CN102476872A - Circulating water treatment method adopting deionized water as supplement water - Google Patents
Circulating water treatment method adopting deionized water as supplement water Download PDFInfo
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- CN102476872A CN102476872A CN2010105574131A CN201010557413A CN102476872A CN 102476872 A CN102476872 A CN 102476872A CN 2010105574131 A CN2010105574131 A CN 2010105574131A CN 201010557413 A CN201010557413 A CN 201010557413A CN 102476872 A CN102476872 A CN 102476872A
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Abstract
The invention relates to a circulating water treatment method adopting deionized water as supplement water. The method comprises a) controlling pH of circulating water at 9-11.5; b) adding a corrosion inhibitor containing borate, gluconate and/or silicate; and c) adding a non chloric disinfectant such as bromine-containing disinfectant and chlorine-containing disinfectant which produces no hypochlorous acid in water. The inventive circulating water treatment method is suitable for treatment of a circulating cooling water system with sewage subjected to secondary treatment firstly and then to double membrane process so as to serve as supplement water, and can effectively control corrosion and microorganism growth.
Description
Technical field
The present invention relates to a kind of circulating water treatment method, relate in particular to a kind of circulating water treatment method of doing moisturizing with deionized water.
Background technology
As everyone knows, in industries such as petrochemical complex, thermal power generation, metallurgy, need to use big water gaging, wherein water coolant accounts for significant proportion, accounts for more than 80% of water of productive use like petroleum chemical enterprise's water coolant water.Nowadays water resources shortage, water saving has become world's theme.Sewage and Zhong Shui are back to the consumption that recirculated water will reduce fresh water greatly, even realize the spot patch fresh water.
The U.S. has realized discharging urban sewage recycling in the power generation cycle water system in the sixties in 20th century, and the nineties has realized reuse of qualified discharge industrial sewage and petrochemical equipment circulating water system.The method of taking is that sewage is carried out advanced treatment, reduces COD, suspended substance and microorganism concn in the qualified discharge sewage, uses the burn into fouling and the mikrobe of water conditioner opertaing device again.
The method that sewage and Zhong Shui are back to recirculated water has two kinds.A kind of is advanced treatment, is about to sewage reuse after passing through coagulation, deposition, filtration, sterilization again after the second-stage treatment.Another kind is two embrane methods, soon feeds the ultrafiltration reverse osmosis unit after the water process coagulation after the second-stage treatment, deposition, the filtration, and water outlet is a deionized water.Two embrane method investment costs are big, still, because there is not the fouling factor in the deionized water; Be applied to circulating cooling make-up water, scale problems can be ignored, and therefore can improve cycles of concentration greatly; But also the expense of having saved Scale inhibitors can also prolong duration of service in addition, saves the overhaul of the equipments expense.It is thus clear that adopt deionized water can reduce the later stage expense.It is corrosion and microbiological manipulation that deionized water is done the problem that circulating cooling make-up water need solve.
CN1338433A discloses in the sewage of qualified discharge and to have added sterilant and carry out disinfection, and adds alkaline matter and makes the pH value be controlled at 9.5-14 to carry out inhibition.Its shortcoming is: because have dissolved oxygen in the water, depend merely on adjusting pH value and can not control corrosion effectively.
CN1524806A discloses the water of high oily(waste)water after oil removal, sedimentation has been introduced circulating water system, simultaneously, adds inorganic base substance and makes the pH value reach 7-11, adds sterilant and corrosion inhibiting and descaling agent.Sterilant selects that Youxiaolin, trichloroisocyanuric acid etc. can produce hypochlorous chlorine series bactericidal agent in water, corrosion inhibiting and descaling agent is selected organophosphorus, Sodium hexametaphosphate 99, Sodium orthomolybdate etc. for use for use.Its shortcoming is: the chlorine series bactericidal agent can lose efficacy under alkaline condition, and phosphorus containg substances such as organophosphorus, Sodium hexametaphosphate 99 are if cause body eutrophication with the sewage discharge meeting.
CN1393411A has studied a kind of composite corrosion inhibitor that is used for deionized water, and compsn is made up of deionized water, polyetheramides, silicate.Different with inhibiter composition of the present invention, and the present invention is the circulating water treatment method.
Summary of the invention
The object of the present invention is to provide a kind of deionized water to do the circulating water treatment method of moisturizing.
For reaching above purpose, the invention provides a kind ofly with the circulating water treatment method of deionized water as moisturizing, may further comprise the steps: a) the pH value of Control Circulation water is at 9-11.5; B) add inhibiter, said inhibiter is a kind of or its mixture in borate, gluconate and the silicate; C) add non-chlorbenside microbial inoculum, said non-chlorbenside microbial inoculum is brominated sterilant and in water, does not produce hypochlorous chloride sterilant.
The present invention is preferably with the pH value of alkaline matter Control Circulation water, and said alkaline matter is a kind of in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood preferably.
Consider price factor, under the close situation of effect, the general particular certain cancers inhibiter of the present invention.
Borate of the present invention is selected from Sodium Tetraborate and potassium borate, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees; Gluconate is selected from Sunmorl N 60S, Potassium Gluconate and Zinc Gluconate; Silicate is selected from sodium metasilicate, Starso, positive potassium silicate and potassium metasilicate, preferably from Starso, more preferably is selected from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate and anhydrous sodium metasilicate.
Sterilant of the present invention is selected from organic bromine series bactericidal agent, RH-893 and quaternary ammonium salt.Said organic bromine is preferably from 2, amino propionic acid amide of 2-dibrominated-3-time and 1-bromo-3-chloro-5, and the 5-dimethyl-is for NSC 9226; Quaternary ammonium salt is selected from single long chain quaternary, dialkyl quaternary ammonium salt and polyquaternium; The preferred self-drifting of said single long chain quaternary is R
1(R
3)
2NR
2The quaternary ammonium salt of X, wherein R
1For carbonatoms be 8-20 chain alkyl, be preferably dodecyl, tetradecyl hexadecyl or octadecyl, R
2For aryl or aralkyl, be preferably the aralkyl that carbonatoms is 7-11, R
3For carbonatoms be 1-4 alkyl, be preferably methyl; X is a chlorine or bromine, preferably from dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, cetalkonium chloride and octadecyl dimethyl benzyl brometo de amonio; It is R that dialkyl quaternary ammonium salt is preferably general formula
4(R
6)
2NR
5The quaternary ammonium salt of X, wherein R
4With R
5Difference, R
4For carbonatoms is the chain alkyl of 12-20, be preferably dodecyl, tetradecyl or hexadecyl, R
5For carbonatoms is the alkyl of 6-10, be preferably octyl or decyl, R
4For carbonatoms is the alkyl of 1-4, X is a chlorine or bromine, is preferably dodecyl dimethyl decyl brometo de amonio, tetradecyl dimethyl-octyl group brometo de amonio, tetradecyl dimethyl decyl brometo de amonio and hexadecyldimethyl benzyl ammonium octyl group brometo de amonio; The preferred autohemagglutination chlorination of polyquaternium-2-hydroxypropyl-1,1-N-dimethylammonium, Poly Dimethyl Diallyl Ammonium Chloride and dimethyl diallyl ammonium chloride/acrylamide copolymer.
Inhibiter according to the invention is preferably the mixture of the two or three inhomogeneity salt that is selected from borate, gluconate and silicate.When inhibiter was the mixture of borate and gluconate, the weight proportion of borate and gluconate was 1:3-3:1; When inhibiter was the mixture of silicate and gluconate, the weight proportion of silicate and gluconate was 2:1-1:2; When inhibiter was the mixture of borate and silicate, borate and silicate weight proportion were 1.5:1-1:5; When inhibiter was the mixture of borate, gluconate and silicate, borate accounted for 25-45 weight %, gluconate 20-35 weight %, silicate and accounts for 25-45 weight %.During as inhibiter, synergistic effect is obvious, can reduce total consumption of salt, and corrosion mitigating effect is good with inhomogeneous salt mixture.Inhibiter according to the invention most preferably is the mixture of borate, gluconate and silicate.
Its effective working concentration was 30-80mg/L when inhibiter according to the invention was single medicament, inhibiter be various medicaments when composite its total effectively working concentration be 20-60mg/L, wherein boratory concentration is with B
4O
7 2-The concentration of meter, gluconate in the concentration of gluconate, silicate with SiO
2Meter.
Sterilant according to the invention was an one-period with 30 days when adding preferably, divided in each cycle to add for four times, whenever added once at a distance from 6-8 days.Order of adding is: add organic bromine for the first time, for the third time, add for the second time RH-893, add the mixture of quaternary ammonium salt the 4th time.Adding concentration is preferably: organic bromine 5-20mg/L, RH-893 30-80mg/L, quaternary ammonium salt 20-50mg/L.
B of the present invention) going on foot described inhibiter can add with the mode of single agent, also can be mixed with composite corrosion inhibitor earlier, composite scale-inhibiting corrosion inhibitor is once added in the recirculated water again, preferably carries out with the latter's mode.Available ordinary method prepares composite corrosion inhibitor of the present invention, and the reinforced order of each component is unimportant, for example can make required composite corrosion inhibitor with borate, silicate, gluconate and water by predetermined mixed.
The addition step of circulating water treatment method of the present invention can be successively by a), b) and c) step carry out, also can carry out a)-c) step by other arbitrary orders, can also carry out these three steps simultaneously.
Method of the present invention is applicable to that the sewage after the second-stage treatment handles the back through two embrane methods and handle as the recirculating cooling water system of moisturizing, can effectively control and corrode and microorganism growth.
Embodiment
Following corrosion inhibitor formula embodiment will help to explain the present invention, but not limit to its scope.Test water is a deionized water, and the carbon steel test piece is the 20# steel.Test water water quality is seen table 1.
Table 1: quality of de-ionized water
The measuring method of water quality is with reference to as follows:
PH value: GB/T 6920-1986 " the mensuration glass electrode method of water pH value "
Specific conductivity: GB/T 6908-2008 " mensuration of BW river water coolant analytical procedure specific conductivity "
Total dissolving admittedly: GB/T 14415-2007 " mensuration of solid matter in industrial circulating cooling water and the BW "
The corrosion inhibition of following embodiment gained and bactericidal property assessment method are following:
Corrosion inhibition: the test piece of 20# qualitative carbon steel is fixed on the lacing film appearance, puts into the test water that is added with the drug concentration that adds by embodiment, 45 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72h, and the weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is: F=(C * △ W)/(A * T * ρ)
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 * 10
7
△ W: the corrosion weight loss of test specimen (g)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
The mensuration of heterotrophic bacterium:Get test water, in sterilisable chamber, adopt 10 times of dilution technologies of former water, test water is diluted to suitable multiple, and the water sample of corresponding extension rate is inoculated in the petridish.Then aseptic culture medium is poured in the petridish, mix, cultivate 72 ± 4h etc. being inverted in the incubator that is placed on 29 ± 1 ℃ after the culture medium solidifying with water sample.After the cultivation, take out petridish, select those petridish to count, colony count multiply by the heterotrophic bacterium number that corresponding dilution training number is this water sample with 30-300 bacterium colony.
Adhere to the mensuration of speed:Test tube is positioned in the bypass of interchanger, takes out test tube after the off-test, clean the test tube outer wall after, constant temperature drying takes by weighing the heavy (W of band bur test tube
1).Clean the inboard wall of test tube bur then, dry, take by weighing the heavy (W of test tube
2), calculate and adhere to speed F '.
F’=7.2×10
5×(W
1-W
2)/（A×t）
A: the area (cm of test specimen
2)
T: corrosion test time (h)
Embodiment 1
Take by weighing the 86.0g sodium borate decahydrate and (contain B
4O
7 2-35.0g) to join the 114.0g deionized water for stirring even, is made into inhibiter 200.0g of the present invention.
The inhibiter and the deionized water of present embodiment are rotated the lacing film experiment; It is 35mg/L that medicament effectively adds concentration; 11.0, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0531mm/a.
Embodiment 2
Take by weighing the 111.8g anhydrous sodium metasilicate and (contain SiO
255.0g) to join the 88.2g deionized water for stirring even, is made into inhibiter 200.0g of the present invention.
The inhibiter and the deionized water of present embodiment are rotated the lacing film experiment; It is 55mg/L that medicament effectively adds concentration; 10.5, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0437mm/a.
Embodiment 3
Taking by weighing the 75.0g Sunmorl N 60S, to join the 25.0g deionized water for stirring even, is made into inhibiter 100.0g of the present invention.
The inhibiter and the deionized water of present embodiment are rotated the lacing film experiment; It is 75mg/L that medicament effectively adds concentration; 10.0, is 45 ℃ in temperature with Pottasium Hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0535mm/a.
Embodiment 4
Borate is (with B
4O
7 2-The meter) and the mass concentration ratio of gluconate be 1:2.5.
Take by weighing 29.5g five hydration sodium tetraborates and (contain B
4O
7 2-15.7g), the 39.3g Zinc Gluconate, it is even to join the 131.2g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 55mg/L that medicament effectively adds concentration; 9.2, is 45 ℃ in temperature with salt of wormwood control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0134mm/a
Embodiment 5
Borate is (with B
4O
7 2-The meter) and the mass concentration ratio of gluconate be 1:1.
Take by weighing 41.7g five hydration potassium tetraborates and (contain B
4O
7 2-20.0g), the 20.0g Potassium Gluconate, it is even to join the 138.3g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 40mg/L that medicament effectively adds concentration; 10.5, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0158mm/a.
Embodiment 6
Borate is (with B
4O
7 2-The meter) and the mass concentration ratio of gluconate be 2:1.
Take by weighing the 49.1g sodium borate decahydrate and (contain B
4O
7 2-20.0g), the 10.0g Sunmorl N 60S, it is even to join the 40.9g deionized water for stirring, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 30mg/L that medicament effectively adds concentration; 11.0, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0155mm/a
Embodiment 7
Borate is (with B
4O
7 2-The meter) and the mass concentration ratio of gluconate be 2.5:1.
Take by weighing 47.2g four hydrations eight Sodium Tetraboratees and (contain B
4O
7 2-17.8g), the 7.2g Sunmorl N 60S, it is even to join the 35.0g deionized water for stirring, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 25mg/L that medicament effectively adds concentration; 11.2, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0159mm/a
Embodiment 8
Silicate is (with SiO
2The meter) and the mass concentration ratio of gluconate be 1.5:1.
Take by weighing the 73.6g water glass and (contain SiO
224.0g), the 16.0g Sunmorl N 60S, it is even to join the 110.4g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 40mg/L that medicament effectively adds concentration; 10.5, is 45 ℃ in temperature with Pottasium Hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0175mm/a.
Embodiment 9
Silicate is (with SiO
2The meter) and the mass concentration ratio of gluconate be 1:1.
Take by weighing the 97.2g metasilicate pentahydrate sodium and (contain SiO
227.5g), the 27.5g Zinc Gluconate, it is even to join the 75.3g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 55mg/L that medicament effectively adds concentration; 10.0, is 45 ℃ in temperature with salt of wormwood control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0187mm/a.
Embodiment 10
Silicate is (with SiO
2The meter) and the mass concentration ratio of gluconate be 1:1.5.
Take by weighing the 20.8g potassium silicate and (contain SiO
210.0g), the 15.0g Potassium Gluconate, it is even to join the 64.2g deionized water for stirring, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 25mg/L that medicament effectively adds concentration; 11.0, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0238mm/a.
Embodiment 11
Borate is (with B
4O
7 2-The meter) and silicate (with SiO
2Meter) mass concentration ratio is 1:1.
Take by weighing the 49.1g sodium borate decahydrate and (contain B
4O
7 2-20.0g), the 70.7g metasilicate pentahydrate sodium (contains SiO
220.0g), it is even to join the 80.2g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 40mg/L that medicament effectively adds concentration; 10.0, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0203mm/a.
Embodiment 12
Borate is (with B
4O
7 2-The meter) and silicate (with SiO
2Meter) mass concentration ratio is 1:2.
Take by weighing 15.6g five hydration sodium tetraborates and (contain B
4O
7 2-8.3g), the 79.1g non-hydrate sodium metasilicate (contains SiO
216.7g), it is even to join the 105.3g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 25mg/L that medicament effectively adds concentration; 10.5, is 45 ℃ in temperature with Pottasium Hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0214mm/a.
Embodiment 13
Borate is (with B
4O
7 2-The meter) and silicate (with SiO
2Meter) mass concentration ratio is 1:3.
Take by weighing 36.5g four water eight Sodium Tetraboratees and (contain B
4O
7 2-13.75g), the 83.8g anhydrous sodium metasilicate (contains SiO
241.25g), it is even to join the 79.7g deionized water for stirring, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 55mg/L that medicament effectively adds concentration; 10.5, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0165mm/a.
Embodiment 14
Borate is (with B
4O
7 2-The meter) and silicate (with SiO
2Meter) mass concentration ratio is 1:4.
Take by weighing 13.1g five hydration sodium tetraborates and (contain B
4O
7 2-7g), the 56.9g anhydrous sodium metasilicate (contains SiO
228g), it is even to join the 30.0g deionized water for stirring, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 35mg/L that medicament effectively adds concentration; 11.0, is 45 ℃ in temperature with Pottasium Hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0187mm/a.
Embodiment 15
Borate is (with B
4O
7 2-Meter) account for 42%, silicate is (with SiO
2Meter) account for 35%, gluconate accounts for 23%.
Take by weighing 19.7g five hydration sodium tetraborates and (contain B
4O
7 2-10.5g), the 30.9g metasilicate pentahydrate sodium (contains SiO
28.75g), that the 5.75g Sunmorl N 60S joins the 43.65g deionized water for stirring is even, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 25mg/L that medicament effectively adds concentration; 10.5, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0129mm/a.
Embodiment 16
Borate is (with B
4O
7 2-Meter) account for 40%, silicate is (with SiO
2Meter) account for 28%, gluconate accounts for 32%.
Take by weighing the 34.4g sodium borate decahydrate and (contain B
4O
7 2-14.0g), the 19.9g anhydrous sodium metasilicate (contains SiO
29.8g), that the 11.2g Zinc Gluconate joins the 34.5g deionized water for stirring is even, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 35mg/L that medicament effectively adds concentration; 10.0, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0137mm/a.
Embodiment 17
Borate is (with B
4O
7 2-Meter) account for 28%, silicate is (with SiO
2Meter) account for 42%, gluconate accounts for 30%.
Take by weighing 26.3g five hydration potassium tetraborates and (contain B
4O
7 2-12.6g), the 48.5g potassium metasilicate (contains SiO
218.9g), that the 13.5g Potassium Gluconate joins the 111.7g deionized water for stirring is even, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 45mg/L that medicament effectively adds concentration; 9.5, is 45 ℃ in temperature with salt of wormwood control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0116mm/a.
Embodiment 18
Borate is (with B
4O
7 2-Meter) account for 35%, silicate is (with SiO
2Meter) account for 35%, gluconate accounts for 30%.
Take by weighing 36.1g five hydration sodium tetraborates and (contain B
4O
7 2-19.25g), the 59.0g water glass (contains SiO
219.25g), that the 16.5g Zinc Gluconate joins the 88.4g deionized water for stirring is even, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor and the deionized water of present embodiment are rotated the lacing film experiment; It is 55mg/L that medicament effectively adds concentration; 9.2, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0105mm/a.
Comparative Examples 1
Doing inhibiter with sodium borate decahydrate separately, join and be rotated the lacing film experiment in the deionized water, is 45 ℃ in temperature, and rotating speed is to record corrosion data such as table 2 behind the operation 72h under the 75r/min condition.
Table 2: sodium tetraborate concentration is to the influence of corrosion of carbon steel
Comparative Examples 2
Doing inhibiter with Sunmorl N 60S separately, join and be rotated the lacing film experiment in the deionized water, is 45 ℃ in temperature, and rotating speed is to record corrosion data such as table 3 behind the operation 72h under the 75r/min condition.
Table 3: the glucono-na concn is to the influence of carbon steel inhibition
Comparative Examples 3
Doing inhibiter with metasilicate pentahydrate sodium separately, join and be rotated the lacing film experiment in the deionized water, is 45 ℃ in temperature, and rotating speed is to record corrosion data such as table 4 behind the operation 72h under the 75r/min condition.
Table 4: sodium silicate silicate is to the influence of carbon steel inhibition
Comparative Examples 4
Through controlling corrosion with the sodium hydroxide adjust pH, be 45 ℃ in temperature separately, rotating speed is to record corrosion data such as table 5 behind the operation 72h under the 75r/min condition.
Table 5:pH value is to the influence of corrosion of carbon steel
Embodiment 20
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-2008 of the People's Republic of China, and controlled variable is following.
Test water quality: test water (deionized water)
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃; The temperature difference: 10 ℃
Days running: 30 days
The A tower: elder generation added the composite corrosion inhibitor among the embodiment 4 in the 1st day; Effectively adding concentration is 55mg/L; Add 2 then; It is 10mg/L that the amino propionic acid amide of 2-dibrominated-3-time (DBNPA) makes its effective concentration in water, and using yellow soda ash to regulate the pH value simultaneously is 10.5, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.The 8th day adds RH-893 concentration is 50mg/L, and the 16th day adds DBNPA concentration is 18mg/L, and the 24th day adds dodecyl benzyl dimethyl ammonium chloride concentration is 25mg/L.Analog result sees Table 6, table 7.
B tower: add 1-bromo-3-chloro-5 earlier; The 5-dimethyl-is for NSC 9226 (BCDMH); Making its effective concentration in water is 8mg/L, adds the composite corrosion inhibitor among the embodiment 16 then, and effectively adding concentration is 35mg/L; Using yellow soda ash to regulate the pH value then is 10.0, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 70mg/L on the 7th day, the 15th day adding BCDMH 15mg/L, the 23rd day adding tetradecyl dimethyl benzyl ammonium chloride 45mg/L.Analog result sees Table 6, table 7.
C tower: regulate pH value to 10.5 with Pottasium Hydroxide; Add the composite corrosion inhibitor among the embodiment 8 then, effectively adding concentration is 40mg/L, then adds DBNPA; Making its effective concentration in water is 10mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 40mg/L on the 8th day, the 16th day adding DBNPA15mg/L, the 23rd day adding dodecyl dimethyl benzyl ammonium bromide 40mg/L.Analog result sees Table 6, table 7.
D tower: add BCDMH earlier; Making its effective concentration in water is 12mg/L, and using yellow soda ash to regulate the pH value then is 11.0, then adds the composite corrosion inhibitor among the embodiment 1; Effectively adding concentration is 35mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 50mg/L on the 8th day, the 16th day adding BCDMH 15mg/L, the 23rd day adding cetalkonium chloride 30mg/L.Analog result sees Table 6, table 7.
The E tower: elder generation added the composite corrosion inhibitor among the embodiment 13 in the 1st day; Effectively adding concentration is 45mg/L; Adding BCDMH then, to make its effective concentration in water be 8mg/L, and using yellow soda ash to regulate the pH value simultaneously is 10.5, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.The 8th day adds RH-893 concentration is 60mg/L, and the 16th day adds BCDMH concentration is 18mg/L, and the 24th day adds octadecyl dimethyl benzyl brometo de amonio concentration is 30mg/L.Analog result sees Table 6, table 7.
F tower: regulate pH value to 9.5 with salt of wormwood; Add the composite corrosion inhibitor among the embodiment 17 then, effectively adding concentration is 45mg/L, then adds DBNPA; Making its effective concentration in water is 10mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 45mg/L on the 8th day, the 16th day adding DBNPA15mg/L, the 23rd day adding dodecyl dimethyl decyl brometo de amonio 40mg/L.Analog result sees Table 6, table 7.
G tower: add BCDMH earlier; Making its effective concentration in water is 10mg/L, adds the composite corrosion inhibitor among the embodiment 5 then, and effectively adding concentration is 40mg/L; Using yellow soda ash to regulate the pH value then is 10.5, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 50mg/L on the 7th day, the 15th day adding BCDMH 15mg/L, the 23rd day adding tetradecyl dimethyl-octyl group brometo de amonio 40mg/L.Analog result sees Table 6, table 7.
H tower: add BCDMH earlier; Making its effective concentration in water is 12mg/L, and using Pottasium Hydroxide to regulate the pH value then is 11.2, then adds the composite corrosion inhibitor among the embodiment 7; Effectively adding concentration is 25mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 50mg/L on the 8th day, the 16th day adding BCDMH 18mg/L, the 23rd day adding tetradecyl dimethyl decyl brometo de amonio 30mg/L.Analog result sees Table 6, table 7.
I tower: regulate pH value to 10.0 with salt of wormwood; Add the composite corrosion inhibitor among the embodiment 9 then, effectively adding concentration is 55mg/L, then adds DBNPA; Making its effective concentration in water is 10mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 55mg/L on the 8th day, the 16th day adding DBNPA15mg/L, the 23rd day adding hexadecyldimethyl benzyl ammonium octyl group brometo de amonio 40mg/L.Analog result sees Table 6, table 7.
J tower: regulate pH value to 10.0 with yellow soda ash; Add DBNPA then, making its effective concentration in water is 10mg/L, then adds the composite corrosion inhibitor among the embodiment 16; Effectively adding concentration is 35mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 40mg/L on the 8th day, the 16th day adding DBNPA15mg/L, the 23rd day adding polychlorostyreneization-2-hydroxypropyl-1,1-N-dimethylammonium 40mg/L.Analog result sees Table 6, table 7.
K tower: add BCDMH earlier; Making its effective concentration in water is 12mg/L, and using yellow soda ash to regulate the pH value then is 10.5, then adds the composite corrosion inhibitor among the embodiment 2; Effectively adding concentration is 55mg/L, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.Added RH-893 60mg/L on the 8th day, the 16th day adding BCDMH 15mg/L, the 23rd day adding Poly Dimethyl Diallyl Ammonium Chloride 30mg/L.Analog result sees Table 6, table 7.
The L tower: elder generation added the composite corrosion inhibitor among the embodiment 3 in the 1st day; Effectively adding concentration is 75mg/L; Adding DBNPA then, to make its effective concentration in water be 10mg/L, and using Pottasium Hydroxide to regulate the pH value simultaneously is 10.5, will control density of corrosion inhibitor in real time afterwards and the pH value remains unchanged.The 8th day adds RH-893 concentration is 50mg/L, and the 16th day adds DBNPA concentration is 18mg/L, and the 24th day adds dimethyl diallyl ammonium chloride/acrylamide copolymer concentration is 30mg/L.Analog result sees Table 6, table 7.
Table 6: dynamic analog test test tube result
Table 7 heterotrophic bacterium monitoring result
The heterotrophic bacterium unit of number: individual/mL
Regulation among the standard GB 50050-2007 " Code for design of industrial recirculating cooling water treatment ", the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a; " the small-sized experimental analogic method of testing laboratory " regulation corrosion of Carbon Steel speed is " fine " level at 0-0.028mm/a in " the water coolant analysis and the TP " of production department of China PetroChemical Corporation and development division establishment; 0.028-0.056mm/a between be " good " level, 0.056-0.070mm/a for " can allow " level; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.Heterotrophic bacterium is controlled at 10
5Below be qualified.
This shows; Using circulating water treatment prescription of the present invention is applied to deionized water and does in the circulating cooling make-up water; The erosion rate of A, B, C, each tower test tube of D all is lower than 0.05mm/a, reaches China Petrochemical Industry's " good level " standard, adheres to speed and all is lower than 7mcm; Reach " good level " standard, heterotrophic bacterium is all less than 1.0 * 10
5In the span of control.
Claims (10)
1. one kind with the circulating water treatment method of deionized water as moisturizing, and it may further comprise the steps: a) the pH value of Control Circulation water is at 9-11.5; B) add inhibiter, said inhibiter is a kind of or its mixture in borate, gluconate and the silicate; C) add non-chlorbenside microbial inoculum, said non-chlorbenside microbial inoculum is brominated sterilant and in water, does not produce hypochlorous chloride sterilant.
2. circulating water treatment method according to claim 1 is characterized in that the pH value with alkaline matter Control Circulation water, and said alkaline matter is a kind of in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood preferably.
3. circulating water treatment method according to claim 1 and 2 is characterized in that borate is selected from Sodium Tetraborate and potassium borate, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees; Gluconate is selected from Sunmorl N 60S, Potassium Gluconate and Zinc Gluconate; Silicate is selected from sodium metasilicate, Starso, positive potassium silicate and potassium metasilicate, preferably from Starso, more preferably from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate, anhydrous sodium metasilicate.
4. according to each described circulating water treatment method of claim 1-3, it is characterized in that non-chlorbenside microbial inoculum is selected from organic bromine series bactericidal agent, RH-893 and quaternary ammonium salt.
5. circulating water treatment method according to claim 4 is characterized in that said organic bromine series bactericidal agent preferably from 2, amino propionic acid amide of 2-dibrominated-3-time and 1-bromo-3-chloro-5, and the 5-dimethyl-is for NSC 9226; Quaternary ammonium salt is selected from single long chain quaternary, dialkyl quaternary ammonium salt and polyquaternium; The preferred self-drifting of said single long chain quaternary is R
1(R
3)
2NR
2The quaternary ammonium salt of X, wherein R
1For carbonatoms be 8-20 chain alkyl, be preferably dodecyl, tetradecyl, hexadecyl or octadecyl, R
2For aryl or aralkyl, be preferably the aralkyl that carbonatoms is 7-11, R
3For carbonatoms be 1-4 alkyl, be preferably methyl; X is a chlorine or bromine, preferably from dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, cetalkonium chloride and octadecyl dimethyl benzyl brometo de amonio; It is R that dialkyl quaternary ammonium salt is preferably general formula
4(R
6)
2NR
5The quaternary ammonium salt of X, wherein R
4With R
5Difference, R
4For carbonatoms is the chain alkyl of 12-20, be preferably dodecyl, tetradecyl or hexadecyl, R
5For carbonatoms is the alkyl of 6-10, be preferably octyl or decyl, R
6For carbonatoms is the alkyl of 1-4, X is a chlorine or bromine, preferred dodecyl dimethyl decyl brometo de amonio, tetradecyl dimethyl-octyl group brometo de amonio, tetradecyl dimethyl decyl brometo de amonio and hexadecyldimethyl benzyl ammonium octyl group brometo de amonio; Polyquaternium is preferably polychlorostyreneization-2-hydroxypropyl-1,1-N-dimethylammonium, Poly Dimethyl Diallyl Ammonium Chloride and dimethyl diallyl ammonium chloride/acrylamide copolymer.
6. according to each described recirculated cooling water treatment process of right 1-5, it is characterized in that inhibiter is the mixture that is selected from two or three inhomogeneity salt of borate, gluconate and silicate.
7. recirculated cooling water treatment process according to claim 6, when it is characterized in that inhibiter is the mixture of borate and gluconate, the weight proportion of borate and gluconate is 1:3-3:1; When inhibiter was the mixture of silicate and gluconate, the weight proportion of silicate and gluconate was 2:1-1:2; When inhibiter was the mixture of borate and silicate, borate and silicate weight proportion were 1.5:1-1:5; When inhibiter was the mixture of borate, gluconate and silicate, borate accounted for 25-45 weight %, gluconate 20-35 weight %, silicate and accounts for 25-45 weight %.
8. recirculated cooling water treatment process according to claim 7 is characterized in that inhibiter is the mixture of borate, gluconate and silicate.
9. according to each described circulating water treatment method of claim 1-8; Its effective working concentration is 30-80mg/L when it is characterized in that single medicament is done inhibiter; Total effectively working concentration of inhibiter was 20-60mg/L when various medicaments was composite, and wherein boratory concentration is with B
4O
7 2-The concentration of meter, gluconate in the concentration of gluconate, silicate with SiO
2Meter.
10. according to each described circulating water treatment method of claim 1-9, it is characterized in that sterilant was an one-period with 30 days when adding, divide in each cycle to add for four times, whenever added once at a distance from 6-8 days; Order of adding is: add organic bromine for the first time, for the third time, add for the second time RH-893, add quaternary ammonium salt or its mixture the 4th time; Adding concentration is preferably: organic bromine 5-20mg/L, RH-893 30-80mg/L, quaternary ammonium salt 20-50mg/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103752118A (en) * | 2014-01-23 | 2014-04-30 | 南通明诺机械有限公司 | Integrated wet dust removal device for sweeper and integrated wet dust removal method thereof |
| CN104386773A (en) * | 2014-10-22 | 2015-03-04 | 无锡日月合金材料有限公司 | Method for purifying circulating water in smelting furnace |
| CN109896641A (en) * | 2019-04-04 | 2019-06-18 | 甘肃陇工智能清洗科技有限公司 | A kind of gas hanging furnace heating circulatory system protective agent |
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| CN1458172A (en) * | 2003-04-20 | 2003-11-26 | 高同柱 | Polynary copolymer containing ether phosphonic acid and sulfon carboxylic acid and process for preparing multifunctional water treating agent |
| CN1636891A (en) * | 2004-10-26 | 2005-07-13 | 南京工业大学 | Treatment method using seawater as circulating cooling water |
| CN201334411Y (en) * | 2008-11-28 | 2009-10-28 | 申汇科技集团有限公司 | Circulating water treatment system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458172A (en) * | 2003-04-20 | 2003-11-26 | 高同柱 | Polynary copolymer containing ether phosphonic acid and sulfon carboxylic acid and process for preparing multifunctional water treating agent |
| CN1636891A (en) * | 2004-10-26 | 2005-07-13 | 南京工业大学 | Treatment method using seawater as circulating cooling water |
| CN201334411Y (en) * | 2008-11-28 | 2009-10-28 | 申汇科技集团有限公司 | Circulating water treatment system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103752118A (en) * | 2014-01-23 | 2014-04-30 | 南通明诺机械有限公司 | Integrated wet dust removal device for sweeper and integrated wet dust removal method thereof |
| CN104386773A (en) * | 2014-10-22 | 2015-03-04 | 无锡日月合金材料有限公司 | Method for purifying circulating water in smelting furnace |
| CN109896641A (en) * | 2019-04-04 | 2019-06-18 | 甘肃陇工智能清洗科技有限公司 | A kind of gas hanging furnace heating circulatory system protective agent |
| CN109896641B (en) * | 2019-04-04 | 2021-08-06 | 甘肃陇工智能清洗科技有限公司 | Protective agent for heating circulation system of gas wall-mounted boiler |
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