CN103319009A - Method for applying desalinated seawater to circulating cooling water system - Google Patents
Method for applying desalinated seawater to circulating cooling water system Download PDFInfo
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Abstract
The invention relates a method for applying desalinated seawater to a circulating cooling water system. The method includes: taking the desalinated seawater as circulating cooling water and applying it in the circulating cooling water system, and adding a pH regulator and a corrosion inhibitor to keep the pH value of the circulating cooling water at 9-12. Specifically, the corrosion inhibitor contains a first inhibitor and a second inhibitor. The first inhibitor is one or more of gluconate, borate, silicate, lignosulfonate and tannin, and the second inhibitor can be urotropin and/or thiourea. The invention also relates to another method for applying the desalinated seawater to the circulating cooling water system. The method includes: applying the desalinated seawater as circulating cooling water into the circulating cooling water system, and adding a corrosion inhibitor and a pH regulator to keep the pH value of the circulating cooling water at 9-12. The corrosion inhibitor contains a first inhibitor, a second inhibitor and a third inhibitor, with the third inhibitor selected from urotropin and/or thiourea. The methods have the characteristics of small corrosion on circulating cooling water equipment and environmental-friendliness.
Description
Technical field
The present invention relates to a kind of sea water desaltination water is applied to method in the recirculating cooling water system.
Background technology
Along with the development of world economy, Freshwater resources day is aobvious deficient, and the utilization of sea water desaltination water more and more is subject to maritime nation's generally attention.According to international desalination association statistics, sea water desaltination contract capacity surpassed 2 * 10 in nearly 5 years
7m
3/ d, near the summation of Past 30 Years, future also will double in 10 years on this basis.Need at present a large amount of waters in industrial production, wherein recirculated cooling water accounts for significant proportion, accounts for more than 80% of water of productive use such as petroleum chemical enterprise's recirculated cooling water water.Sea water desaltination water is back to industrial circulating cooling water will greatly reduces fresh water as the consumption of recirculated cooling water, thus the problem of solution fresh water undersupply.
At present, sea water desaltination mainly takes the method for reverse osmosis method to obtain.Seawater is after reverse-osmosis treated, and its desalination water has that content of mineral substances is few, the characteristics of slant acidity (the pH value is 6.5～7.5).In addition, contain more chlorion in the sea water desaltination water, have slight corrodibility, sea water desaltination water easily causes pipeline and equipment corrosion as in the process of industrial circulating cooling water, therefore, need to process accordingly sea water desaltination water.The method of the processing sea water desaltination water of present stage mainly is to add to contain the mineral materials such as calcium, magnesium in sea water desaltination water, with stabilizing water quality and protect water system to avoid being corroded.But can cause again the fouling of equipment after adding calcium, magnesium material, so need in sea water desaltination water, add Scale inhibitors.The adding of Scale inhibitors causes unnecessary material and the consumption of the energy.Directly utilize water treatment agent to come the corrosion of operating device and the breeding of microorganism can reduce sea water desaltination water as the cost of recirculated water, simplification of flowsheet is so that sea water desaltination water has better development prospect in application facet.
At present, the domestic prescription that is used as the sea water desaltination water treatment of industrial circulating cooling water mostly is the organic phospho acid prescription, and sterilant adopts Babysafe, strong chlorine oil, quaternary ammonium salt etc. more.Organic phospho acid have good chemical stability, not facile hydrolysis, can anti-comparatively high temps, in the treating processes of recirculated cooling water, can have inhibition and scale inhibition function concurrently, although the working concentration of organic phospho acid in recirculated cooling water only is 4-10mg/L, the phosphorus content in the organic phospho acid still can pollute environment at this moment.After the sterilant such as strong chlorine oil, Babysafe used, residual tricarbimide can cause organism increase in the water in water, and this type organic than hard degradation, also can cause environmental issue at occurring in nature then.
CN1636891A discloses with the treatment process of a kind of seawater as recirculated cooling water, and the method is processed and desalinized seawater by add inhibiter, Scale inhibitors, oxidisability biocide, non-oxidative bactericide in seawater.Contain the organophosphorus medicament in the Scale inhibitors in the method, unfavorable to environmental protection.
CN1231347A discloses a kind of novel corrosion inhibitor that iron and steel corrodes that suppresses in the 10%-25% salt solution, be by thiocarbamide, nitranol, and primary zinc phosphate and urotropine form.This invention is in higher salt solution, and up to 98%, but sustained release dosage consumption that should invention is high to the corrosion inhibition rate of A3 steel.
CN1281824A discloses a kind of method for disinfection for circulating water system, in containing the recirculated water of sterilant, add inorganic alkaline compound and make the pH value reach 9-12, described sterilant is selected from quaternary ammonium salt, quaternary phosphonium salt, isothiazolinone, DICHLOROISOCYANURIC ACID or trichloroisocyanuric acid.Although this patent has been controlled the growth of bacterium to a certain extent, aspect the corrosion of equipment, do not provide what method at the controlled circulation water coolant, and the inhibiter that this invention is used is unfavorable to environmental protection as the organic phosphates inhibiter in recirculated water.
CN1338435A discloses in recirculated cooling water and to have added alkaline matter and make the pH value be controlled at 9.5-14 to carry out inhibition.Yet owing to having dissolved oxygen in the water, depend merely on adjusting pH value and can not effectively control corrosion, and contain a certain amount of chlorion in the sea water desaltination water, can further add the impact of heavy corrosion.
CN1919752A discloses a kind of environment-friendly composite corrosion and scale inhibitor, it is characterized in that the inhibition component in this environment-friendly composite corrosion and scale inhibitor is comprised of one or more materials in molybdate, tungstate, borate, organic substituted carboxylic acid or the organic heterocyclic compounds, the scale inhibition component is comprised of one or more materials in natural high moleculer eompound, epoxy succinic acids material or the acrylic terpolymer.Although the method can have effectively recirculated cooling water is carried out slowly-releasing, the concentration that adds of the corrosion inhibiting and descaling agent of this invention is 300-500mg/L, adds the concentration height uneconomical.
CN101283686A provides a kind of sterilant for industrial circulating cooling water system, it is characterized in that being formed by following material: be by weight percentage 5-chloro-2-isobutyl--4-isothiazoline-3-ketone and the mixture of 2-isobutyl--4-isothiazoline-3-ketone or the mixture 1%～3% of 5-chloro-2-butyl-4-isothiazoline-3-ketone and 2-butyl-4-isothiazoline-3-ketone, solubility promoter 3%～10%, stablizer 0.1%～1.0%, all the other are water.Wherein the composition of sterilant is complicated, and should invention only for the sterilization of industrial circulating cooling water.
Summary of the invention
Easily circulating water equipment is caused the shortcoming of corrosion when the object of the invention is to overcome present sea water desaltination water as recirculated cooling water, a kind of sea water desaltination water be applied to method in recirculating cooling water system little to the corrosion of circulating water equipment is provided.
The invention provides and a kind of sea water desaltination water is applied to method in the recirculating cooling water system, the method comprises sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, and adding inhibiter and pH adjusting agent, make the pH value of recirculated cooling water be 9-12, wherein, described inhibiter contains the first inhibiter and the second inhibiter, described the first inhibiter is selected from one or more in water miscible gluconate, borate, silicate, sulfonated lignin and the tannin, and described the second inhibiter is selected from urotropine and/or thiocarbamide.
The present invention also provides a kind of sea water desaltination water has been applied to method in the recirculating cooling water system, the method comprises sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, and adding inhibiter and pH adjusting agent, make the pH value of recirculated cooling water be 9-12, wherein, described inhibiter contains the first inhibiter, the second inhibiter and the 3rd inhibiter, described the first inhibiter is selected from water miscible vanadate, in tungstate and the molybdate one or more, described the second inhibiter is selected from water miscible gluconate, borate, silicate, in sulfonated lignin and the tannin one or more, described the 3rd inhibiter is selected from urotropine and/or thiocarbamide.
Compare with the existing method that sea water desaltination water is applied in the recirculating cooling water system, the method that sea water desaltination water is applied to recirculating cooling water system provided by the invention can be controlled sea water desaltination water effectively to the corrosion of circulating cooling wetting system.For example, the corrosion coupon that adds sodium lignosulfonate, urotropine and thiocarbamide among the embodiment 4 and be inhibiter is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.026mm/a, and in the Comparative Examples 4 when the concentration of sodium lignosulfonate is 100mg/L, corrosion coupon is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.427mm/a; With respect to the treatment process of controlling separately the sea water desaltination water of corrosion in the Comparative Examples 8 with the sodium hydroxide adjust pH, add five hydration sodium tetraborates among the embodiment 2, thiocarbamide is that the corrosion coupon of inhibiter is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.043mm/a, and be the treatment process of controlling the sea water desaltination water of corrosion at 10 o'clock with the sodium hydroxide adjust pH only in the Comparative Examples 8, corrosion coupon is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 1.034mm/a.For another example, add 12 water sodium orthovanadates among the embodiment 16, Sunmorl N 60S, urotropine is that the corrosion coupon of inhibiter is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.039mm/a, and the inhibiter in the Comparative Examples 9 is 12 water sodium orthovanadate 50mg/L, during Sunmorl N 60S 100mg/L, corrosion coupon is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.073mm/a; With respect to the treatment process of controlling separately the sea water desaltination water of corrosion in the Comparative Examples 8 with the sodium hydroxide adjust pH, anhydrous wolframic acid sodium among the embodiment 20, anhydrous molybdic acid sodium, tannin, urotropine is that inhibiter pH value is that 10.2 ± 0.1 o'clock corrosion coupon is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.027mm/a, and be the treatment process of controlling the sea water desaltination water of corrosion at 10 o'clock with the sodium hydroxide adjust pH only in the Comparative Examples 8, corrosion coupon is 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 1.034mm/a, present method has reduced the corrosion of sea water desaltination water to the circulating cooling wetting system effectively.
Embodiment
According to of the present invention sea water desaltination water is applied to method in the circulating water system, the method comprises sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, and adding inhibiter and pH adjusting agent, make the pH value of recirculated cooling water be 9-12, wherein, described inhibiter contains the first inhibiter and the second inhibiter, described the first inhibiter is selected from one or more in water miscible gluconate, borate, silicate, sulfonated lignin and the tannin, and described the second inhibiter is selected from urotropine and/or thiocarbamide.
Among the present invention, it can be that recirculating cooling water system uses sea water desaltination water as recirculated cooling water fully that sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, also can use sea water desaltination water as moisturizing, namely the part recirculated cooling water is above-mentioned sea water desaltination water.
The first inhibiter and the second inhibiter can successively add, and also can add simultaneously.Add simultaneously fashionablely, can add separately, also can add with form of mixtures.
The method according to this invention, although the weight ratio of various described the first inhibiter and the second inhibiter all can realize purpose of the present invention, preferably, the weight ratio of described the first inhibiter and the second inhibiter is 1: 0.5-3 is preferably 1: 1-2.Adopt the first inhibiter of above-mentioned weight ratio and the second inhibiter can reduce better corrosion to the circulating cooling wetting system.
The method according to this invention, although the first inhibiter of various types of service all can be realized purpose of the present invention, the type of service of the first inhibiter can be powder type, also can be the solution form.Also be the solution form no matter the type of service of the first inhibiter is powder type, preferably, the concentration of described the first inhibiter in recirculated cooling water is 10-200mg/L, is preferably further 20-150mg/L.When described the first inhibiter was selected from gluconate, borate, silicate, sulfonated lignin and the tannin one or more, boratory concentration was with B
4O
7 2-The concentration of meter, gluconate in the concentration of Sunmorl N 60S, silicate with SiO
2The concentration of meter, sulfonated lignin is in the sulfomethylated lignin acid group.
The method according to this invention, although the second inhibiter of various types of service all can be realized purpose of the present invention, the type of service of the second inhibiter can be powder type, also can be the solution form.Also be the solution form no matter the type of service of the second inhibiter is powder type, preferably, the concentration of described the second inhibiter in recirculated cooling water is 10-180mg/L, more preferably 20-170mg/L.
The method according to this invention, the present invention does not have particular requirement to the kind of described gluconate, and preferably, described gluconate is selected from one or more in Sunmorl N 60S, Potassium Gluconate and the Zinc Gluconate, more preferably Sunmorl N 60S.
The method according to this invention, the present invention does not have particular requirement to described boratory kind, and preferably, described borate is selected from Sodium Tetraborate and/or potassium borate.Further under the preferable case, described Sodium Tetraborate is selected from one or more in sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees.
The method according to this invention, the present invention does not have particular requirement to the kind of described silicate, and preferably, described silicate is selected from one or more in sodium metasilicate, Starso, positive potassium silicate and the potassium metasilicate, more preferably Starso.When silicate was Starso, described Starso was preferably one or more in metasilicate pentahydrate sodium, non-hydrate sodium metasilicate and the anhydrous sodium metasilicate.
The method according to this invention, the present invention does not have particular requirement to the kind of described sulfonated lignin, and preferably, described sulfonated lignin are preferably sodium lignosulfonate and/or calcium lignin sulphonate, further are preferably sodium lignosulfonate.
The method according to this invention, preferably, described is Sunmorl N 60S, metasilicate pentahydrate sodium, sodium borate decahydrate, calcium lignin sulphonate and tannin, described the second inhibiter is urotropine, and the weight ratio of Sunmorl N 60S, metasilicate pentahydrate sodium, sodium borate decahydrate, calcium lignin sulphonate and tannin is 1: 1.5-1.7: 0.5-0.7: 1.5-1.7: 0.5-0.7.When inhibiter is the combination of grape sodium saccharate, metasilicate pentahydrate sodium, sodium borate decahydrate, calcium lignin sulphonate, tannin and urotropine, can reduce further the corrosion to the circulating cooling wetting system.
The method according to this invention, preferably, when adopting two component inhibiter, chlorine ion concentration is 150-750mg/L in the recirculated cooling water.When the chlorine ion concentration of recirculated cooling water is 150-750mg/L, can reduce further the corrosion to the circulating cooling wetting system.
According to of the present invention sea water desaltination water is applied to method in the circulating water system, under the another kind of preferable case, the method comprises sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, and adding inhibiter and pH adjusting agent, make the pH value of recirculated cooling water be 9-12, wherein, described inhibiter contains the first inhibiter, the second inhibiter and the 3rd inhibiter, described the first inhibiter is selected from water miscible vanadate, in tungstate and the molybdate one or more, described the second inhibiter is selected from water miscible gluconate, borate, silicate, in sulfonated lignin and the tannin one or more, described the 3rd inhibiter is selected from urotropine and/or thiocarbamide.
The method according to this invention, although the weight ratio of various described the first inhibiter, the second inhibiter and the 3rd inhibiter all can realize purpose of the present invention, preferably, the weight ratio of described the first inhibiter, the second inhibiter and the 3rd inhibiter can be 1: 1-3: 0.5-3 is preferably 1: 2-3: 1.5-3.Adopt the first inhibiter, the second inhibiter and the 3rd inhibiter of above-mentioned weight ratio can reduce better corrosion to the circulating cooling wetting system.
The method according to this invention, in the situation that adopt above-mentioned three component inhibiter, although the first inhibiter of various types of service all can be realized purpose of the present invention, the type of service of the first inhibiter can be powder type, also can be the solution form.Also be the solution form no matter the type of service of the first inhibiter is powder type, preferably, the concentration of described the first inhibiter in recirculated cooling water is 10-150mg/L, further is preferably 15-80mg/L.When described the first inhibiter was selected from vanadate, tungstate and the molybdate one or more, wherein, the concentration of vanadate was with VO
4 3-Meter, tungstate are with WO
4 2-The concentration of meter, molybdate is with MoO
4 2-Meter.
The treatment in accordance with the present invention method, in the situation that adopt above-mentioned three component inhibiter, although the second inhibiter of various types of service all can be realized purpose of the present invention, the type of service of the second inhibiter can be powder type, also can be the solution form.Also be the solution form no matter the type of service of the second inhibiter is powder type, preferably, the concentration of described the second inhibiter in recirculated cooling water is 10-150mg/L, is preferably further 20-120mg/L.When described the second inhibiter was selected from gluconate, borate, silicate, sulfonated lignin and the tannin one or more, boratory concentration was with B
4O
7 2-The concentration of meter, gluconate in the concentration of Sunmorl N 60S, silicate with SiO
2The concentration of meter, sulfonated lignin is in the sulfomethylated lignin acid group.
The treatment in accordance with the present invention method, in the situation that adopt above-mentioned three component inhibiter, although the 3rd inhibiter of various types of service all can be realized purpose of the present invention, the type of service of the 3rd inhibiter can be powder type, also can be the solution form.Also be the solution form no matter the type of service of the 3rd inhibiter is powder type, preferably, the concentration of described the 3rd inhibiter in recirculated cooling water is 30-150mg/L, is preferably further 50-120mg/L.
The method according to this invention, the present invention does not have particular requirement to the kind of described vanadate, preferably, described vanadate is selected from one or more in 12 water sodium orthovanadates, two water sodium metavanadates, anhydrous sodium metavanadate and the potassium metavanadate, more preferably from 12 water sodium orthovanadates.
The method according to this invention, the present invention does not have particular requirement to the kind of described tungstate, and preferably, described tungstate is selected from one or more in anhydrous wolframic acid sodium, tungstate dihydrate acid sodium and the anhydrous wolframic acid potassium, more preferably tungstate dihydrate acid sodium, anhydrous wolframic acid sodium.
The method according to this invention, the present invention does not have particular requirement to the kind of described molybdate, and preferably, described molybdate is selected from anhydrous molybdic acid sodium, Sodium Molybdate Dihydrate and five water potassium molybdates; Sodium Molybdate Dihydrate more preferably.
The method according to this invention, preferably, described the first inhibiter is anhydrous molybdic acid potassium and 12 water sodium orthovanadates, described the second inhibiter is Sunmorl N 60S, metasilicate pentahydrate sodium and tannin, described the 3rd inhibiter is urotropine, the weight ratio of anhydrous molybdic acid potassium and 12 water sodium orthovanadates is 1: 1-1.2, the weight ratio of Sunmorl N 60S, metasilicate pentahydrate sodium and tannin is 1: 1-1.2:1: 1-1.2.When adopting aforementioned inhibiter, can reduce further the corrosion to the circulating cooling wetting system.
The method according to this invention, the present invention does not have particular requirement to sea water desaltination water, and preferably, in the situation that adopts three kinds of inhibiter components, the chlorine ion concentration in the recirculated cooling water is 150-1000mg/L.When the chlorine ion concentration of recirculated cooling water is 150-1000mg/L, can reduce further the corrosion to the circulating cooling wetting system.
No matter the method according to this invention adopts two component inhibiter or three component inhibiter, and the present invention does not have particular requirement to the kind of described pH adjusting agent, and various pH adjusting agents of the prior art all can realize goal of the invention.Preferably, described pH adjusting agent is inorganic alkaline compound.The present invention does not have particular requirement to described inorganic alkaline compound, and preferably, described inorganic alkaline compound is selected from one or more in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood.
No matter the method according to this invention adopts two component inhibiter or three component inhibiter, and the method can also comprise carries out sterilization with recirculating cooling water system.Wherein, the method for described sterilization is selected from one or more in ultraviolet-sterilization, ozone sterilization and the hydrogen peroxide sterilization.
Among the present invention, described ultraviolet-sterilization can carry out with reference to the method for the ultraviolet-sterilization of routine of the prior art, for example, can adopt UV-device irradiation cycle water coolant.Prior art is disclosed all to can be used for the present invention, the uviolizing recirculated cooling water that the present invention preferably adopts the ultraviolet device to produce by the ultraviolet device of generation; Described ultraviolet device is preferably the low-pressure high-strength ultraviolet lamp; The power of described ultraviolet lamp is preferably 100-300W.When adopting ultraviolet-sterilization, preferably, account for global cycle amount 20-60 volume % through the recirculated cooling water of ultraviolet-sterilization.
Described ozone sterilization can carry out with reference to the method for ozone sterilization conventional in the prior art, and for example, described ozone is produced by ozonizer.When adopting ozone sterilization, the ozone amount in the recirculated cooling water is controlled at 0.05-0.20mg/L.
Described hydrogen peroxide sterilization can be carried out with reference to the method for hydrogen peroxide sterilization conventional in the prior art, does not repeat them here.Under the preferable case, it is to add 1-3 time that hydrogen peroxide adds frequency every day, and the effective concentration that adds is 2-15mg/L.
Describe the present invention in detail below in conjunction with embodiment, but be not used for limiting the present invention.
In following examples, test water is the recirculated cooling water of preparation, and the carbon steel test piece is the 20# steel.The test of the water quality preparation of the recirculated cooling water when table 1 is depicted as according to the circulating water equipment initial launch water quality of 1# recirculated cooling water.After circulating water equipment steady running, evaporation and after concentrated the water quality of recirculated cooling water and formulated test with the water quality of 2# or 3# recirculated cooling water.Test after the steady running of employing simulation loop wetting system is done the rotary hanging plate experiment with 2# or 3# recirculated cooling water.Table 2 wherein, the 2# recirculated cooling water is adopted in the rotary hanging plate experiment in 3; Table 6 wherein, the 3# recirculated cooling water is adopted in the rotary hanging plate experiment in 7.
The water quality of table 1 test water
| Sea water desaltination water kind and numbering | The pH value | Cl -/(mg/L) | Specific conductivity (μ s/cm) |
| When circulating water equipment is initial (1#) | 6.5 | 200 | 200 |
| After circulating water equipment is stable (2#) | - | 700 | 700 |
| After circulating water equipment is stable (3#) | - | 900 | 900 |
In following examples, the testing method that relates to is as follows:
1, pH value: GB/T 6920-1986 " the mensuration glass electrode method of water pH value "
2, specific conductivity: GB/T 6908-2008 " mensuration of boiler feed water and water coolant analytical procedure specific conductivity "
3, erosion rate: the test piece of 20# qualitative carbon steel is fixed on the lacing film instrument, put 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, the weight of test piece is calculated average corrosion rate before and after the record test.The regulation of " the small-sized experimental analogic method of testing laboratory " is evaluated in " water coolant analysis and the test method " of corrosion speed quality employing standard GB/T 50050-2007 " Code for design of industrial recirculating cooling water treatment " and production department of China PetroChemical Corporation and development division establishment.
The average corrosion rate calculation formula is:
C: computational constant, take mm/a (millimeter/year) during as unit, C=8.76 * 10
7
Δ 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)
4, the mensuration of heterotrophic bacterium: get the test water sample, in sterilisable chamber, adopt 10 times of dilution technologies of former water, the test water sample is diluted to suitable multiple, and the water sample of corresponding extension rate is inoculated in the culture dish.Then aseptic culture medium is poured in the culture dish, mix with water sample, cultivate 72 ± 4h etc. being inverted in the incubator that is placed on 29 ± 1 ℃ after the culture medium solidifying.After the cultivation, take out culture dish, select those culture dish with 30-300 bacterium colony to count, colony number be multiply by the heterotrophic bacterium number that corresponding dilution training number is this water sample.The regulation of " the small-sized experimental analogic method of testing laboratory " in " water coolant analysis and the test method " of the evaluation employing standard GB/T 50050-2007 " Code for design of industrial recirculating cooling water treatment " of heterotrophic bacterium number and production department of China PetroChemical Corporation and development division establishment.
5, adhere to the mensuration of speed: test tube is installed 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).Then clean the inboard wall of test tube bur, dry, take by weighing the heavy (W of test tube
2), calculate and adhere to speed F '.
A: the area (cm of test specimen
2); T: corrosion test time (h)
Among following examples 1-14, the Comparative Examples 1-8, the recirculated cooling water that the determination test of erosion rate is used is the 2# recirculated cooling water shown in the table 1, the cumulative volume of sea water desaltination water of test usefulness is 2L, and the pH value of the kind of the pH adjusting agent of the concentration of inhibiter, test usefulness and recirculated cooling water in the recirculated cooling water, the erosion rate that records are respectively shown in table 2 and table 3.
Among following examples 16-28, the Comparative Examples 9-18, the recirculated cooling water that the determination test of erosion rate is used is the 3# recirculated cooling water shown in the table 1, the cumulative volume of sea water desaltination water of test usefulness is 2L, and the pH value of the kind of the pH adjusting agent of the concentration of inhibiter, test usefulness and recirculated cooling water in the recirculated cooling water, the erosion rate that records are respectively shown in table 6 and table 7.
Table 2
Table 3
Embodiment 15
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 (PRC), and the control parameter is as follows.
The water quality of test initial sum make up water: 1# recirculated cooling water as shown in table 1
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
Days running: 20 days
System's internal recycle water cumulative volume: 180L
Cycles of concentration: utilize specific conductivity control
The A tower: press composite corrosion inhibitor composition and concentration among the embodiment 3, first inhibiter is added in the 1# sea water desaltination water such as table 1, regulating the pH value with sodium hydroxide simultaneously is 11.6 ± 0.1.The water outlet of drawing 60L/h enters bypass (namely pressing the water of recirculated cooling water internal circulating load 60 volume % through ultraviolet-sterilization), through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 150W again.After specific conductivity reached 700 μ s/cm, the specific conductivity of controlling its circulating water system maintained 700 μ s/cm.Analog result sees Table 4, table 5.
B tower: press composite corrosion inhibitor composition and concentration among the embodiment 5, first inhibiter is added in the 1# sea water desaltination water such as table 1.Ozonizer is opened, so that the concentration of ozone reaches 0.20mg/L in the recirculating cooling water system, regulating the pH value with potassium hydroxide simultaneously is 9.8 ± 0.1, and after specific conductivity reached 700 μ s/cm, the specific conductivity of controlling its circulating water system maintained 700 μ s/cm.Analog result sees Table 4, table 5.
C tower: press composite corrosion inhibitor composition and concentration among the embodiment 9, first inhibiter is added in the 1# sea water desaltination water such as table 1, regulating the pH value with potassium hydroxide is 11.5 ± 0.1, adds simultaneously hydrogen peroxide, add every day 2 times, the hydrogen peroxide effective concentration that adds is 13mg/L.After specific conductivity reached 700 μ s/cm, the specific conductivity of controlling its circulating water system maintained 700 μ s/cm.Analog result sees Table 4, table 5.
D tower: press composite corrosion inhibitor composition and concentration among the embodiment 11, first inhibiter is added in the 1# sea water desaltination water such as table 1.Ozonizer is opened, so that the concentration of ozone reaches 0.08mg/L in the recirculating cooling water system, regulating the pH value with sodium hydroxide simultaneously is 10.8 ± 0.1, will control in real time density of corrosion inhibitor afterwards.Move the 5th day and rise, the water outlet of drawing 25L/h enters bypass (namely pressing the water of recirculated cooling water internal circulating load 25 volume % through ultraviolet-sterilization), through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 120W again.After specific conductivity reached 700 μ s/cm, the specific conductivity of controlling its circulating water system maintained 700 μ s/cm.Analog result sees Table 4, table 5.
E tower: press composite corrosion inhibitor composition and concentration among the embodiment 12, first inhibiter is added in the 1# sea water desaltination water such as table 1, regulating the pH value with potassium hydroxide is 11.2 ± 0.1, add simultaneously hydrogen peroxide, add every day 1 time, the hydrogen peroxide effective concentration that adds maintains 3mg/L, moving the 15 day rises, the water outlet of drawing 30L/h enters bypass (namely pressing the water of recirculated cooling water internal circulating load 30 volume % through ultraviolet-sterilization), through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 200W again.After specific conductivity reached 700 μ s/cm, the specific conductivity of controlling its circulating water system maintained 700 μ s/cm.Analog result sees Table 4, table 5.
Table 4 dynamic analog test test tube result
Table 5 heterotrophic bacterium monitoring result (the heterotrophic bacterium unit of number: individual/mL)
| Sample time | The 1st day | The 5th day | The 10th day | The 15th day | The 20th day |
| The A tower | 2.6×10 3 | 4.7×10 3 | 6.0×10 3 | 7.8×10 3 | 1.2×10 4 |
| The B tower | 6.9×10 2 | 2.5×10 3 | 2.0×10 4 | 8.8×10 3 | 2.5×10 4 |
| The C tower | 1.2×10 3 | 1.5×10 3 | 3.4×10 3 | 5.9×10 3 | 2.9×10 4 |
| The D tower | 1.1×10 3 | 2.5×10 3 | 3.4×10 3 | 5.3×10 3 | 3.5×10 4 |
| The E tower | 3.0×10 3 | 1.5×10 3 | 3.4×10 3 | 1.3×10 3 | 8.5×10 3 |
This shows, the present invention adds the method in the recirculating cooling water system that sea water desaltination water is applied to of two kinds of inhibiter, the erosion rate of A, B, C, D, each tower test tube of E all is lower than 0.034mm/a, reaches " the small-sized experimental analogic method of testing laboratory " " good level " standard in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment; Adhere to speed and all be lower than 7mcm, reach " good level " standard in " the small-sized experimental analogic method of testing laboratory " in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment; Heterotrophic bacterium is all less than 1.0 * 10
5In the span of control, meet the criterion of acceptability in " the small-sized experimental analogic method of testing laboratory " in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment.
Table 6
Table 7
Embodiment 29
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 (PRC), and the control parameter is as follows.
The water quality of test initial sum make up water: 1# recirculated cooling water as shown in table 1
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
Days running: 20 days
System's internal recycle water cumulative volume: 180L
Cycles of concentration: utilize specific conductivity control
A ' tower: press composite corrosion inhibitor composition and concentration among the embodiment 18, first inhibiter is added in the 1# recirculated cooling water such as table 1, regulating the pH value with potassium hydroxide simultaneously is 11.3 ± 0.1.The water outlet of drawing 55L/h enters bypass (namely pressing the water of recirculated cooling water internal circulating load 55 volume % through ultraviolet-sterilization), through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 250W again.After specific conductivity reached 900 μ s/cm, the specific conductivity of controlling its circulating water system maintained 900 μ s/cm.Analog result sees Table 8, table 9.
B ' tower: press composite corrosion inhibitor composition and concentration among the embodiment 19, first inhibiter is added in the 1# recirculated cooling water such as table 1.Ozonizer is opened, so that the concentration of ozone reaches 0.24mg/L in the recirculating cooling water system, regulating the pH value with yellow soda ash simultaneously is 10.2 ± 0.1, and after specific conductivity reached 900 μ s/cm, the specific conductivity of controlling its circulating water system maintained 900 μ s/cm.Analog result table 8, table 9.
C ' tower: press composite corrosion inhibitor composition and concentration among the embodiment 21, first inhibiter is added in the 1# recirculated cooling water such as table 1, regulating the pH value with sodium hydroxide is 9.3 ± 0.1, adds simultaneously hydrogen peroxide, add every day 2 times, the hydrogen peroxide concentration that adds is 10mg/L.After specific conductivity reached 900 μ s/cm, the specific conductivity of controlling its circulating water system maintained 900 μ s/cm.Analog result sees Table 8, table 9.
D ' tower: press composite corrosion inhibitor composition and concentration among the embodiment 27, first inhibiter is added in the 1# recirculated cooling water such as table 1.Ozonizer is opened, so that the concentration of ozone reaches 0.12mg/L in the recirculating cooling water system, regulating the pH value with sodium hydroxide simultaneously is 10.8 ± 0.1.Move the 5th day and rise, the water outlet of drawing 30L/h enters bypass (namely pressing the water of recirculated cooling water internal circulating load 40 volume % through ultraviolet-sterilization), through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 200W again.After specific conductivity reached 900 μ s/cm, the specific conductivity of controlling its circulating water system maintained 900 μ s/cm.Analog result sees Table 8, table 9.
E ' tower: press composite corrosion inhibitor composition and concentration among the embodiment 28, first inhibiter is added in the 1# recirculated cooling water such as table 1, regulating the pH value with sodium hydroxide is 11.3 ± 0.1, add simultaneously hydrogen peroxide, add every day 2 times, make its hydrogen peroxide concentration maintain 4mg/L, move the tenth day and rise, the water outlet of drawing 35L/h enters bypass (namely pressing the water of recirculated cooling water internal circulating load 35 volume % through ultraviolet-sterilization), through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 200W again.After specific conductivity reached 900 μ s/cm, the specific conductivity of controlling its circulating water system maintained 900 μ s/cm.Analog result sees Table 8, table 9.
Table 8 dynamic analog test test tube result
Table 9 heterotrophic bacterium monitoring result (the heterotrophic bacterium unit of number: individual/mL)
| Sample time | The 1st day | The 5th day | The 10th day | The 15th day | The 20th day |
| A ' tower | 3.6×10 3 | 4.9×10 3 | 6.2×10 3 | 7.9×10 3 | 1.1×10 4 |
| B ' tower | 8.0×10 2 | 2.6×10 3 | 2.3×10 4 | 5.8×10 3 | 2.9×10 4 |
| C ' tower | 1.5×10 3 | 1.9×10 3 | 3.1×10 3 | 5.3×10 3 | 1.9×10 4 |
| D ' tower | 4.9×10 3 | 2.5×10 3 | 4.4×10 3 | 5.3×10 3 | 3.0×10 4 |
| E ' tower | 3.7×10 3 | 2.5×10 3 | 3.8×10 3 | 2.3×10 3 | 9.5×10 3 |
This shows, use the method in the recirculating cooling water system that sea water desaltination water is applied to of the above-mentioned three kinds of inhibiter of adding of the present invention, the erosion rate of A ', B ', C ', D ', each tower test tube of E ' all is lower than 0.031mm/a, reaches " the small-sized experimental analogic method of testing laboratory " " good level " standard in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment; Adhere to speed and all be lower than 7mcm, reach " good level " standard in " the small-sized experimental analogic method of testing laboratory " in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment; Heterotrophic bacterium is all less than 1.0 * 10
5In the span of control, meet the criterion of acceptability in " the small-sized experimental analogic method of testing laboratory " in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment.
Claims (17)
1. one kind is applied to method in the recirculating cooling water system with sea water desaltination water, the method comprises sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, and adding inhibiter and pH adjusting agent, make the pH value of recirculated cooling water be 9-12, wherein, described inhibiter contains the first inhibiter and the second inhibiter, described the first inhibiter is selected from one or more in water miscible gluconate, borate, silicate, sulfonated lignin and the tannin, and described the second inhibiter is selected from urotropine and/or thiocarbamide.
2. method according to claim 1, wherein, the weight ratio of described the first inhibiter and the second inhibiter is 1: 0.5-3 is preferably 1: 1-2.
3. method according to claim 1, wherein, the concentration of described the first inhibiter in recirculated cooling water is 10-200mg/L, is preferably 20-150mg/L.
4. method according to claim 1 and 2, wherein, the concentration of the second inhibiter in recirculated cooling water is 10-180mg/L, is preferably 20-170mg/L.
5. method according to claim 1, wherein, described gluconate is selected from one or more in Sunmorl N 60S, Potassium Gluconate and the Zinc Gluconate; Described borate is selected from Sodium Tetraborate and/or potassium borate; Described silicate is selected from one or more in sodium metasilicate, Starso, positive potassium silicate and the potassium metasilicate; Described sulfonated lignin are sodium lignosulfonate and/or calcium lignin sulphonate.
6. according to claim 2 or 5 described methods, wherein, described the first inhibiter is Sunmorl N 60S, metasilicate pentahydrate sodium, sodium borate decahydrate, calcium lignin sulphonate and tannin, described the second inhibiter is urotropine, and the weight ratio of Sunmorl N 60S, metasilicate pentahydrate sodium, sodium borate decahydrate, calcium lignin sulphonate and tannin is 1: 1.5-1.7: 0.5-0.7: 1.5-1.7: 0.5-0.7.
7. method according to claim 1 and 2, wherein, the chlorine ion concentration of described recirculated cooling water is 150-750mg/L.
8. one kind is applied to method in the recirculating cooling water system with sea water desaltination water, the method comprises sea water desaltination water is applied in the recirculating cooling water system as recirculated cooling water, and adding inhibiter and pH adjusting agent, make the pH value of recirculated cooling water be 9-12, wherein, described inhibiter contains the first inhibiter, the second inhibiter and the 3rd inhibiter, described the first inhibiter is selected from water miscible vanadate, in tungstate and the molybdate one or more, described the second inhibiter is selected from water miscible gluconate, borate, silicate, in sulfonated lignin and the tannin one or more, described the 3rd inhibiter is selected from urotropine and/or thiocarbamide.
9. method according to claim 8, wherein, the weight ratio of described the first inhibiter, the second inhibiter and the 3rd inhibiter is 1: 1-3: 0.5-3 is preferably 1: 2-3: 1.5-3.
10. method according to claim 8, wherein, the concentration of described the first inhibiter in recirculated cooling water is 10-150mg/L, is preferably 15-80mg/L.
11. method according to claim 8, wherein, the concentration of described the second inhibiter in recirculated cooling water is 10-150mg/L, is preferably 20-120mg/L.
12. method according to claim 8, wherein, the concentration of described the 3rd inhibiter in recirculated cooling water is 30-150mg/L, is preferably 50-120mg/L.
13. method according to claim 8, wherein, described vanadate is selected from one or more in 12 water sodium orthovanadates, two water sodium metavanadates, anhydrous sodium metavanadate and the potassium metavanadate; Described tungstate is selected from one or more in anhydrous wolframic acid sodium, tungstate dihydrate acid sodium and the anhydrous wolframic acid potassium; Described molybdate is selected from one or more in anhydrous molybdic acid sodium, Sodium Molybdate Dihydrate and the five water potassium molybdates.
14. according to claim 8 or 13 described methods, wherein, described the first inhibiter is anhydrous molybdic acid potassium and 12 water sodium orthovanadates, described the second inhibiter is Sunmorl N 60S, metasilicate pentahydrate sodium and tannin, described the 3rd inhibiter is urotropine, the weight ratio of anhydrous molybdic acid potassium and 12 water sodium orthovanadates is 1: 1-1.2, the weight ratio of Sunmorl N 60S, metasilicate pentahydrate sodium and tannin is 1: 1-1.2: 1: 1-1.2.
15. method according to claim 8, wherein, the chlorine ion concentration of described recirculated cooling water is 150-1000mg/L.
16. according to claim 1 or 8 described methods, wherein, described pH adjusting agent is inorganic alkaline compound; Be preferably in sodium hydroxide, potassium hydroxide, yellow soda ash and the salt of wormwood one or more.
17. according to claim 1 or 8 described methods, wherein, the method also comprises carries out sterilization to recirculating cooling water system, and the method for described sterilization is selected from one or more in ultraviolet-sterilization, ozone sterilization and the hydrogen peroxide sterilization.
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