CN102476872B - 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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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 large water gaging, wherein water coolant accounts for significant proportion, as petroleum chemical enterprise's water coolant water accounts for the more than 80% of water of productive use.Nowadays water resources shortage, water saving has become world theme.Sewage and Zhong Shui are back to recirculated water by greatly reducing the consumption of fresh water, even realize spot patch fresh water.
The U.S. realized and can discharge urban sewage recycling in power generation cycle water system in the sixties in 20th century, and the nineties has realized qualified discharge Waste Water Reuse and petrochemical equipment circulating water system.The method of taking is that sewage is carried out to advanced treatment, reduces COD, suspended substance and microorganism concn in qualified discharge sewage, then uses corrosion and scaling and the microorganism of water conditioner operating device.
The method that sewage and Zhong Shui are back to recirculated water has two kinds.One is advanced treatment, by sewage reuse after coagulation, precipitation, filtration, sterilization again after second-stage treatment.Another kind is two embrane methods, passes into ultrafiltration reverse osmosis device by the water after second-stage treatment after coagulation, precipitation, filtration, and water outlet is deionized water.Two embrane method investment costs are large, still, because there is no the fouling factor in deionized water, be applied to circulating cooling make-up water, scale problems can be ignored, and therefore can greatly improve cycles of concentration, but also the expense of having saved Scale inhibitors, in addition can also extension device working life, save overhaul of the equipments expense.Visible employing deionized water can reduce later stage expense.It is corrosion and microbiological manipulation that deionized water does the problem that circulating cooling make-up water need to solve.
CN1338433A discloses in the sewage of qualified discharge and has added sterilant to carry out disinfection, and adds alkaline matter to make pH value be controlled at 9.5-14 and carries out inhibition.Its shortcoming is: because there is dissolved oxygen in water, depend merely on and regulate pH value can not effectively control corrosion.
CN1524806A discloses the water after oil removal, sedimentation by high oily(waste)water and has introduced circulating water system, meanwhile, adds inorganic base substance to make pH value reach 7-11, adds sterilant and corrosion inhibiting and descaling agent.Sterilant selects clorox, trichloroisocyanuric acid etc. can in water, produce hypochlorous chlorine series bactericidal agent, corrosion inhibiting and descaling agent is selected organophosphorus, Sodium hexametaphosphate 99, Sodium orthomolybdate etc.Its shortcoming is: under alkaline condition, chlorine series bactericidal agent can lose efficacy, if the phosphorus containg substances such as organophosphorus, Sodium hexametaphosphate 99 cause body eutrophication with sewage discharge meeting.
CN1393411A has studied a kind of composite corrosion inhibitor for deionized water, and composition is made up of deionized water, polyetheramides, silicate.Different from inhibiter composition of the present invention, and the present invention is 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 object, the invention provides a kind of circulating water treatment method using deionized water as moisturizing, comprise the following steps: a) the pH value of controlled circulation water is at 9-11.5; B) add inhibiter, described inhibiter is a kind of or its mixture in borate, gluconate and silicate; C) add non-chlorbenside microbial inoculum, described non-chlorbenside microbial inoculum is brominated sterilant and in water, does not produce hypochlorous chloride sterilant.
The present invention is preferably by the pH value of alkaline matter controlled circulation water, and described alkaline matter is the one in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood preferably.
Consider price factor, in the situation that effect is close, 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 hydration 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, is more preferably selected from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate and anhydrous sodium metasilicate.
Sterilant of the present invention is selected from organo bromine microbicide, isothiazolinone and quaternary ammonium salt.Described organic bromine is preferably chloro-5 from 2,2-, bis-bromo-3-time aminopropan acid amides and the bromo-3-of 1-, and 5-dimethyl is for glycolylurea; Quaternary ammonium salt is selected from single long chain quaternary, dialkyl quaternary ammonium salt and polyquaternium; The preferred self-drifting of described single long chain quaternary is R
1(R
3)
2nR
2the quaternary ammonium salt of X, wherein R
1for the carbonatoms chain alkyl that is 8-20, be preferably dodecyl, tetradecyl hexadecyl or octadecyl, R
2for aryl or aralkyl, be preferably the aralkyl that carbonatoms is 7-11, R
3for the carbonatoms alkyl that is 1-4, be preferably methyl, X is 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 the chain alkyl that carbonatoms is 12-20, be preferably dodecyl, tetradecyl or hexadecyl, R
5for the alkyl that carbonatoms is 6-10, be preferably octyl or decyl, R
4for the alkyl that carbonatoms is 1-4, X is 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-2-of polyquaternium hydroxypropyl-1,1-N-dimethylammonium, Poly Dimethyl Diallyl Ammonium Chloride and dimethyl diallyl ammonium chloride/acrylamide copolymer.
Inhibiter of the present invention is preferably the mixture of the two or three inhomogeneity salt that is selected from borate, gluconate and silicate.When inhibiter is the mixture of borate and gluconate, the weight proportion of borate and gluconate is 1:3-3:1; When inhibiter is the mixture of silicate and gluconate, the weight proportion of silicate and gluconate is 2:1-1:2; When inhibiter is the mixture of borate and silicate, borate and silicate weight proportion are 1.5:1-1:5; When inhibiter is the mixture of borate, gluconate and silicate, borate accounts for 25-45 % by weight, gluconate 20-35 % by weight, silicate and accounts for 25-45 % by weight.With inhomogeneous salt mixture, during as inhibiter, synergistic effect is obvious, can reduce total consumption of salt, and corrosion mitigating effect is good.Inhibiter of the present invention most preferably is the mixture of borate, gluconate and silicate.
When inhibiter of the present invention is single medicament, its effective working concentration is 30-80mg/L, 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 of the present invention preferably in the time adding take 30 days as one-period, point add for four times in each cycle, added once every 6-8 days.Order of adding is: add for the first time, for the third time organic bromine, add for the second time isothiazolinone, add the mixture of quaternary ammonium salt the 4th time.Adding concentration is preferably: organic bromine 5-20mg/L, isothiazolinone 30-80mg/L, quaternary ammonium salt 20-50mg/L.
Inhibiter described in b) step of the present invention can add in the mode of single dose, also can first be mixed with composite corrosion inhibitor, then composite scale-inhibiting corrosion inhibitor is once added in recirculated water, preferably carries out in the latter's mode.Available ordinary method is prepared composite corrosion inhibitor of the present invention, and the reinforced order of each component is unimportant, for example, borate, silicate, gluconate and water can be mixed in predetermined ratio, can make required composite corrosion inhibitor.
The addition step of circulating water treatment method of the present invention can be successively undertaken by a), b) and c) step, also can be undertaken a) by other arbitrary orders-c) step, can also carry out these three steps simultaneously.
Method of the present invention is applicable to the recirculating cooling water system processing as moisturizing after two embrane methods are processed of sewage after second-stage treatment, can effectively control corrosion and microorganism growth.
Embodiment
Corrosion inhibitor formula embodiment below will contribute to illustrate the present invention, but not limit to its scope.Test water is deionized water, and carbon steel test piece is 20# steel.Test water water quality is in 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 boiler feed water river water coolant analytical procedure specific conductivity "
Total molten solid: GB/T 14415-2007 " mensuration of solid matter in industrial circulating cooling water and boiler feed water "
The corrosion inhibition of following embodiment gained and bactericidal property assessment method are as follows:
corrosion inhibition: the test piece of 20# qualitative carbon steel is fixed on lacing film instrument, puts into the test water that is added with the drug concentration adding by embodiment, 45 ± 1 ℃ of steady temperatures, keep rotating speed 75rpm rotation 72h, and before and after record test, the weight of test piece, calculates average corrosion rate.
Average corrosion rate calculation formula is: F=(C × △ W)/(A × T × ρ)
C: computational constant, take mm/a (millimeter/year) during as unit, C=8.76 × 10
7
△ W: the corrosion weight loss (g) of test specimen
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 culture dish.Then aseptic culture medium is poured in culture dish, mix with water sample, cultivate 72 ± 4h etc. being inverted after culture medium solidifying to be placed in the incubator of 29 ± 1 ℃.After cultivation, take out culture dish, select those culture dish with 30-300 bacterium colony to count, colony number is multiplied by corresponding dilution and trains number and be the heterotrophic bacterium number of this water sample.
adhere to the mensuration of speed:test tube is positioned in the bypass of interchanger, takes out test tube after off-test, clean after test tube outer wall, constant temperature drying, takes the heavy (W of band bur test tube
1).Then clean inboard wall of test tube bur, be dried, take 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 86.0g sodium borate decahydrate (containing B
4o
7 2-35.0g) join 114.0g deionized water for stirring even, be made into inhibiter 200.0g of the present invention.
The inhibiter of the present embodiment and deionized water are rotated to coupon test, it is 35mg/L that medicament effectively adds concentration, 11.0, be 45 ℃ in temperature by sodium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0531mm/a.
Embodiment 2
Take 111.8g anhydrous sodium metasilicate (containing SiO
255.0g) join 88.2g deionized water for stirring even, be made into inhibiter 200.0g of the present invention.
The inhibiter of the present embodiment and deionized water are rotated to coupon test, it is 55mg/L that medicament effectively adds concentration, 10.5, be 45 ℃ in temperature by sodium carbonate control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0437mm/a.
Embodiment 3
Taking 75.0g Sunmorl N 60S, to join 25.0g deionized water for stirring even, is made into inhibiter 100.0g of the present invention.
The inhibiter of the present embodiment and deionized water are rotated to coupon test, it is 75mg/L that medicament effectively adds concentration, 10.0, be 45 ℃ in temperature by potassium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0535mm/a.
Embodiment 4
Borate is (with B
4o
7 2-meter) and the mass concentration ratio of gluconate be 1:2.5.
Take 29.5g five hydration sodium tetraborates (containing B
4o
7 2-15.7g), 39.3g Zinc Gluconate, join 131.2g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 55mg/L that medicament effectively adds concentration, 9.2, be 45 ℃ in temperature by salt of wormwood control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0134mm/a
Embodiment 5
Borate is (with B
4o
7 2-meter) and the mass concentration ratio of gluconate be 1:1.
Take 41.7g five hydration potassium tetraborates (containing B
4o
7 2-20.0g), 20.0g Potassium Gluconate, join 138.3g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 40mg/L that medicament effectively adds concentration, 10.5, be 45 ℃ in temperature by sodium carbonate control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0158mm/a.
Embodiment 6
Borate is (with B
4o
7 2-meter) and the mass concentration ratio of gluconate be 2:1.
Take 49.1g sodium borate decahydrate (containing B
4o
7 2-20.0g), 10.0g Sunmorl N 60S, join 40.9g deionized water for stirring even, be made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 30mg/L that medicament effectively adds concentration, 11.0, be 45 ℃ in temperature by sodium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0155mm/a
Embodiment 7
Borate is (with B
4o
7 2-meter) and the mass concentration ratio of gluconate be 2.5:1.
Take 47.2g tetra-hydration eight Sodium Tetraboratees (containing B
4o
7 2-17.8g), 7.2g Sunmorl N 60S, join 35.0g deionized water for stirring even, be made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 25mg/L that medicament effectively adds concentration, 11.2, be 45 ℃ in temperature by sodium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0159mm/a
Embodiment 8
Silicate is (with SiO
2meter) and the mass concentration ratio of gluconate be 1.5:1.
Take 73.6g water glass (containing SiO
224.0g), 16.0g Sunmorl N 60S, join 110.4g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 40mg/L that medicament effectively adds concentration, 10.5, be 45 ℃ in temperature by potassium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0175mm/a.
Embodiment 9
Silicate is (with SiO
2meter) and the mass concentration ratio of gluconate be 1:1.
Take 97.2g metasilicate pentahydrate sodium (containing SiO
227.5g), 27.5g Zinc Gluconate, join 75.3g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 55mg/L that medicament effectively adds concentration, 10.0, be 45 ℃ in temperature by salt of wormwood control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0187mm/a.
Embodiment 10
Silicate is (with SiO
2meter) and the mass concentration ratio of gluconate be 1:1.5.
Take 20.8g potassium silicate (containing SiO
210.0g), 15.0g Potassium Gluconate, join 64.2g deionized water for stirring even, be made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 25mg/L that medicament effectively adds concentration, 11.0, be 45 ℃ in temperature by sodium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0238mm/a.
Embodiment 11
Borate is (with B
4o
7 2-meter) and silicate (with SiO
2meter) mass concentration ratio be 1:1.
Take 49.1g sodium borate decahydrate (containing B
4o
7 2-20.0g), 70.7g metasilicate pentahydrate sodium is (containing SiO
220.0g), join 80.2g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 40mg/L that medicament effectively adds concentration, 10.0, be 45 ℃ in temperature by sodium carbonate control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0203mm/a.
Embodiment 12
Borate is (with B
4o
7 2-meter) and silicate (with SiO
2meter) mass concentration ratio be 1:2.
Take 15.6g five hydration sodium tetraborates (containing B
4o
7 2-8.3g), 79.1g non-hydrate sodium metasilicate is (containing SiO
216.7g), join 105.3g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 25mg/L that medicament effectively adds concentration, 10.5, be 45 ℃ in temperature by potassium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0214mm/a.
Embodiment 13
Borate is (with B
4o
7 2-meter) and silicate (with SiO
2meter) mass concentration ratio be 1:3.
Take 36.5g tetra-water eight Sodium Tetraboratees (containing B
4o
7 2-13.75g), 83.8g anhydrous sodium metasilicate is (containing SiO
241.25g), join 79.7g deionized water for stirring even, be made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 55mg/L that medicament effectively adds concentration, 10.5, be 45 ℃ in temperature by sodium carbonate control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0165mm/a.
Embodiment 14
Borate is (with B
4o
7 2-meter) and silicate (with SiO
2meter) mass concentration ratio be 1:4.
Take 13.1g five hydration sodium tetraborates (containing B
4o
7 2-7g), 56.9g anhydrous sodium metasilicate is (containing SiO
228g), join 30.0g deionized water for stirring even, be made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 35mg/L that medicament effectively adds concentration, 11.0, be 45 ℃ in temperature by potassium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 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 19.7g five hydration sodium tetraborates (containing B
4o
7 2-10.5g), 30.9g metasilicate pentahydrate sodium is (containing SiO
28.75g), that 5.75g Sunmorl N 60S joins 43.65g deionized water for stirring is even, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 25mg/L that medicament effectively adds concentration, 10.5, be 45 ℃ in temperature by sodium hydroxide control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 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 34.4g sodium borate decahydrate (containing B
4o
7 2-14.0g), 19.9g anhydrous sodium metasilicate is (containing SiO
29.8g), that 11.2g Zinc Gluconate joins 34.5g deionized water for stirring is even, is made into composite corrosion inhibitor 100.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 35mg/L that medicament effectively adds concentration, 10.0, be 45 ℃ in temperature by sodium carbonate control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 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 26.3g five hydration potassium tetraborates (containing B
4o
7 2-12.6g), 48.5g potassium metasilicate is (containing SiO
218.9g), that 13.5g Potassium Gluconate joins 111.7g deionized water for stirring is even, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 45mg/L that medicament effectively adds concentration, 9.5, be 45 ℃ in temperature by salt of wormwood control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 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 36.1g five hydration sodium tetraborates (containing B
4o
7 2-19.25g), 59.0g water glass is (containing SiO
219.25g), that 16.5g Zinc Gluconate joins 88.4g deionized water for stirring is even, is made into composite corrosion inhibitor 200.0g of the present invention.
The composite corrosion inhibitor of the present embodiment and deionized water are rotated to coupon test, it is 55mg/L that medicament effectively adds concentration, 9.2, be 45 ℃ in temperature by sodium carbonate control pH value, rotating speed is under 75r/min condition, to move that to record erosion rate after 72h be 0.0105mm/a.
Comparative example 1
Doing inhibiter with sodium borate decahydrate separately, join in deionized water and be rotated coupon test, is 45 ℃ in temperature, and rotating speed is to record corrosion data as table 2 after moving 72h under 75r/min condition.
Table 2: the impact of sodium tetraborate concentration on corrosion of carbon steel
Comparative example 2
Doing inhibiter with Sunmorl N 60S separately, join in deionized water and be rotated coupon test, is 45 ℃ in temperature, and rotating speed is to record corrosion data as table 3 after moving 72h under 75r/min condition.
Table 3: the impact of gluconic acid na concn on carbon steel inhibition
Comparative example 3
Doing inhibiter with metasilicate pentahydrate sodium separately, join in deionized water and be rotated coupon test, is 45 ℃ in temperature, and rotating speed is to record corrosion data as table 4 after moving 72h under 75r/min condition.
Table 4: the impact of sodium silicate silicate on carbon steel inhibition
Comparative example 4
By controlling corrosion with sodium hydroxide adjust pH, be 45 ℃ in temperature separately, rotating speed is to record corrosion data as table 5 after moving 72h under 75r/min condition.
The impact of table 5:pH value on corrosion of carbon steel
Embodiment 20
For simulated field, carry out dynamic analog test.Dynamic analog test method is undertaken by the chemical industry standard HG/T2160-2008 of the People's Republic of China (PRC), controls parameter as follows.
Test water quality: test water (deionized water)
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃; The temperature difference: 10 ℃
Days running: 30 days
A tower: first add the composite corrosion inhibitor in embodiment 4 on the 1st day, effectively adding concentration is 55mg/L, then add 2, it is 10mg/L that 2-bis-bromo-3-time aminopropan acid amides (DBNPA) make its effective concentration in water, regulate pH value with sodium carbonate is 10.5 simultaneously, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.The 8th day adds isothiazolinone 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 is in table 6, table 7.
B tower: first add the bromo-3-of 1-chloro-5,5-dimethyl is for glycolylurea (BCDMH), making its effective concentration in water is 8mg/L, then add the composite corrosion inhibitor in embodiment 16, effectively adding concentration is 35mg/L, then regulating pH value with sodium carbonate is 10.0, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 7th day, add isothiazolinone 70mg/L, within the 15th day, add BCDMH 15mg/L, within the 23rd day, add tetradecyl dimethyl benzyl ammonium chloride 45mg/L.Analog result is in table 6, table 7.
C tower: by potassium hydroxide adjusting pH value to 10.5, then add the composite corrosion inhibitor in embodiment 8, effectively adding concentration is 40mg/L, then adds DBNPA, making its effective concentration in water is 10mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 40mg/L, within the 16th day, add DBNPA15mg/L, within the 23rd day, add dodecyl dimethyl benzyl ammonium bromide 40mg/L.Analog result is in table 6, table 7.
D tower: first add BCDMH, making its effective concentration in water is 12mg/L, and then regulating pH value with sodium carbonate is 11.0, then adds the composite corrosion inhibitor in embodiment 1, effectively adding concentration is 35mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 50mg/L, within the 16th day, add BCDMH 15mg/L, within the 23rd day, add cetalkonium chloride 30mg/L.Analog result is in table 6, table 7.
E tower: first add the composite corrosion inhibitor in embodiment 13 on the 1st day, effectively adding concentration is 45mg/L, then adding BCDMH, to make its effective concentration in water be 8mg/L, and regulate pH value with sodium carbonate is 10.5 simultaneously, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.The 8th day adds isothiazolinone concentration is 60mg/L, and the 16th day adds BCDMH concentration is 18mg/L, and within the 24th day, adding octadecyl dimethyl benzyl brometo de amonio concentration is 30mg/L.Analog result is in table 6, table 7.
F tower: by salt of wormwood adjusting pH value to 9.5, then add the composite corrosion inhibitor in embodiment 17, effectively adding concentration is 45mg/L, then adds DBNPA, making its effective concentration in water is 10mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 45mg/L, within the 16th day, add DBNPA15mg/L, within the 23rd day, add dodecyl dimethyl decyl brometo de amonio 40mg/L.Analog result is in table 6, table 7.
G tower: first add BCDMH, making its effective concentration in water is 10mg/L, then adds the composite corrosion inhibitor in embodiment 5, and effectively adding concentration is 40mg/L, then regulating pH value with sodium carbonate is 10.5, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 7th day, add isothiazolinone 50mg/L, within the 15th day, add BCDMH 15mg/L, within the 23rd day, add tetradecyl dimethyl octyl group brometo de amonio 40mg/L.Analog result is in table 6, table 7.
H tower: first add BCDMH, making its effective concentration in water is 12mg/L, and then regulating pH value with potassium hydroxide is 11.2, then adds the composite corrosion inhibitor in embodiment 7, effectively adding concentration is 25mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 50mg/L, within the 16th day, add BCDMH 18mg/L, within the 23rd day, add tetradecyl dimethyl decyl brometo de amonio 30mg/L.Analog result is in table 6, table 7.
I tower: by salt of wormwood adjusting pH value to 10.0, then add the composite corrosion inhibitor in embodiment 9, effectively adding concentration is 55mg/L, then adds DBNPA, making its effective concentration in water is 10mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 55mg/L, within the 16th day, add DBNPA15mg/L, within the 23rd day, add hexadecyldimethyl benzyl ammonium octyl group brometo de amonio 40mg/L.Analog result is in table 6, table 7.
J tower: by sodium carbonate adjusting pH value to 10.0, then add DBNPA, making its effective concentration in water is 10mg/L, then adds the composite corrosion inhibitor in embodiment 16, effectively adding concentration is 35mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 40mg/L, within the 16th day, add DBNPA15mg/L, within the 23rd day, add polychlorostyrene-2-hydroxypropyl-1,1-N-dimethylammonium 40mg/L.Analog result is in table 6, table 7.
K tower: first add BCDMH, making its effective concentration in water is 12mg/L, and then regulating pH value with sodium carbonate is 10.5, then adds the composite corrosion inhibitor in embodiment 2, effectively adding concentration is 55mg/L, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.Within the 8th day, add isothiazolinone 60mg/L, within the 16th day, add BCDMH 15mg/L, within the 23rd day, add Poly Dimethyl Diallyl Ammonium Chloride 30mg/L.Analog result is in table 6, table 7.
L tower: first add the composite corrosion inhibitor in embodiment 3 on the 1st day, effectively adding concentration is 75mg/L, then adding DBNPA, to make its effective concentration in water be 10mg/L, and regulate pH value with potassium hydroxide is 10.5 simultaneously, will control in real time density of corrosion inhibitor afterwards and pH value remains unchanged.The 8th day adds isothiazolinone 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 is in 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 in standard GB/T 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; In " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, the corrosion speed of " the small-sized experimental analogic method of testing laboratory " regulation carbon steel is " fine " level at 0-0.028mm/a, between 0.028-0.056mm/a, being " good " level, is " can allow " level at 0.056-0.070mm/a; 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
5be below qualified.
As can be seen here, applying circulating water treatment prescription of the present invention is applied to deionized water and does in circulating cooling make-up water, the erosion rate of A, B, the each tower test tube of C, D is all lower than 0.05mm/a, reach China Petrochemical Industry's " good level " standard, adhere to speed all lower than 7mcm, reach " good level " standard, heterotrophic bacterium is all being less than 1.0 × 10
5in span of control.
Claims (15)
1. the circulating water treatment method using deionized water as moisturizing, it comprises the following steps: a) the pH value of controlled circulation water is at 9-11.5; B) add inhibiter, described inhibiter is a kind of or its mixture in borate, gluconate and silicate; C) add non-chlorbenside microbial inoculum, described non-chlorbenside microbial inoculum is brominated sterilant and in water, does not produce hypochlorous chloride sterilant, described non-chlorbenside microbial inoculum is selected from organo bromine microbicide, isothiazolinone and quaternary ammonium salt, sterilant in the time adding take 30 days as one-period, in each cycle, divide and add for four times, added once every 6-8 days, order of adding is: add for the first time, for the third time organic bromine, add for the second time isothiazolinone, add quaternary ammonium salt or its mixture the 4th time.
2. circulating water treatment method according to claim 1, is characterized in that the pH value with alkaline matter controlled circulation water.
3. circulating water treatment method according to claim 2, is characterized in that described alkaline matter is selected from the one in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood.
4. circulating water treatment method according to claim 1, is characterized in that borate is selected from Sodium Tetraborate and potassium borate; 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.
5. circulating water treatment method according to claim 4, is characterized in that borate is selected from Sodium Tetraborate; Silicate is selected from Starso.
6. circulating water treatment method according to claim 5, is characterized in that borate is selected from sodium borate decahydrate, five hydration sodium tetraborates and four hydration eight Sodium Tetraboratees; Silicate is selected from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate, anhydrous sodium metasilicate.
7. according to the circulating water treatment method described in claim 1-6 any one, it is characterized in that described organo bromine microbicide is selected from 2,2-, bis-bromo-3-time aminopropan acid amides and the bromo-3-of 1-is chloro-5,5-dimethyl is for glycolylurea; Quaternary ammonium salt is selected from single long chain quaternary, dialkyl quaternary ammonium salt and polyquaternium.
8. circulating water treatment method according to claim 7, is characterized in that it is R that described single long chain quaternary is selected from general formula
1(R
3)
2nR
2the quaternary ammonium salt of X, wherein R
1for carbonatoms be 8-20 chain alkyl, R
2for aryl or aralkyl, R
3for the alkyl that carbonatoms is 1-4, X is chlorine or bromine; It is R that dialkyl quaternary ammonium salt is selected from general formula
4(R
6)
2nR
5the quaternary ammonium salt of X, wherein R
4with R
5difference, R
4for carbonatoms be 12-20 chain alkyl, R
5for carbonatoms be 6-10 alkyl, R
6for the alkyl that carbonatoms is 1-4, X is chlorine or bromine; Polyquaternium is selected from polychlorostyrene-2-hydroxypropyl-1,1-N-dimethylammonium, Poly Dimethyl Diallyl Ammonium Chloride and dimethyl diallyl ammonium chloride/acrylamide copolymer.
9. circulating water treatment method according to claim 8, is characterized in that R in described single long chain quaternary general formula
1for dodecyl, tetradecyl, hexadecyl or octadecyl, R
2for carbonatoms be 7-11 aralkyl, R
3for methyl; R in dialkyl quaternary ammonium salt general formula
4for dodecyl, tetradecyl or hexadecyl, R
5for octyl or decyl.
10. circulating water treatment method according to claim 7, is characterized in that described single long chain quaternary is selected 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; Dialkyl quaternary ammonium salt is selected from 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.
11. according to the circulating water treatment method described in right 1-6 any one, it is characterized in that inhibiter is the mixture that is selected from two or three inhomogeneity salt of borate, gluconate and silicate.
12. circulating water treatment methods according to claim 11, while 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 is the mixture of silicate and gluconate, the weight proportion of silicate and gluconate is 2:1-1:2; When inhibiter is the mixture of borate and silicate, borate and silicate weight proportion are 1.5:1-1:5; When inhibiter is the mixture of borate, gluconate and silicate, borate accounts for 25-45 % by weight, gluconate 20-35 % by weight, silicate and accounts for 25-45 % by weight.
13. circulating water treatment methods according to claim 12, is characterized in that inhibiter is the mixture of borate, gluconate and silicate.
14. according to the circulating water treatment method described in claim 1-6 any one, while it is characterized in that single medicament does inhibiter, its effective working concentration is 30-80mg/L, when various medicaments is composite, total effectively working concentration of inhibiter is 20-60mg/L, and wherein boratory concentration is with B
4o
7 2-the concentration of meter, gluconate in the concentration of gluconate, silicate with SiO
2meter.
15. according to the circulating water treatment method described in claim 1-6 any one, it is characterized in that sterilant adds concentration and is: organic bromine 5-20 mg/L, isothiazolinone 30-80 mg/L, quaternary ammonium salt 20-50 mg/L.
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