CN109422356A - Circulating cooling water containing sulfur composition for treating and its application - Google Patents
Circulating cooling water containing sulfur composition for treating and its application Download PDFInfo
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- CN109422356A CN109422356A CN201710758389.XA CN201710758389A CN109422356A CN 109422356 A CN109422356 A CN 109422356A CN 201710758389 A CN201710758389 A CN 201710758389A CN 109422356 A CN109422356 A CN 109422356A
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- circulating cooling
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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Abstract
The present invention relates to recirculated cooling water fields, are related to the method for circulating cooling water containing sulfur composition for treating and its application with circulating cooling water containing sulfur processing.Specifically, the present invention provides a kind of circulating cooling water containing sulfur composition for treating, the composition contains sulfide-oxidizing enzyme, zinc salt, dirt dispersion agent and optional pH adjusting agent.When handling using composition provided by the invention circulating cooling water containing sulfur, the heat exchanger tube in the circulation of sulfur-bearing can be made to keep lower corrosion of carbon steel rate and adherency rate.
Description
Technical field
The present invention relates to recirculated cooling water fields, and in particular, to a kind of circulating cooling water containing sulfur composition for treating and
It is applied and the method for circulating cooling water containing sulfur processing.
Background technique
With the worsening shortages of petroleum resources, petroleum chemical enterprise has to the processing capacity for increasing high-sulphur crude.High sulfur-bearing is former
The corrosion of oily heat exchanging device in process is extremely serious, and dielectric leakage to the phenomenon that recirculated water happens occasionally, and gives recirculated water
The Handling of Stabilizing Water Quality of system brings more serious influence, or even keeps original water treatment agent ineffective, aggravates
The corrosion and fouling of heat exchanger of water circulating system, and then the leakiness aggravation of material, form vicious circle, pacify to process units
Entirely, the threat of long-term operation has increased trend.
After hydrogen sulfide containing processing medium is leak into recirculated water, caused by water pollution and its to the main table of the harm of system
It is present: to promote the corrosion of carbon steel；Destroy the bactericidal effect of oxidizing bactericide；It is precipitated with divalent ions such as zinc；Cause to follow
The decline of ring water pH value；Promote the decomposition of Quadrafos.
CN1958848A provides a kind of method of inhibition circulating cooling water containing sulfur corrosion, comprising: control sulfur-bearing recirculated water
Basicity with calcium carbonate is 250-350mg/L, and composite corrosion inhibitor is added in recirculated cooling water, and additional amount is let out in recirculated water
It leaks 5-40 times of sulphion mass concentration, containing concentration is 2-24 weight % selected from 1-hydroxy ethylene-1,1-diphosphonic in described composite corrosion inhibitor
Acid, hydroxyl phosphino- acetic acid, aminotrimethylenephosphonic acid, ethylene diamine tetra methylene phosphonic acid, 2- phosphino- -1,2,4- tricarboxylic acids-butane and its
One of sylvite, sodium salt, Polyol Phosphate and polyethers alcamines phosphate or in which two or more mixture it is organic
Corrosion inhibiter, surplus are water.
CN103572297A provides a kind of processing method of circulating cooling water containing sulfur, comprising: to circulating cooling water containing sulfur
Middle addition ferrous iron and/or ferric water soluble chelate compound, with the quality of the sulphion in recirculated cooling water for 1, the water of iron
The dosage of dissolubility chelate is calculated as 5-20 with iron.
CN1618743A provides a kind of composite slow-corrosion scale resistor, which includes organic phospho acid, organic
Phosphine carboxylic acid and homopolymer containing carboxylic acid group or copolymer, the phosphine carboxylic acid be hydroxyethylidene diphosphonic acid guanidine-acetic acid or hydroxyethylidene diphosphonic acid guanidine-acetic acid with
2- phosphonic acid base -1,2, the mixture of 4- butane tricarboxylate.And it is used for circulating cooling water containing sulfur processing.
As it can be seen that circulating water treatment at present mostly controls corrosion and scaling and biological sludge in industrial in a manner of adding chemical agent
System, mostly to adjust water treatment agent formula, increases corrosion inhibiting and descaling agent, dispersing agent and oxidized form sterilization for leaking sulfur cycle water system
The dosage of agent and water frequently is changed to cope with, not only cause the waste of water resource and water treatment agent, a large amount of chemical agents are with circulation
Water sewerage outlet, has also aggravated environmental pressure.Therefore, it is quite necessary to find a kind of recirculated water especially suitable for sulfur-bearing
Processing method.
Summary of the invention
The purpose of the invention is to overcome drawbacks described above of the existing technology, provide at a kind of circulating cooling water containing sulfur
The method of reason composition and its application and circulating cooling water containing sulfur processing.Using composition provided by the invention to sulfur-bearing
When recirculated cooling water is handled, can make heat exchanger tube in the circulation of sulfur-bearing keep lower corrosion of carbon steel rate and
Adhere to rate.
To achieve the goals above, in a first aspect, the present invention provides a kind of circulating cooling water containing sulfur composition for treating,
Wherein, the composition contains sulfide-oxidizing enzyme, zinc salt, dirt dispersion agent and optional pH adjusting agent.
Second aspect, the present invention also provides application of the above-mentioned composition in circulating cooling water containing sulfur processing.
The third aspect, the present invention also provides a kind of methods of circulating cooling water containing sulfur processing, wherein this method comprises:
Sulfide-oxidizing enzyme, zinc salt, dirt dispersion agent and optional pH adjusting agent are added into circulating cooling water containing sulfur system.
The present invention in the collecting-tank of circulating cooling water containing sulfur system by adding sulfide-oxidizing enzyme, zinc salt and antiscaling dispersion
Agent, and the pH value for controlling circulating cooling water containing sulfur can make changing in the circulation of sulfur-bearing in particular range (8-9.5)
The adherency rate of heat pipe is maintained at 9.7mcm hereinafter, corrosion of carbon steel rate is maintained at 0.069mm/a or less.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of circulating cooling water containing sulfur composition for treating, wherein the composition contains
Sulfide-oxidizing enzyme, zinc salt, dirt dispersion agent and optional pH adjusting agent.
In the present invention, with S2-Meter, the sulfur content of the circulating cooling water containing sulfur is preferably 0.01-5mg/L, more preferably
0.1-4mg/L, further preferably 0.5-3mg/L.
According to the present invention, relative to every L circulating cooling water containing sulfur, the content of the sulfide-oxidizing enzyme is preferably 5-400mg, more
Preferably 10-200mg.The weight of microorganism involved in the present invention is in terms of cell butt.
According to the present invention, the sulfide-oxidizing enzyme is preferably Thiobacillus (Thiobacillus), Beggiatoa
(Beggiatoa) and at least one of Thiothrix (Thiothrix) bacterium, more preferably at least one of Thiobacillus
Bacterium, further preferably Thiobacillus thioxidans (Thiobacillus thiooxidans), grate sulfur thiobacillus (Thiobacillus
) and at least one of thiobacillus denitrificans (Thiobacillus denitrificans) thioparus.
In the present invention, to the form of the sulfide-oxidizing enzyme, there is no particular limitation, as long as being put into recirculated cooling water
It is active in system, for example, the form of the sulfide-oxidizing enzyme can be at least one in pulvis, bacteria suspension and emulsion
Kind, preferably pulvis.
In the present invention, to the source of the sulfide-oxidizing enzyme, there is no particular limitation, for example, commercially available from can be by routine
Means directly obtain；Strain can also be obtained by conventional means, then by conventional microbial culture method to strain
It carries out voluntarily expanding culture acquisition.
According to the present invention, described with Zn2+The zinc salt of meter and the weight ratio of the dirt dispersion agent are preferably 0.0067-
1.25:1, more preferably 0.02-0.5:1, further preferably 0.025-0.4:1.
According to the present invention, to the type of the zinc salt, there is no particular limitation, as long as can provide free Zn in water2+
, for example, the zinc salt can be zinc sulfate and/or zinc chloride.
According to the present invention, the dirt dispersion agent is preferably that carboxylic acid quasi polymer, organic phosphine acid compounds, sulfonic acid are birdsed of the same feather flock together
Close object, carboxylic acid-at least one of sulfonic acid quasi polymer and natural phenolic substance；It is highly preferred that the dirt dispersion agent is poly-
Acrylic acid, acrylic copolymer, poly, maleic acid, poly- sulfonated phenylethylene, acrylic acid-Sodium Allyl Sulfonate are total
Polymers, 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), aminotrimethylenephosphonic acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), ethanamidine
Base ethylene-diphosphonic acid (AEDP), phosphine carboxylic acid, triol ester, hexa-atomic alcohol ester, alkanolamine ester, sodium humate, tannin and lignosulfonate
At least one of；It is further preferred that the dirt dispersion agent is polyacrylic acid, poly- sulfonated phenylethylene, 1-hydroxy ethylene-1,1-diphosphonic
At least one of acid, aminotrimethylenephosphonic acid and tannin.
There is no particular limitation in source of the present invention to the dirt dispersion agent, for example, can pass through conventional commercially available hand
Section obtains.
In the present invention, the content of the pH adjusting agent makes the pH of circulating cooling water containing sulfur be preferably 8-9.5.The present invention
To the type of the pH adjusting agent, there is no particular limitation, can be various sour agent commonly used in the art and/or alkaline agent；It is excellent
Selection of land, the pH adjusting agent are inorganic acid and/or inorganic base；It is highly preferred that the pH adjusting agent is sulfuric acid, hydrochloric acid, nitric acid, carbon
At least one of sour hydrogen sodium, saleratus, sodium hydroxide and potassium hydroxide.
According to the present invention, the sulfide-oxidizing enzyme, the zinc salt, the dirt dispersion agent and the pH adjusting agent are individually separated
It saves.
Second aspect, the present invention also provides application of the above-mentioned composition in circulating cooling water containing sulfur processing；Preferably,
With S2-Meter, the sulfur content of the circulating cooling water containing sulfur are 0.01-5mg/L, preferably 0.1-4mg/L, 0.5-3mg/L.
In a preferred embodiment of the invention, in the circulating cooling water containing sulfur, with CaCO3The Ca of meter2+
Concentration is 200-300mg/L, more preferably 250-270mg/L；With CaCO3The total hardness of meter is 300-500mg/L, more preferably
400-420mg/L；With CaCO3The total alkalinity of meter is 150-200mg/L, more preferably 160-170mg/L；Cl-Concentration is 50-
100mg/L, more preferably 80-90mg/L；COD value is 5-40mg/L, more preferably 10-20mg/L；Ammonia nitrogen in terms of N element contains
Amount is 0.1-5mg/L, more preferably 0.5-2mg/L；PH value is 6-9, more preferably 8-8.5；With S2-The sulfur content of meter is 0.01-
5mg/L, preferably 0.1-4mg/L, 0.5-3mg/L.
In the present invention, Ca2+Detect reference standard GB/T 6910-2006；Total alkalinity detects reference standard GB/T
15451-2006；Total hardness detects reference standard GB/T 6909-2008；Cl-Concentration Testing reference standard GB/T 15453-
2008；PH value detects reference standard GB/T 6920-1986；COD detects reference standard GB/T 15456-2008；Ammonia-nitrogen content inspection
Survey reference standard HG/T 2158-2011；Sulfur content detects reference standard GB/T16489-1996.
The third aspect, the present invention also provides a kind of methods of circulating cooling water containing sulfur processing, this method comprises: will vulcanization
Bacterium, zinc salt, dirt dispersion agent and optional pH adjusting agent are added into circulating cooling water containing sulfur system；Preferably, with S2-Meter,
The sulfur content of the circulating cooling water containing sulfur is 0.01-5mg/L, more preferably 0.1-4mg/L, further preferably 0.5-3mg/
L。
In the present invention, the composition of the circulating cooling water containing sulfur is as described above, details are not described herein.
In the present invention, it when the circulating cooling water containing sulfur system carries out moisturizing, needs that it is concentrated, it is described dense
The multiple of contracting makes the Cl of the circulating cooling water containing sulfur before moisturizing-The Cl of concentration and the moisturizing-The ratio of concentration is preferably 1.5-
3.5:1 more preferably 1.8-3.2:1.
According to the present invention, the dosing method of the sulfide-oxidizing enzyme preferably adds step by step.It is highly preferred that the sulfide-oxidizing enzyme
The frequency that adds be to add within every 5-15 days primary, add within preferably every 8-10 days once.It is further preferred that containing relative to every L
Sulfur cycle cooling water, the dosage of the sulfide-oxidizing enzyme are 5-400mg, preferably 10-200mg.
In a preferred embodiment of the invention, the substep, which is added, adds including adding for the first time with subsequent.More
Preferably, relative to every L recirculated cooling water, the dosage for the first time of the sulfide-oxidizing enzyme is more than or equal to subsequent dosage, preferably greatly
In subsequent dosage.It is further preferred that the dosage for the first time of the sulfide-oxidizing enzyme is 200-400mg, preferably 200-
300mg；Subsequent dosage is 5-400mg, preferably 10-200mg.
In method of the present invention, type, source and the form of the sulfide-oxidizing enzyme are as described above, no longer superfluous herein
It states.
According to the present invention, to the dosing method of the zinc salt, there is no particular limitation, as long as guaranteeing circulating cooling water containing sulfur
In Zn2+Concentration keep in a specific range, it is preferable that the Zn in circulating cooling water containing sulfur2+Concentration be maintained at
0.2-5mg/L, more preferably 0.5-2mg/L.In the present invention, Zn in circulating cooling water containing sulfur2+Concentration can be according to zinc salt
Dosage and the amount of recirculated cooling water and the amount of recirculated cooling water of discharge of supplement determine.
According to the present invention, to the dosing method of the dirt dispersion agent, there is no particular limitation, as long as guaranteeing to contain sulfur cycle
The concentration of dirt dispersion agent in cooling water is kept in a specific range, it is preferable that the dirt dispersion agent adds
Amount is so that the concentration of dirt dispersion agent described in circulating cooling water containing sulfur remains 4-30mg, more preferably 5-20mg.In this hair
In bright, the concentration of dirt dispersion agent can be according to the dosage of dirt dispersion agent and the circulation of supplement in circulating cooling water containing sulfur
The amount of the recirculated cooling water of the amount and discharge of cooling water determines.
According to the present invention, the dosage of the pH adjusting agent makes the pH of circulating cooling water containing sulfur be 8-9.5.
In method of the present invention, the zinc salt, the type of dirt dispersion agent and pH adjusting agent and source are as above
Described, details are not described herein.
In the present invention, the recirculating cooling water system can be system commonly used in the art, for example, the circulation
Cooling water system includes following part: collecting-tank, circulating pump, heat exchanger and cooling tower, wherein each section is connected by pipeline.
In situations where it is preferred, the position that adds of the sulfide-oxidizing enzyme is the collecting-tank in circulating cooling water containing sulfur system；
Preferably, the position that adds of the zinc salt is the collecting-tank in circulating cooling water containing sulfur system；It is highly preferred that the antiscaling dispersion
The position that adds of agent is the collecting-tank in circulating cooling water containing sulfur system；It is further preferred that the pH adjusting agent adds position
The collecting-tank being set in circulating cooling water containing sulfur system.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
The water quality of test moisturizing is as shown in table 1, and by being passed through H thereto2S to simulate circulating cooling water containing sulfur,
In, Ca2+Concentration, total alkalinity and total hardness are with CaCO3Meter, ammonia-nitrogen content is in terms of N, and sulfur content is with S2-Meter.
Ca2+Detect reference standard GB/T 6910-2006；Total alkalinity detects reference standard GB/T15451-2006；Total hardness
Detect reference standard GB/T 6909-2008；Cl-Detect reference standard GB/T15453-2008；PH value detects reference standard GB/T
6920-1986；COD detects reference standard GB/T15456-2008；Ammonia nitrogen detects reference standard HG/T 2158-2011；Sulfur content
Detect reference standard GB/T16489-1996.
Table 1
For the scene of simulating, dynamic simulation test has been carried out.Dynamic simulation test method presses People's Republic of China's chemical industry
Professional standard HG/T2160-2008 is carried out, and test piece and test tube material are 20#Carbon steel or copper.
The corrosion of carbon steel rate and adherency rate of the circulating cooling water containing sulfur of dynamic simulation test detection after processing.
Embodiment 1
The present embodiment is for illustrating circulating cooling water containing sulfur processing method provided by the invention.
Water quality: the test water in table 1
Cycles of concentration (the Cl of recirculated cooling water-The Cl of concentration and supplement water-The ratio of concentration): 2.3 ± 0.2
PH:8.2 ± 0.2
Flow velocity: 1m/s
Processing: H is passed through into recirculated water2S, the theoretical sulphur concentration for maintaining recirculated water are 2mg/L (with S2-Meter)；To collecting-tank
Thiobacillus thioxidans (purchased from BNCC strain library, article No. ATCC19377) is inside added, dosage is every L recirculated water 200mg, hereafter
It adds within every 10 days once, each dosage is every L recirculated water 100mg；Zinc sulfate is added into collecting-tank, so that recirculated cooling water
Middle Zn2+Concentration be maintained at 1.2mg/L；Polyacrylic acid is added into collecting-tank (to be had purchased from the calm and peaceful water process science and technology share in Shandong
Limit company), keeping the content of polyacrylic acid in every L recirculated water is 12mg.
Inlet temperature of the recirculated water at heat exchanger entrance: 32 ± 1 DEG C
The circulation water entrance temperature difference: 8-10 DEG C
Runing time: 60 days
Dynamic simulation test the results are shown in Table 2.
Embodiment 2
The present embodiment is for illustrating circulating cooling water containing sulfur processing method provided by the invention.
Water quality: the test water in table 1
Cycles of concentration (the Cl of recirculated cooling water-The Cl of concentration and supplement water-The ratio of concentration): 2.3 ± 0.2
PH:8.5 ± 0.2
Flow velocity: 1m/s
Processing: H is passed through into recirculated water2S, the theoretical sulphur concentration for maintaining recirculated water are 3mg/L (with S2-Meter)；To collecting-tank
Grate sulfur thiobacillus (purchased from BNCC strain library, article No. BNCC223406) is inside added, dosage is every L recirculated water 200mg, hereafter often
It adds within 10 days once, each dosage is every L recirculated water 60mg；Zinc chloride is added into collecting-tank, so that in recirculated cooling water
Zn2+Concentration be maintained at 1.5mg/L；Poly- sulfonated phenylethylene is added into collecting-tank (purchased from the calm and peaceful water process science and technology share in Shandong
Co., Ltd), keeping the content of polyacrylic acid in every L recirculated water is 10mg.
Inlet temperature of the recirculated water at heat exchanger entrance: 32 ± 1 DEG C
The circulation water entrance temperature difference: 8-10 DEG C
Runing time: 60 days
Dynamic simulation test the results are shown in Table 2.
Embodiment 3
The present embodiment is for illustrating circulating cooling water containing sulfur processing method provided by the invention.
Water quality: the test water in table 1
Cycles of concentration (the Cl of recirculated cooling water-The Cl of concentration and supplement water-The ratio of concentration): 2.3 ± 0.2
PH:9.0 ± 0.2
Flow velocity: 1m/s
Processing: H is passed through into recirculated water2S, the theoretical sulphur concentration for maintaining recirculated water are 1mg/L (with S2-Meter)；To collecting-tank
Thiobacillus denitrificans (purchased from BNCC strain library, article No. ATCC23644) is inside added, dosage is every L recirculated water 200mg, hereafter often
It adds within 10 days once, each dosage is every L recirculated water 150mg；Zinc sulfate is added into collecting-tank, so that in recirculated cooling water
Zn2+Concentration be maintained at 1mg/L；HEDP (purchased from the calm and peaceful water process Science and Technology Co., Ltd. in Shandong) is added into recirculated water,
The content for keeping HEDP in every L recirculated water is 15mg.
Inlet temperature of the recirculated water at heat exchanger entrance: 32 ± 1 DEG C
The circulation water entrance temperature difference: 8-10 DEG C
Runing time: 60 days
Dynamic simulation test the results are shown in Table 2.
Embodiment 4
The present embodiment is for illustrating circulating cooling water containing sulfur processing method provided by the invention.
Water quality: the test water in table 1
Cycles of concentration (the Cl of recirculated cooling water-The Cl of concentration and supplement water-The ratio of concentration): 2.3 ± 0.2
PH:8.2 ± 0.2
Flow velocity: 1m/s
Processing: H is passed through into recirculated water2S, the theoretical sulphur concentration for maintaining recirculated water are 0.5mg/L (with S2-Meter)；To catchmenting
It is added in pond Thiobacillus thioxidans (with embodiment 1), dosage is every L recirculated water 200mg, is added within hereafter every 10 days once, often
Secondary dosage is every L recirculated water 10mg；Zinc chloride is added into collecting-tank, so that Zn in recirculated cooling water2+Concentration be maintained at
0.5mg/L；ATMP (purchased from the calm and peaceful water process Science and Technology Co., Ltd. in Shandong) is added into collecting-tank, keeps every L recirculated water
The content of middle ATMP is 20mg.
Inlet temperature of the recirculated water at heat exchanger entrance: 32 ± 1 DEG C
The circulation water entrance temperature difference: 8-10 DEG C
Runing time: 60 days
Dynamic simulation test the results are shown in Table 2.
Embodiment 5
The present embodiment is for illustrating circulating cooling water containing sulfur processing method provided by the invention.
Water quality: the test water in table 1
Cycles of concentration (the Cl of recirculated cooling water-The Cl of concentration and supplement water-The ratio of concentration): 2.3 ± 0.2
PH:8.5 ± 0.2
Flow velocity: 1m/s
Processing: H is passed through into recirculated water2S, the theoretical sulphur concentration for maintaining recirculated water are 2mg/L (with S2-Meter)；To collecting-tank
It inside adds grate sulfur thiobacillus (with embodiment 2), dosage is every L recirculated water 200mg, adds within hereafter every 10 days primary, throwing every time
Dosage is every L recirculated water 200mg；Zinc sulfate is added into collecting-tank, so that Zn in recirculated cooling water2+Concentration be maintained at 2mg/
L；Tannin (purchased from Zhengzhou City Wei Feng Biotechnology Co., Ltd) is added into collecting-tank, keeps tannic acid in every L recirculated water
Content is 5mg.
Inlet temperature of the recirculated water at heat exchanger entrance: 32 ± 1 DEG C
The circulation water entrance temperature difference: 8-10 DEG C
Runing time: 60 days
Dynamic simulation test the results are shown in Table 2.
Embodiment 6
The present embodiment is for illustrating circulating cooling water containing sulfur processing method provided by the invention.
It is carried out according to the method for embodiment 2, unlike, the pH of control loop water is 7.5 ± 0.2.Dynamic simulation test
It the results are shown in Table 2.
Comparative example 1
It carries out according to the method for embodiment 1, unlike, the sulfur oxide sulphur that embodiment 1 uses is not added into collecting-tank
Bacillus.Dynamic simulation test the results are shown in Table 2.
Comparative example 2
It is carried out according to the method for embodiment 2, unlike, the zinc chloride that embodiment 2 uses is not added into collecting-tank.It is dynamic
State analog reslt is shown in Table 2.
Comparative example 3
It carries out according to the method for embodiment 1, unlike, the polyacrylic acid that embodiment 1 uses is not added into collecting-tank.
Dynamic simulation test the results are shown in Table 2.
Table 2
By the result of above embodiments 1-6 and comparative example 1-3 being compared as can be seen that the present invention will be by that will contain sulphur
Change bacterium, zinc salt, dirt dispersion agent and optional pH adjusting agent composition add into circulating cooling water containing sulfur system, can be with
The heat exchanger tube in the circulation of sulfur-bearing is set to keep lower corrosion of carbon steel rate and adherency rate.
Particularly, by the way that the result of above embodiments 1-5 and embodiment 6 compares it is found that in preferred reality of the invention
It applies in mode, by adding sulfide-oxidizing enzyme, zinc salt and dirt dispersion agent in the collecting-tank of circulating cooling water containing sulfur system, especially
It is to control the pH value of circulating cooling water containing sulfur in particular range (8-9.5), the heat exchange in the circulation of sulfur-bearing can be made
The adherency rate of pipe is maintained at 9.7mcm hereinafter, corrosion of carbon steel rate is maintained at 0.069mm/a or less.
Meanwhile the composition that the present invention uses has the advantages that environmentally protective based on biological product (such as sulfide-oxidizing enzyme).
In addition, circulating water cooling treatment provided by the invention may be directly applied in existing recirculating cooling water system with composition,
Without additionally increasing advanced treatment device, to greatly reduce processing cost.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of circulating cooling water containing sulfur composition for treating, which is characterized in that the composition contains sulfide-oxidizing enzyme, zinc salt, resistance
Dirty dispersing agent and optional pH adjusting agent.
2. composition according to claim 1, wherein relative to every L circulating cooling water containing sulfur, the sulfide-oxidizing enzyme contains
Amount is 5-400mg, preferably 10-200mg；
Preferably, described with Zn2+The zinc salt of meter and the weight ratio of the dirt dispersion agent are 0.02-0.5:1, preferably
0.025-0.4:1；
It is highly preferred that the content of the pH adjusting agent makes the pH of circulating cooling water containing sulfur be 8-9.5；
It is further preferred that the pH adjusting agent is sulfuric acid, hydrochloric acid, nitric acid, sodium bicarbonate, saleratus, sodium hydroxide and hydrogen
At least one of potassium oxide.
3. composition according to claim 1 or 2, wherein the sulfide-oxidizing enzyme be Thiobacillus (Thiobacillus),
At least one of Beggiatoa (Beggiatoa) and Thiothrix (Thiothrix) bacterium, preferably in Thiobacillus extremely
A kind of few bacterium, more preferably Thiobacillus thioxidans (Thiobacillus thiooxidans), grate sulfur thiobacillus
At least one of (Thiobacillus thioparus) and thiobacillus denitrificans (Thiobacillus denitrificans).
4. composition according to claim 1 or 2, wherein the zinc salt is zinc sulfate and/or zinc chloride.
5. composition according to claim 1 or 2, wherein the dirt dispersion agent is carboxylic acid quasi polymer, organic phospho acid
Class compound, sulfonic acid quasi polymer, carboxylic acid-at least one of sulfonic acid quasi polymer and natural phenolic substance；
Preferably, the dirt dispersion agent is polyacrylic acid, acrylic copolymer, poly, maleic acid, polysulfonate
Styrene, acrylic acid-Sodium Allyl Sulfonate copolymer, 1-hydroxy ethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediamine tetraacetic methene
Phosphonic acids, ethanamidine base ethylene-diphosphonic acid, phosphine carboxylic acid, triol ester, hexa-atomic alcohol ester, alkanolamine ester, sodium humate, tannin and sulfonation are wooden
At least one of element；
It is highly preferred that the dirt dispersion agent is polyacrylic acid, poly- sulfonated phenylethylene, 1-hydroxy ethylidene-1,1-diphosphonic acid, amino trimethylene first
At least one of base phosphonic acids and tannin.
6. composition described in any one of -5 according to claim 1, wherein the sulfide-oxidizing enzyme, the zinc salt, the resistance
Dirty dispersing agent and the pH adjusting agent are individually separated preservation.
7. application of the composition described in any one of claim 1-6 in circulating cooling water containing sulfur processing；Preferably, with
S2-Meter, the sulfur content of the circulating cooling water containing sulfur are 0.01-5mg/L, preferably 0.1-4mg/L, more preferably 0.5-3mg/
L。
8. a kind of method of circulating cooling water containing sulfur processing, which is characterized in that this method comprises: by sulfide-oxidizing enzyme, zinc salt, scale inhibition
Dispersing agent and optional pH adjusting agent are added into circulating cooling water containing sulfur system；
Preferably, with S2-Meter, the sulfur content of the circulating cooling water containing sulfur are 0.01-5mg/L, preferably 0.1-4mg/L, more excellent
It is selected as 0.5-3mg/L.
9. the frequency that adds of the sulfide-oxidizing enzyme is to add within every 5-15 days once according to the method described in claim 8, wherein,
It adds within preferably every 8-10 days primary；
Preferably, relative to every L circulating cooling water containing sulfur, each dosage of the sulfide-oxidizing enzyme is 5-400mg, preferably
10-200mg。
10. according to the method described in claim 8, wherein, the dosage of the zinc salt makes Zn in circulating cooling water containing sulfur2+'s
Concentration is maintained at 0.2-5mg/L, preferably 0.5-2mg/L；
Preferably, the dosage of the dirt dispersion agent keeps the concentration of dirt dispersion agent described in circulating cooling water containing sulfur
In 4-30mg/L, preferably 5-20mg/L；
Preferably, the dosage of the pH adjusting agent makes the pH of circulating cooling water containing sulfur be 8-9.5.
11. the method according to any one of claim 8-10, wherein the position that adds of the sulfide-oxidizing enzyme is sulfur-bearing
Collecting-tank in recirculating cooling water system；
Preferably, the position that adds of the zinc salt is the collecting-tank in circulating cooling water containing sulfur system；
Preferably, the position that adds of the dirt dispersion agent is the collecting-tank in circulating cooling water containing sulfur system；
Preferably, the position that adds of the pH adjusting agent is the collecting-tank in circulating cooling water containing sulfur system.
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| CN201710758389.XA CN109422356A (en) | 2017-08-29 | 2017-08-29 | Circulating cooling water containing sulfur composition for treating and its application |
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| JPS5888094A (en) * | 1981-11-17 | 1983-05-26 | Ebara Infilco Co Ltd | Purification of organic filthy water |
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2017
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| JPS5888094A (en) * | 1981-11-17 | 1983-05-26 | Ebara Infilco Co Ltd | Purification of organic filthy water |
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