CN109422351A - Circulating cooling water containing sulfur processing system and its application - Google Patents
Circulating cooling water containing sulfur processing system and its application Download PDFInfo
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- CN109422351A CN109422351A CN201710758305.2A CN201710758305A CN109422351A CN 109422351 A CN109422351 A CN 109422351A CN 201710758305 A CN201710758305 A CN 201710758305A CN 109422351 A CN109422351 A CN 109422351A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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 processing system and its application with circulating cooling water containing sulfur processing.Specifically, the present invention provides a kind of circulating cooling water containing sulfur processing system, which contains ecological floating island, sulfide-oxidizing enzyme, dirt dispersion agent and optional oxygen consumption agent.When handling using system 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 processing system and its
Using and circulating cooling water containing sulfur processing method.
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 system and its application and circulating cooling water containing sulfur processing.Using system provided by the invention to containing sulfur cycle
When cooling water is handled, the heat exchanger tube in the circulation of sulfur-bearing can be made to keep lower corrosion of carbon steel rate and adherency
Rate.
To achieve the goals above, in a first aspect, the present invention provides a kind of circulating cooling water containing sulfur processing system,
In, which contains ecological floating island, sulfide-oxidizing enzyme, dirt dispersion agent and optional oxygen consumption agent.
Second aspect, the present invention also provides application of the above-mentioned system 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, this method comprises: by ecological
Chinampa, sulfide-oxidizing enzyme, dirt dispersion agent and optional oxygen consumption 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 ecological floating island, sulfide-oxidizing enzyme and scale inhibition point
Powder, and control circulating cooling water containing sulfur dissolved oxygen concentration in particular range (≤2mg/L), the circulation of sulfur-bearing can be made
The adherency rate of heat exchanger tube in water system is maintained at 9.2mcm hereinafter, corrosion of carbon steel rate is maintained at 0.066mm/a or less.
Detailed description of the invention
Fig. 1 is the schematic diagram for the recirculating cooling water system that the present invention uses.
Description of symbols
A collecting-tank B circulating pump
C heat exchanger D cooling tower
A water inlet line b outlet conduit
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 processing systems, wherein the system contains ecology
Chinampa, sulfide-oxidizing enzyme, dirt dispersion agent and optional oxygen consumption 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.
In the present invention, term " ecological floating island " refers to a kind of by engineer's construction, floats on the water surface, with bamboo and wood
Or artificial synthesized high molecular material is matrix or carrier, for planting higher aquatic plants or terrestrial plant, for animals and plants and
The biological and ecological facility that microorganism grows, multiplies, inhabiting.There is no particular limitation for type of the present invention to the ecological floating island,
It can be type of this field conventionally used for water body purification.In situations where it is preferred, the ecological floating island includes floatable load
Body and the plant to grow nonparasitically upon another plant on the carrier, wherein the plant can be the terrestrial plant of water plant and/or improvement, more
Preferably water plant, more preferably reed, greatly one of drift and water hyacinth or a variety of.
In the present invention, to the source of the ecological floating island, there is no particular limitation, for example, can voluntarily prepare, it can also
To be obtained by conventional commercially available means.
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.
In the present invention, the gross area of the ecological floating island can carry out conventional selection according to the volume of recirculated water, as long as
It can achieve the purpose of water body purification and microorganism attachment, for example, the ecological floating island provided to follow relative to every L sulfur-bearing
Ring cooling water, the gross area of the ecological floating island are 1-8cm2, preferably 1.5-6cm2。
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, 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 oxygen consumption agent can be carried out according to the concentration of dissolved oxygen in circulating cooling water containing sulfur
Setting, it is preferable that the content of the oxygen consumption agent makes concentration≤2mg/L of dissolved oxygen in circulating cooling water containing sulfur, more preferably
≤1mg/L。
According to the present invention, the oxygen consumption agent can reduce oxygen content in water for common various in this field and (or disappear
Oxygen in water consumption) substance, for example, can be at least one of selected from sodium sulfite, hydrazine hydrate and dimethyl ketone oxime.
According to the present invention, the ecological floating island, the sulfide-oxidizing enzyme, the dirt dispersion agent and the oxygen consumption agent be respectively
It is retained separately.
According to the present invention, the system also contains regulator；Preferably, the regulator is in hydrochloric acid, sulfuric acid and nitric acid
At least one；It is highly preferred that the content of the regulator makes the recirculated cooling water with CaCO3The calcium degree and basicity of meter it
With for 500-1500mg/L, preferably 600-1000mg/L.
Second aspect, the present invention also provides application of the above-mentioned system 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, more preferably 0.1-4mg/L, further preferably
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, more preferably 0.1-4mg/L, further preferably 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: by ecological
Chinampa, sulfide-oxidizing enzyme, dirt dispersion agent and optional oxygen consumption agent are added into circulating cooling water containing sulfur system.
In the present invention, the composition of the circulating cooling water containing sulfur is as described above, details are not described herein.
In method of the present invention, the gross area of the ecological floating island can carry out conventional according to the volume of recirculated water
Selection, as long as can achieve the purpose of water body purification, for example, relative to every L circulating cooling water containing sulfur, the ecological floating island
The gross area be 1-8cm2, preferably 1.5-6cm2。
In the present invention, the ecological floating island can be used for a long time, as long as the plant in ecological floating island keeps survival.
In the present invention, the type of the ecological floating island and composition are as described above, details are not described herein.
According to the present invention, the dosing method of the sulfide-oxidizing enzyme preferably adds step by step.Preferably, the sulfide-oxidizing enzyme
Adding frequency is to add within every 5-15 days once, is added within preferably every 8-10 days primary.It is highly preferred that containing sulfur cycle relative to every L
Cooling water, each 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.It is excellent
Selection of land, 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 greater than
Subsequent dosage.It is highly preferred that the dosage for the first time of the sulfide-oxidizing enzyme is 200-400mg, preferably 200-300mg；It is 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 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 is maintained at 4-30mg/L, more preferably 5-20mg/L.?
In the present invention, the concentration of dirt dispersion agent can be according to the dosage of dirt dispersion agent and supplement in circulating cooling water containing sulfur
The amount of the recirculated cooling water of the amount and discharge of recirculated cooling water determines.
According to the present invention, the dosage of the oxygen consumption agent makes concentration≤2mg/ of dissolved oxygen in circulating cooling water containing sulfur
L, preferably≤1mg/L.
In method of the present invention, the type and source of the dirt dispersion agent and oxygen consumption agent as described above,
This is repeated no more.
In the present invention, the circulating cooling water containing sulfur system can be system commonly used in the art, for example, as schemed
Shown in 1, the recirculating cooling water system includes: collecting-tank A, circulating pump B, heat exchanger C, cooling tower D, condensate make-up piping a and row
Sewage conduct b, wherein collecting-tank A, circulating pump B, heat exchanger C and cooling tower D are sequentially connected by pipeline.It was actually using
Recirculated water in Cheng Zhong, collecting-tank A enters heat exchanger C through circulating pump B, and the recirculated water after exchanging heat enters cooling tower D, after cooling
Recirculated water return to collecting-tank A, complete one circulation.During continuous circulating cooling, vapor is lost, recirculated water is constantly dense
Contracting, discharge reduction, it is therefore desirable to through moisturizing pipeline a supplement water, when recirculated water concentration to a certain extent, need to be arranged through blow-off line b
Part recirculated water is out to reduce each ion concentration in recirculated water.
In situations where it is preferred, the position that adds of the ecological floating island is the collecting-tank in circulating cooling water containing sulfur system；
Preferably, the position that adds of the sulfide-oxidizing enzyme is the collecting-tank A in circulating cooling water containing sulfur system；It is highly preferred that the resistance
The position that adds of dirty dispersing agent is the collecting-tank A in circulating cooling water containing sulfur system；It is further preferred that the oxygen consumption agent
Adding the entrance that position is circulating pump B in circulating cooling water containing sulfur system, (namely the water outlet in collecting-tank A enters circulating pump B
Add oxygen consumption agent thereto before).
According to the present invention, the method also includes: control the circulating cooling water containing sulfur with CaCO3The calcium degree and basicity of meter
The sum of be 500-1500mg/L, preferably 600-1000mg/L.
In the present invention, to the mode of the control, there is no particular limitation, as long as can guarantee circulating cooling water containing sulfur
Calcium degree and the sum of basicity keep within the above range (500-1500mg/L), for example, the control can be using concentration
Mode, alternatively, the mode of the control may include: to add regulator into the circulating cooling water containing sulfur system,
In, the regulator is at least one of hydrochloric acid, sulfuric acid and nitric acid.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
Ecological floating island plants Co., Ltd purchased from Hebei province, shampoo plant chinampa, source, and main group becomes high density polyphenyl second
Alkene carrier and reed；
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/T 15451-2006；It is total hard
Degree detection reference standard GB/T 6909-2008；Cl-Detect 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 detects reference standard HG/T 2158-2011；
Sulfur content detects 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
The sum of calcium degree and basicity are controlled (with CaCO3Meter) it is 700mg/L
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)；Ecology is floating
Island (3cm2/ L recirculated water) it is placed in collecting-tank；Thiobacillus thioxidans is added into collecting-tank (purchased from BNCC strain library, article No.
ATCC19377), dosage is every L recirculated water 200mg, is added within hereafter every 10 days once, and each dosage is every L recirculated water
100mg；Polyacrylic acid (purchased from the calm and peaceful water process Science and Technology Co., Ltd. in Shandong) is added into collecting-tank, and every L is kept to recycle
The content of polyacrylic acid is 12mg in water；Sodium sulfite is added in the inlet of the circulating pump of circulation, keeps heat exchanger
Dissolved oxygen concentration is less than 1mg/L in the recirculated water of exit.
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
The sum of calcium degree and basicity are controlled (with CaCO3Meter) it is 900mg/L
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)；Ecology is floating
Island (1.5cm2/ L recirculated water) it is placed in collecting-tank；Grate sulfur thiobacillus is added into collecting-tank (purchased from BNCC strain library, article No.
BNCC223406), dosage is every L recirculated water 200mg, is added within hereafter every 10 days once, and each dosage is every L recirculated water
60mg；Poly- sulfonated phenylethylene (purchased from the calm and peaceful water process Science and Technology Co., Ltd. in Shandong) is added into collecting-tank, and every L is kept to follow
The content of poly- sulfonated phenylethylene is 10mg in ring water；Hydrazine hydrate is added in the inlet of the circulating pump of circulation, keeps changing
Dissolved oxygen concentration is less than 1mg/L in the recirculated water of hot device exit.
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
The sum of calcium degree and basicity are controlled (with CaCO3Meter) it is 800mg/L
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)；Ecology is floating
Island (6cm2/ L recirculated water) it is placed in collecting-tank；Thiobacillus denitrificans are added into collecting-tank (purchased from BNCC strain library, article No.
ATCC23644), dosage is every L recirculated water 200mg, is added within hereafter every 10 days once, and each dosage is every L recirculated water
150mg；HEDP (purchased from the calm and peaceful water process Science and Technology Co., Ltd. in Shandong) is added into collecting-tank, is kept in every L recirculated water
The content of HEDP is 15mg；Dimethyl ketone oxime is added in the inlet of the circulating pump of circulation, is kept at heat exchanger exit
Dissolved oxygen concentration is less than 1mg/L in recirculated water.
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
The sum of calcium degree and basicity are controlled (with CaCO3Meter) it is 1000mg/L
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)；It will be ecological
Chinampa (3cm2/ L recirculated water) it is placed in collecting-tank；Thiobacillus thioxidans (with embodiment 1), dosage are added into collecting-tank
It for every L recirculated water 200mg, adds within hereafter every 10 days once, each dosage is every L recirculated water 10mg；It is added into collecting-tank
ATMP (is purchased from the calm and peaceful water process Science and Technology Co., Ltd. in Shandong), and keeping the content of ATMP in every L recirculated water is 20mg；It is following
The inlet of the circulating pump of ring water system adds sodium sulfite, and dissolved oxygen concentration is less than in recirculated water at holding heat exchanger exit
1mg/L。
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
The sum of calcium degree and basicity are controlled (with CaCO3Meter) it is 600mg/L
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)；Ecology is floating
Island (3cm2/ L recirculated water) it is placed in collecting-tank；Grate sulfur thiobacillus (with embodiment 2) is added into collecting-tank, dosage is every
L recirculated water 200mg is added once for hereafter every 10 days, and each dosage is every L recirculated water 200mg；Tannin is added into recirculated water
(being purchased from Zhengzhou City Wei Feng Biotechnology Co., Ltd), keeping the content of tannin in every L recirculated water is 5mg；In circulating water
The inlet of the circulating pump of system adds dimethyl ketone oxime, and dissolved oxygen concentration is less than 1mg/L in recirculated water at holding heat exchanger exit.
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 carries out according to the method for embodiment 1, unlike, the sum of calcium degree and basicity are controlled (with CaCO3Meter) it is 1200mg/
L.Dynamic simulation test the results are shown in Table 2.
Embodiment 7
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, hydrazine hydrate is not added, is dissolved in recirculated water at heat exchanger exit
The concentration of oxygen is 1.5-2mg/L.Dynamic simulation test the results are shown in Table 2.
Comparative example 1
It is carried out according to the method for embodiment 2, unlike, ecological floating island is not added in collecting-tank.Dynamic simulation test
It the results are shown in Table 2.
Comparative example 2
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 3
It is carried out according to the method for embodiment 2, unlike, the polysulfonate benzene that embodiment 2 uses is not added into collecting-tank
Ethylene.Dynamic simulation test the results are shown in Table 2.
Table 2
By the result of above embodiments 1-7 and comparative example 1-3 being compared as can be seen that the present invention will be by that will contain life
State chinampa, sulfide-oxidizing enzyme, dirt dispersion agent and optional oxygen consumption agent system add into circulating cooling water containing sulfur system, can
So that the heat exchanger tube in the circulation of sulfur-bearing keeps lower corrosion of carbon steel rate and adherency rate.
Particularly, by the way that the result of above embodiments 1-5 and embodiment 6 and 7 compare it is found that of the invention preferred
In embodiment, by adding ecological floating island, sulfide-oxidizing enzyme and antiscaling dispersion in the collecting-tank of circulating cooling water containing sulfur system
Agent, and control circulating cooling water containing sulfur dissolved oxygen concentration in particular range (≤2mg/L), the recirculated water of sulfur-bearing can be made
The adherency rate of heat exchanger tube in system is maintained at 9.2mcm hereinafter, corrosion of carbon steel rate is maintained at 0.066mm/a or less.
Meanwhile the system that the present invention uses has the advantages that environmentally protective based on biological product (such as sulfide-oxidizing enzyme).Separately
Outside, circulating water cooling treatment provided by the invention may be directly applied in existing recirculating cooling water system with system, and nothing
Advanced treatment device need to additionally be increased, 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 (13)
1. a kind of circulating cooling water containing sulfur processing system, which is characterized in that the system contains ecological floating island, sulfide-oxidizing enzyme, resistance
Dirty dispersing agent and optional oxygen consumption agent.
2. system according to claim 1, wherein relative to every L circulating cooling water containing sulfur, total face of the ecological floating island
Product is 1-8cm2, preferably 1.5-6cm2；
Preferably, relative to every L circulating cooling water containing sulfur, the content of the sulfide-oxidizing enzyme is 5-400mg, preferably 10-
200mg；
Preferably, the content of the dirt dispersion agent is maintained at the concentration of dirt dispersion agent described in circulating cooling water containing sulfur
4-30mg/L, preferably 5-20mg/L；
Preferably, the content of the oxygen consumption agent makes concentration≤2mg/L of dissolved oxygen in circulating cooling water containing sulfur, preferably≤
1mg/L。
3. system according to claim 1 or 2, wherein the sulfide-oxidizing enzyme is Thiobacillus (Thiobacillus), shellfish
At least one of family name's sulphur Pseudomonas (Beggiatoa) and Thiothrix (Thiothrix) bacterium, preferably in Thiobacillus at least
A kind of bacterium, more preferably Thiobacillus thioxidans (Thiobacillus thiooxidans), grate sulfur thiobacillus (Thiobacillus
) and at least one of thiobacillus denitrificans (Thiobacillus denitrificans) thioparus.
4. system according to claim 1 or 2, wherein the dirt dispersion agent is carboxylic acid quasi polymer, organic phosphine acids
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.
5. system according to claim 1 or 2, wherein the oxygen consumption agent is selected from sodium sulfite, hydrazine hydrate and dimethyl
At least one of ketoxime.
6. system described in any one of -5 according to claim 1, wherein the ecological floating island, the sulfide-oxidizing enzyme, described
Dirt dispersion agent and the oxygen consumption agent are individually separated preservation.
7. system described in any one of -6 according to claim 1, wherein the system also contains regulator, the adjusting
Agent is at least one of hydrochloric acid, sulfuric acid and nitric acid；
Preferably, the content of the regulator makes the circulating cooling water containing sulfur with CaCO3The sum of the calcium degree of meter and basicity are
500-1500mg/L, preferably 600-1000mg/L.
8. application of the system described in any one of claim 1-7 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.
9. a kind of method of circulating cooling water containing sulfur processing, which is characterized in that this method comprises: by ecological floating island, sulfide-oxidizing enzyme,
Dirt dispersion agent and optional oxygen consumption 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.
10. according to the method described in claim 9, wherein, relative to every L circulating cooling water containing sulfur, the ecological floating island it is total
Area is 1-8cm2, preferably 1.5-6cm2。
11. 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 9, 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。
12. according to the method described in claim 9, wherein, the dosage of the dirt dispersion agent makes circulating cooling water containing sulfur
Described in the concentration of dirt dispersion agent be maintained at 4-30mg/L, preferably 5-20mg/L；
Preferably, the dosage of the oxygen consumption agent makes concentration≤2mg/L of dissolved oxygen in circulating cooling water containing sulfur, preferably≤
1mg/L。
13. the method according to any one of claim 9-12, wherein the position that adds of the ecological floating island is sulfur-bearing
Collecting-tank in recirculating cooling water system；
Preferably, 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 dirt dispersion agent is the collecting-tank in circulating cooling water containing sulfur system；
Preferably, the oxygen consumption agent add position be circulating cooling water containing sulfur system in circulating pump entrance.
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