CN102050508A - Sewage treatment method for circulating cooling water system - Google Patents

Sewage treatment method for circulating cooling water system Download PDF

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Publication number
CN102050508A
CN102050508A CN2009102360937A CN200910236093A CN102050508A CN 102050508 A CN102050508 A CN 102050508A CN 2009102360937 A CN2009102360937 A CN 2009102360937A CN 200910236093 A CN200910236093 A CN 200910236093A CN 102050508 A CN102050508 A CN 102050508A
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China
Prior art keywords
cooling water
water system
electrolysis
sewer
recirculating cooling
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CN2009102360937A
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Inventor
李本高
侯钰
谭丽
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN2009102360937A priority Critical patent/CN102050508A/en
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Abstract

The invention relates to a sewage treatment method for a circulating cooling water system. The invention provides the sewage treatment method for the circulating cooling water system, wherein the method comprises a step of electrolyzing the sewage of the circulating cooling water system. By using the sewage treatment method for the circulating cooling water system, Cl- in the sewage of the circulating cooling water system can be effectively removed, the number of heterotrophic bacteria can be reduced to a certain degree, the corrosion rate is reduced, and the water quality reaches the requirement of recycled circulating cooling water; and in addition, the method provided by the invention is simple and convenient to operate, and has low cost.

Description

A kind of recirculating cooling water system sewer treatment process
Technical field
The invention relates to a kind of recirculating cooling water system sewer treatment process.
Background technology
At the open type industrial circulating cooling water system, with evaporation various impurity are constantly concentrated, water quality characteristic changes, and makes the scaling tendency of water quality strengthen Cl as hardness and basicity increase -The concentration increase strengthens the corrodibility of water quality, and particularly the stress corrosion trend to stainless steel equipment increases greatly, and organic concentration increases and promotes that biological clay grows.Therefore be Control Circulation water water quality, must replenish new water (being make up water) and discharge dense water (being sewer).
At present, to recirculating cooling water system blowdown water handling reclamation, general employing is flocculated, precipitates, filters, is carried out membrane sepn again, as electrodialysis, reverse osmosis, nanofiltration etc.For example " recirculated water sewer reuse technology is analyzed and industrial application " (Shandong petrochemical complex, 2003,31 (3): adopt coagulating sedimentation, secondary filter and electrodialysis combination process 231-232); After the flocculation sediment of US 20030127391A1 proposition employing reverse osmosis technology and CN 101172724A, the filtration treatment, part water is directly as the make up water reuse of recirculated cooling water, another part is handled the back reuse through nanofiltration system, the two returns recirculating cooling water system after mixing according to a certain percentage, realize the recycling of recirculated cooling water, reduce the moisturizing and the blowdown of circulating water system.The membrane separation technique of these methods employings requires high to influent quality, make the pretreatment technology long flow path, causes the big and engineering reliability reduction of investment; And the life-span of film is short, causes the running cost costliness; In addition, the dense water of membrane sepn generation still needs further processing.
Summary of the invention
The objective of the invention is to overcome in the prior art and remove Cl in the processing of recirculating cooling water system sewer -Complex process, and can not reduce Cl simultaneously by same technology -With the shortcoming of heterotrophic bacterium content, provide the Cl in a kind of cost reduction recirculating cooling water system sewer low, simple to operate -And the method for heterotrophic bacterium content.
The invention provides a kind of recirculating cooling water system sewer treatment process, wherein, this method comprises carries out electrolytic step with the recirculating cooling water system sewer.
The present invention adopts the Cl in the electrolytic process reduction recirculated cooling water sewer -Concentration makes most of Cl -In electrolyzer, be converted into Cl by anodic oxidation reactions 2, most of Cl 2Thereby the Cl in the reduction sewer of from water, overflowing -Concentration, small part Cl 2Generate HClO with the water reaction, can be used for circulating water sterilizing with fungicidal activity.
Use recirculating cooling water system sewer treatment process provided by the invention, can effectively remove the Cl in the recirculating cooling water system sewer -, and can obviously reduce number of heterotrophic bacteria, and reduce erosion rate, make water quality reach the requirement of reuse recirculated cooling water; In addition, method provided by the invention is easy and simple to handle, and cost is low.
Embodiment
According to recirculating cooling water system sewer treatment process provided by the invention, wherein, this method comprises carries out electrolytic step with the recirculating cooling water system sewer.
Electrolysis of the present invention can be carried out in electrolyzer, and described electrolyzer can comprise electrolyzer and rectifier power source, and wherein rectifier power source provides direct current to electrolyzer.
The method according to this invention, the Cl of described recirculating cooling water system sewer -Content has no particular limits, and can in very large range change because of the water quality difference.
In the electrolyzer of the present invention, the electrode pad number can be right for 1-100, and preferred 1-50 is right, and more preferred 1-40 is right.Each battery lead plate area can be 0.01-100m 2, preferred 1-50m 2, more preferred 1-30m 2Determine according to handling the water yield; Each can be connected to pole plate also can be in parallel.Wherein, the area of each electrode pad is meant the single face area that each electrode contacts with electrolytic solution.
The electrode that electrolyzer of the present invention uses is conventional corrosion-resistant electrode, and for example body material is a titanium, and the surface is coated with one or more in metal platinum, iridium, ruthenium, tantalum, the palladium, one or more in the perhaps above-mentioned metal oxide.Described electrolyzer uses the negative electrode and the anode material of electrode can be the same or different.
Electrolytic every pair of polar plate voltage of the present invention can be 1-10V, preferred 1.5-6V.
The electrolytic time of the present invention can be 1min-2h, preferred 10min-1h.
According to the present invention, method of the present invention can combine with existing recirculating cooling water system sewer treatment process, for example, can be before or after electrolysis, one or more in adding tenderizer, the coagulating agent etc. can also comprise filtering step.The selection of existing circulating water treatment method can be selected according to pending recirculating cooling water system sewer water quality.When the suspension content of sewer is too high, can adopt filtering method to reduce suspension content.When the blowdown water hardness is too high, can adopt the method that adds tenderizer to reduce hardness.When the petroleum content in the recirculated water is too high, can adopt the method that adds coagulating agent to reduce petroleum content.
Under the preferable case, method of the present invention also comprises makes described recirculating cooling water system sewer contact with coagulating agent, isolates floss wherein then.
Under the preferable case, method of the present invention also is included in before the described electrolysis and/or after the electrolysis, described recirculating cooling water system sewer is contacted with tenderizer.
The kind of described tenderizer and consumption are conventionally known to one of skill in the art, and for example, described tenderizer can be selected from the oxide compound of calcium and oxide compound, oxyhydroxide, carbonate, supercarbonate and phosphoric acid salt or its mixture of oxyhydroxide and lithium, sodium and potassium.For example, can be CaO, Ca (OH) 2, Na 2O, K 2O, Li 2O, LiOH, NaOH, KOH, Li 2CO 3, Na 2CO 3, K 2CO 3, LiHCO 3, NaHCO 3, KHCO 3, Li 3PO 3, Na 3PO 3, K 3PO 3In one or more.The consumption of tenderizer can be 50-2000mg/L, preferred 150-800mg/L.
Described filtering method is conventionally known to one of skill in the art, and for example, described filtration can be in sand filtration, micro-filtration, ultrafiltration and the fiber filter etc. one or more.
The kind of described coagulating agent and consumption are conventionally known to one of skill in the art, for example, described coagulating agent can be selected from one or more in aluminium salt, molysite and polymkeric substance thereof and the organic polymer, be preferably in Tai-Ace S 150, alum, iron trichloride hydrate, ferrous sulfate hydrate, polyaluminium sulfate, polymerize aluminum chloride, polymerization chlorine sulphur aluminium, polymerised sulphur sial, polymerization iron, polyacrylamide, sodium polyacrylate, polyvinyl pyridine, the polymine one or more, more preferably polymerize aluminum chloride and polyacrylamide.The consumption of coagulating agent can be 50-2000mg/L, preferred 150-800mg/L.
Described petroleum-type is meant the mixture of various hydro carbons in the sewage.
According to method provided by the invention, can handle various recirculating cooling water system sewers, for example one or more in the recirculating cooling water system sewer of the recirculating cooling water system sewer of the recirculating cooling water system sewer in chemical plant, power plant and refinery.Method provided by the invention is when being used to handle the high recirculating cooling water system sewer of chloride ion content, and its advantage is more remarkable.When using method provided by the invention to handle the high recirculating cooling water system sewer of chloride ion content, by electrolysis, chlorion forms chlorine, part chlorine directly overflows, another part chlorine leach is in water, form hypochlorous acid, because hypochlorous acid is a kind of strong oxidizer, can be used in sterilization, when method therefore provided by the invention is handled the high recirculating cooling water system sewer of chloride ion content, can reduce the chloride ion content in the recirculating cooling water system sewer on the one hand, thereby reduce corrosion to equipment, reach reuse standard, can also kill the bacterium in the recirculating cooling water system sewer on the other hand, thereby further improve water quality.
Below in conjunction with specific embodiment the present invention is further specified.
The suspension content that relates among the embodiment 1-6, Ca 2+Concentration, Cl -The analytical procedure of concentration, petroleum-type and erosion rate is respectively:
Suspended substance: the gravimetry method of water quality suspended substance (GB 11901-89);
Ca 2+: the mensuration of calcium, magnesium ion in the industrial circulating cooling water, EDTA volumetry (GB/T15452-1995);
Cl -: the mensuration of chlorion in the industrial circulating cooling water, silver nitrate titration method (GB/T15453-1995);
Petroleum-type: the mensuration of water quality, petroleum-type and vegetable and animals oils, infrared spectrophotometry (GB/T16488-1996);
Erosion rate: the mensuration of water conditioner sustained release performance, rotary hanging plate method (GB/T 18175-2000).
" water and effluent monitoring analytical procedure " (State Environmental Protection Administration is adopted in the analysis of total heterotrophic bacteria count; water and effluent monitoring analytical procedure editorial committee, China Environmental Science Press, in December, 2002; the 4th edition first impression, the 694-697 page or leaf) disclosed plate count.
Embodiment 1
The sewer of certain generating plant circulation-water system, Cl -(positively charged ion mainly is Na to the content height +, Ca 2+, Mg 2+), the composition before it is handled is as shown in table 1.Adopt the electrolytic process of the inventive method to handle, the size of electrolyzer is 5m * 2m * 2m, and 5 pairs of series connection electrode pads are installed in the electrolyzer, and anode and cathode base material are titanium, surperficial platinum plating, and each battery lead plate area is 2m 2, every counter electrode polar plate voltage is 2.5V; Electrolysis 15min, Cl after the analysis electrolysis -Concentration, total heterotrophic bacteria count and erosion rate, the result is as shown in table 1.
Table 1
Project Before the electrolysis After the processing
Cl -/mg·L -1 832 150
A total heterotrophic bacteria count/mL -1 1.0×10 5 6.3×10 4
Erosion rate/mma -1 0.0500 0.0025
Embodiment 2
The sewer of certain generating plant circulation-water system, Cl -And Ca 2+The content height, the composition before it is handled is as shown in table 2, adopts the inventive method to carry out electrolysis, the size of electrolyzer is 5m * 3m * 5m, and 2 pairs of series connection electrode pads are installed in the electrolyzer, and anode and cathode base material are titanium, the surface is plated ruthenium and palladium respectively, and each battery lead plate area is 20m 2, every counter electrode polar plate voltage 3.5V; Electrolysis 30min.Cl after the analysis electrolysis -Concentration, total heterotrophic bacteria count and erosion rate, the result is as shown in table 2.Add tenderizer NaOH after the electrolysis, adding concentration is 200mg/L.Analyze Ca 2+Concentration and erosion rate, the result is as shown in table 2.
Table 2
Project Before the processing After the electrolysis After the processing
?Ca 2+/mg·L -1 497 - 106
?Cl -/mg·L -1 526 103 -
A total heterotrophic bacteria count/mL -1 2.5×10 5 8.4×10 4 -
Erosion rate/mma -1 0.0195 0.0040 -
Embodiment 3
The sewer of certain chemical plant first circulating water system, Cl -With the suspension content height, the composition before it is handled is as shown in table 3, adopts the electrolysis of the inventive method to handle.The size of electrolyzer is 10m * 4m * 4m, and 8 pairs of electrode pads in parallel are installed in the electrolyzer, and the anode substrate material is a titanium, surperficial platinum plating, and the cathode base material is a titanium, surface plating iridium; Each battery lead plate area is 9m 2, every counter electrode polar plate voltage is 4.5V; Electrolysis 20min; Cl after the analysis electrolysis -Concentration, total heterotrophic bacteria count and erosion rate, the result is as shown in table 3.(filtrate is the polyester macrofiber, and the silk footpath is 14-16 μ m, porosity 90%, specific surface area 8000m to carry out fiber filter after the electrolysis 2/ m 3, the filtering layer height is 2m), analyze concentration of suspension and erosion rate, the result is as shown in table 3.
Table 3
Figure B2009102360937D0000061
Embodiment 4
The sewer of certain chemical plant the 3rd circulating water system, Cl -, Ca 2+With the suspension content height, composition before it is handled is as shown in table 4, adopt the electrolysis of the inventive method, the size of electrolyzer is 10m * 5m * 5m, and 40 pairs of series connection electrode pads are installed in the electrolyzer, and the anode substrate material is a titanium, surface plating tantalum, the cathode base material is a titanium, surperficial platinum plating, and each battery lead plate area is 8m 2, every counter electrode polar plate voltage is 5.0V; Electrolysis 40min; Cl after the analysis electrolysis -Concentration, total heterotrophic bacteria count and erosion rate, the result is as shown in table 4.Add tenderizer NaOH, adding concentration is 300mg/L; Carry out then sand filtration (filtrate is a quartz sand, particle diameter 0.5-1.2mm, porosity is 44%, specific surface area is 5600m 2/ m 3, the filtering layer height is 2m), analyze concentration of suspension, Ca concentration and erosion rate, the result is as shown in table 4.
Table 4
Figure B2009102360937D0000071
Embodiment 5
The sewer of certain refinery first circulating water system, Cl -, suspended substance and petroleum content height, the composition before it is handled is as shown in table 5, adopts the electrolysis of the inventive method, the size of electrolyzer is 6m * 2m * 6m, and 1 counter electrode plate is installed in the electrolyzer, and it is titanium that anode and negative electrode are body material, the surface platinum plating, each battery lead plate area is 25m 2, the voltage on every counter electrode plate is 4.5V, electrolysis 1h; Cl after the analysis electrolysis -Ionic concn, total heterotrophic bacteria count and erosion rate, the result is as shown in table 5.Add Tai-Ace S 150 and polyacrylamide amine mixt, add concentration and be respectively 300mg/L and 50mg/L, altogether 350mg/L; And (filtrate is the polyester macrofiber, and the silk footpath is 14-16 μ m, porosity 80%, specific surface area 7400m to adopt fiber filter 2/ m 3, the filtering layer height is 3m), analyze suspended substance, petroleum-type and erosion rate, the result is as shown in table 5.
Table 5
Project Before the processing After the electrolysis After the processing
Suspended substance/mgL -1 28.0 - 4.3
Petroleum-type/mgL -1 204.4 - 8.3
Cl-/mg·L -1 835 136 -
A total heterotrophic bacteria count/mL -1 3.0×10 5 7.0×10 4 -
Erosion rate/mma -1 0.0134 0.0023 -
Embodiment 6
The sewer of certain refinery second circulating water system, Cl -, Ca 2+, suspended substance and petroleum content height, the composition before it is handled is as shown in table 6, adopts the electrolysis of the inventive method, the size of electrolyzer is 8m * 7m * 7m, and 10 pairs of placed in-line battery lead plates are installed in the electrolyzer, and it is titanium that anode and negative electrode are body material, surface plating palladium, each battery lead plate area is 36m 2, the voltage on every counter electrode plate is 3.5V, electrolysis 15min; Cl after the analysis electrolysis -Concentration, total heterotrophic bacteria count and erosion rate, the result is as shown in table 6.The adding tenderizer is NaOH, and adding concentration is 250mg/L; Add coagulating agent, coagulating agent is the mixture of polymerize aluminum chloride and polyacrylamide, adds concentration and is respectively 100mg/L and 50mg/L, altogether 150mg/L; And employing micro-filtration (6 groups of polysulfones micro-filtration membrane modules that specification is 4.0inch * 40inch).Analyze concentration of suspension, Ca 2+Concentration, petroleum content and erosion rate, the result is as shown in table 6.
Table 6
Project Before the processing After the electrolysis After the processing
Suspended substance/mgL -1 20.0 - 2.5
Ca 2+/mg·L -1 295 - 74
Petroleum-type/mgL -1 133.6 - 7.7
Cl -/mg·L -1 394 83 -
A total heterotrophic bacteria count/mL -1 2.2×10 5 8.7×10 4 -
Erosion rate/mma -1 0.0168 0.0036 -
From the table 1-6 the result as can be seen, method provided by the invention can reduce the Cl in the recirculated water effectively -Content can reduce the total heterotrophic bacteria count in the water simultaneously, and erosion rate is reduced.And method of the present invention can combine with water treatment method such as existing softening, coagulation and filtrations.

Claims (8)

1. the treatment process of a recirculating cooling water system sewer is characterized in that, this method comprises carries out electrolysis with described recirculating cooling water system sewer.
2. method according to claim 1, wherein, described electrolysis is carried out in electrolyzer, described electrolyzer comprises electrolyzer and at least one pair of battery lead plate, described electrolytic method comprises described battery lead plate and recirculating cooling water system sewer is placed electrolyzer, then described battery lead plate is applied electric field.
3. method according to claim 2, wherein, the quantity of described battery lead plate is that 1-100 is right, the area of each battery lead plate is 0.01-100m 2
4. method according to claim 3, wherein, the quantity of described battery lead plate is that 1-50 is right, the area of each battery lead plate is 1-50m 2
5. method according to claim 4, wherein, described electrolytic voltage is 1-10V, the described electrolytic time is 1min-2h.
6. method according to claim 5, wherein, described electrolytic voltage is 1.5-6V, the described electrolytic time is 10min-1h.
7. method according to claim 1, wherein, this method also is included in before the described electrolysis and/or after the electrolysis, described recirculating cooling water system sewer is contacted with coagulating agent, isolates floss wherein then.
8. according to claim 1 or 7 described methods, wherein, this method also is included in before the described electrolysis and/or after the electrolysis, described recirculating cooling water system sewer is contacted with tenderizer.
CN2009102360937A 2009-10-27 2009-10-27 Sewage treatment method for circulating cooling water system Pending CN102050508A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102897949A (en) * 2012-10-15 2013-01-30 邯郸市奥博水处理有限公司 Drug special for reverse-osmosis concentrate water zero emission and use method thereof
CN103420454A (en) * 2013-08-05 2013-12-04 上海电力学院 Method for removing organic phosphorus of sewerage of circulating cooling water system
CN104556311A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Circulating cooling water sterilizing method and application
CN105102918A (en) * 2012-12-20 2015-11-25 兰德股份公司 Cooling process
CN105819594A (en) * 2015-01-09 2016-08-03 中国石油化工股份有限公司 Recirculated cooling water processing method
CN111302549A (en) * 2020-04-03 2020-06-19 中国华能集团清洁能源技术研究院有限公司 Electrochemical pretreatment system and method for circulating water sewage

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102897949A (en) * 2012-10-15 2013-01-30 邯郸市奥博水处理有限公司 Drug special for reverse-osmosis concentrate water zero emission and use method thereof
CN105102918A (en) * 2012-12-20 2015-11-25 兰德股份公司 Cooling process
CN105102918B (en) * 2012-12-20 2018-06-22 兰德股份公司 Cooling means
CN103420454A (en) * 2013-08-05 2013-12-04 上海电力学院 Method for removing organic phosphorus of sewerage of circulating cooling water system
CN104556311A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Circulating cooling water sterilizing method and application
CN104556311B (en) * 2013-10-22 2018-09-28 中国石油化工股份有限公司 A kind of method for disinfection of recirculated cooling water and application
CN105819594A (en) * 2015-01-09 2016-08-03 中国石油化工股份有限公司 Recirculated cooling water processing method
CN111302549A (en) * 2020-04-03 2020-06-19 中国华能集团清洁能源技术研究院有限公司 Electrochemical pretreatment system and method for circulating water sewage

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Application publication date: 20110511