogeneous catalyst device reacts, carry out COD degradation, stay for some time; Described one-level flocculation deposition apparatus comprises the first reactive tank, the first flocculation tank and the first subsider; Described cross-flow heterogeneous catalyst device comprises the first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit that connect successively, is provided with reaction column, is filled with catalyzer in described reaction column in described cross-flow heterogeneous catalyst device;

Reacted waste water is entered secondary flocculation deposition apparatus, and enter the second intermediate water tank after precipitation water outlet adjustment pH, mud arranges concentration outward;

Pretreated waste water enters ultra-filtration equipment through more medium filter, then enters reverse osmosis unit; Described ultra-filtration equipment comprises more medium filter, ultrafiltration system and ultrafiltration water tank; Described reverse osmosis unit comprises first-stage reverse osmosis system and two-stage reverse osmosis system.

Water outlet pH is generally adjusted to 7-9.

According to coking waste water reuse treatment process of the present invention, preferably, the mol ratio of described hydrogen peroxide and catalyzer is 2 ~ 4:1.

Further, described catalyzer is noble metal catalyst.

Or described catalyzer is Fe 2+class catalyzer.Such as can be ferrous sulfate.

According to coking waste water reuse treatment process of the present invention, preferably, the described residence time is 4-8 hour.

According to coking waste water reuse treatment process of the present invention, preferably, be provided with hyperfiltration membrane assembly in described ultrafiltration system, hyperfiltration membrane assembly adopts external pressing type hollow fibrous membrane.

According to coking waste water reuse treatment process of the present invention, preferably, the material of described macaroni yarn selects wetting ability special type improvement PVDF.PVDF requires to have wetting ability, not easily adheres to pollutent, has high filtration flux.

The present invention discloses a kind of coking waste water reuse treatment process, especially adopts conventional biochemical treatment process Persistent organic pollutants for coking chemical waste water, i.e. coking wastewater deep treatment reuse technology.The present invention is through the multinomial catalyzed oxidation → ultrafiltration → ro treatment technology of dosing coagulating treatment → cross-flow the coking chemical waste water after biochemistry, by multiple-effect oxidation means, used water difficult to degradate is oxidized, reduce the pollutents such as COD, T-CN, chromophoric group and the SS in waste water, creating good running environment for follow-up embrane method process makes stable water outlet reach the requirement of reuse standard, reduces dense water and arranges impact on environment outward.The present invention is simple to operate, stable, can be applied to coking chemical waste water both domestic and external and other industrial effluent reusing art breading, effectively can solve the requirement of wastewater to reach standard reuse and process the high problem of energy consumption.

Membrane filtration pattern of the present invention is micro-cross flow filter, and ultrafiltration system is provided with a set of automatic back-flushing device, and need clean film when ultrafiltration and reverse osmosis membrane reach certain pressure reduction, back washing device is for cleaning film.Ultrafiltration is produced water water pump lifting and is entered reverse osmosis unit, be designed to one-level two sections, the reverse osmosis rate of recovery, about 70%, produces water conductivity at 50us/cm, after dense water collects oxidizing reaction, COD reaches 150mg/L and drains into plant area's flushing cinder, produces water and again utilizes as the make up water of recirculated water.In first-stage reverse osmosis system, accessible dense water collecting device, is further processed dense water.

The invention has the beneficial effects as follows:

The present invention is shorter relative to treatment scheme, treatment effect stable, production run cost is lower, operation operation is easy, producing water ratio is stablized, can effectively process difficult degradation biochemical waste water, make water outlet meet the requirement of reuse standard, decreasing pollution thing, on the impact of environment, is increased economic efficiency.

The present invention effectively can carry out advanced treatment and reclamation for coking chemical waste water, treatment scheme is shorter simultaneously, treatment effect stable, production run cost is lower, operation operation is easy, producing water ratio is stablized, can effectively process difficult degradation biochemical waste water, water outlet is made to meet the requirement of reuse standard, decreasing pollution thing, on the impact of environment, is increased economic efficiency.Coking wastewater deep treatment reuse field can be widely used in.Before entering film process, can effectively reduce COD content.Following table 1 is each stage COD data.

Table 1 different time each stage COD data

Accompanying drawing explanation

Fig. 1 is setting drawing of the present invention.

In figure, the former tank of 1-, 2-first reactive tank, 3-first flocculation tank, 4-first subsider, 5-cross-flow heterogeneous catalyst device, 6-first intermediate water tank, 7-second reactive tank, 8-second flocculation tank, 9-second subsider, 10-second intermediate water tank, 11-more medium filter, 12-ultrafiltration system, 13-ultrafiltration water tank, 14-first-stage reverse osmosis system, 15-two-stage reverse osmosis system, 16-reuse water tank, 17-reaction column.

Embodiment

Embodiment 1

As shown in Figure 1, a kind of coking waste water reuse device, comprise former tank 1, first reactive tank 2, first flocculation tank 3, first subsider 4 and the first intermediate water tank 6 that connect successively, between described first subsider 4 and the first intermediate water tank 6, be provided with cross-flow heterogeneous catalyst device 7, cross-flow heterogeneous catalyst device 7 comprises two catalytic units, the first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit; Be respectively arranged with reaction column 17 in first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit, in reaction column, be filled with catalyzer.Reaction column 17 is in sleeking structural arrangement.

The outlet of the first intermediate water tank 6 is connected with the entrance of the second reactive tank 7, second reactive tank 7 is connected successively with the second flocculation tank 8, second subsider 9, second intermediate water tank 10, the outlet of described second intermediate water tank 10 is connected by the entrance of respective pump assembly with more medium filter 11, the outlet of more medium filter 11 is connected with the entrance of ultrafiltration system 12, the outlet of described ultrafiltration system 12 is connected with the entrance of ultrafiltration water tank 13, and the outlet of ultrafiltration water tank 13 is connected with first-stage reverse osmosis system 14, two-stage reverse osmosis system 15 and reuse water tank 16 successively.

Coking waste water reuse treatment process: waste water entered one-level flocculation sediment, cross-flow heterogeneous catalyst device, secondary flocculation sediment, strainer, ultra-filtration equipment and reverse osmosis unit successively, waste water enters into ultrafiltration and reverse osmosis membrane processing after dosing precipitation and the process of multinomial cross-flow catalytic unit, after ultrafiltration and reverse osmosis membrane processing, effluent quality reaches open type circular water replenishing standard.Concrete steps are:

Pre-treatment: extract biochemical secondary clarifier effluent and enter former tank and carry out water quality and quantity homogenizing, enter one-level flocculation deposition apparatus again and carry out flocculation sediment, supernatant liquor after precipitation enters cross-flow heterogeneous catalyst device, the catalyzer added in hydrogen peroxide and described cross-flow heterogeneous catalyst device carries out reacting that (catalyzer is ferrous sulfate, the mol ratio of hydrogen peroxide and ferrous sulfate is 3:1), carry out COD degradation, stop 7 hours; Described one-level flocculation deposition apparatus comprises the first reactive tank, the first flocculation tank and the first subsider; Described cross-flow heterogeneous catalyst device comprises the first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit that connect successively, is provided with reaction column, is filled with catalyzer in reaction column in described cross-flow heterogeneous catalyst device;

Reacted waste water is entered secondary flocculation deposition apparatus, and enter the second intermediate water tank after precipitation water outlet adjustment pH to 7-9, mud arranges concentration outward; Pretreated waste water enters ultra-filtration equipment through more medium filter, then enters reverse osmosis unit; Described ultra-filtration equipment comprises more medium filter, ultrafiltration system and ultrafiltration water tank; Described reverse osmosis unit comprises first-stage reverse osmosis system and two-stage reverse osmosis system.

Embodiment 2

Catalyzer is ferrous sulfate, and the mol ratio of hydrogen peroxide and ferrous sulfate is 4:1, and the residence time is 6 hours, and other are with embodiment 1.

Embodiment 3

Catalyzer is ferrous sulfate, and the mol ratio of hydrogen peroxide and ferrous sulfate is 2:1, and the residence time is 8 hours, and other are with embodiment 1.

The processing data of embodiment 1-3 asks for an interview table 2.

Water quality after the process of table 2 embodiment 1-3 coking waste water reuse

The present invention, by the difficult biochemical waste water of process, makes water outlet meet the requirement of reuse standard, finally realizes the object of coking waste water reuse, reduce efflux wastewater to the impact of environment, can economize on resources, can discharge by decreasing pollution thing again, realize the target of economic benefit and environmental benefit doulbe-sides' victory.

Claims (10)

1. a coking waste water reuse device, comprise the former tank, the first reactive tank, the first flocculation tank, the first subsider and the first intermediate water tank that connect successively, it is characterized in that: between described first subsider and the first intermediate water tank, be provided with cross-flow heterogeneous catalyst device, described cross-flow heterogeneous catalyst device comprises the first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit that connect successively; Be respectively arranged with reaction column in described first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit, in described reaction column, be filled with catalyzer;
The outlet of described first intermediate water tank is connected with the entrance of the second reactive tank, second reactive tank is connected successively with the second flocculation tank, the second subsider, the second intermediate water tank, the outlet of described second intermediate water tank is connected with the entrance of more medium filter by respective pump assembly, the outlet of more medium filter is connected with the entrance of ultrafiltration system, the outlet of described ultrafiltration system is connected with the entrance of ultrafiltration water tank, and the outlet of ultrafiltration water tank is connected with first-stage reverse osmosis system, two-stage reverse osmosis system and reuse water tank successively.
2. coking waste water reuse device according to claim 1, is characterized in that, the outlet of described second intermediate water tank is connected with the entrance of described ultrafiltration system.
3. coking waste water reuse device according to claim 1, is characterized in that, is provided with hyperfiltration membrane assembly in described ultrafiltration system.
4. a coking waste water reuse treatment process, is characterized in that: comprise the following steps:
Pre-treatment: extract biochemical secondary clarifier effluent and enter former tank and carry out water quality and quantity homogenizing, enter one-level flocculation deposition apparatus again and carry out flocculation sediment, supernatant liquor after precipitation enters cross-flow heterogeneous catalyst device, the catalyzer added in hydrogen peroxide and described cross-flow heterogeneous catalyst device reacts, carry out COD degradation, stay for some time; Described one-level flocculation deposition apparatus comprises the first reactive tank, the first flocculation tank and the first subsider; Described cross-flow heterogeneous catalyst device comprises the first cross-flow heterogeneous catalyst unit and the second cross-flow heterogeneous catalyst unit that connect successively, is provided with reaction column, is filled with catalyzer in described reaction column in described cross-flow heterogeneous catalyst device;
Reacted waste water is entered secondary flocculation deposition apparatus, and enter the second intermediate water tank after precipitation water outlet adjustment pH, mud arranges concentration outward;
Pretreated waste water enters ultra-filtration equipment through more medium filter, then enters reverse osmosis unit; Described ultra-filtration equipment comprises more medium filter, ultrafiltration system and ultrafiltration water tank; Described reverse osmosis unit comprises first-stage reverse osmosis system and two-stage reverse osmosis system.
5. coking waste water reuse treatment process according to claim 1, is characterized in that, the mol ratio of described hydrogen peroxide and catalyzer is 2 ~ 4:1.
6. the coking waste water reuse treatment process according to claim 4 or 5, is characterized in that, described catalyzer is noble metal catalyst.
7. the coking waste water reuse treatment process according to claim 4 or 5, is characterized in that, described catalyzer is Fe 2+class catalyzer.
8. coking waste water reuse treatment process according to claim 4, is characterized in that, the described residence time is 4-8 hour.
9. coking waste water reuse treatment process according to claim 4, is characterized in that, is provided with hyperfiltration membrane assembly in described ultrafiltration system, and hyperfiltration membrane assembly adopts external pressing type hollow fibrous membrane.
10. coking waste water reuse treatment process according to claim 9, is characterized in that, the material of described macaroni yarn selects wetting ability special type improvement PVDF.
CN201410508142.9A 2014-09-28 2014-09-28 Coking wastewater reuse device and treatment technology CN105439312A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0439770A2 (en) * 1990-01-30 1991-08-07 Thyssen Still Otto Anlagentechnik GmbH Process for removing harmful substances and recovering valuable substances from a coking plant waste water stream
CN101781039A (en) * 2010-03-05 2010-07-21 中冶焦耐(大连)工程技术有限公司 Technology for deeply processing coking wastewater through combining catalytic oxidation method and membrane separation technique
CN102942270A (en) * 2012-11-29 2013-02-27 湖南湘牛环保实业有限公司 Technology for deeply treating and recycling biochemical effluent of coking wastewater

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0439770A2 (en) * 1990-01-30 1991-08-07 Thyssen Still Otto Anlagentechnik GmbH Process for removing harmful substances and recovering valuable substances from a coking plant waste water stream
CN101781039A (en) * 2010-03-05 2010-07-21 中冶焦耐(大连)工程技术有限公司 Technology for deeply processing coking wastewater through combining catalytic oxidation method and membrane separation technique
CN102942270A (en) * 2012-11-29 2013-02-27 湖南湘牛环保实业有限公司 Technology for deeply treating and recycling biochemical effluent of coking wastewater

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