CN103319007A - Method for reuse of reclaimed water in circulating cooling water - Google Patents
Method for reuse of reclaimed water in circulating cooling water Download PDFInfo
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- CN103319007A CN103319007A CN2012100765875A CN201210076587A CN103319007A CN 103319007 A CN103319007 A CN 103319007A CN 2012100765875 A CN2012100765875 A CN 2012100765875A CN 201210076587 A CN201210076587 A CN 201210076587A CN 103319007 A CN103319007 A CN 103319007A
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Abstract
The invention relates to a method for reuse of reclaimed water in circulating cooling water. The method comprises the steps of: (1) filtering reclaimed water and taking the filtered reclaimed water as make-up water of circulating cooling water; (2) adding a scale and corrosion inhibitor into the circulating cooling water, with the scale and corrosion inhibitor containing: A) polyaspartic acid and/or polyepoxysuccinic acid; B) a phosphorus-free copolymer containing a carboxylic acid group; C) a zinc salt and optionally D) a copper corrosion inhibitor; and (3) adding a bactericide and a nonionic surfactant into the circulating cooling water before and/or at the same time of and/or after adding the scale and corrosion inhibitor into the circulating cooling water. According to the method, the use of the reclaimed water as the make-up water of circulating cooling water in a circulating cooling water system can prevent the formation of calcium phosphate scale and the generation of corrosion and biological slime. Therefore, the use of the reclaimed water as the make-up water of circulating cooling water is effective.
Description
Technical field
The present invention relates to a kind of in water be back to the method for recirculated cooling water, more particularly, the present invention relates to through the treatment process of secondary biochemical treatment water outlet as the recirculating cooling water system moisturizing.
Background technology
China is the very poor country of water resources, and water resources ownership per capita is about world occupancy volume per person's 1/4.Lack of water has become the restraining factors of urban economy development and people's lives improvement, and middle water reuse solves the good method of water shortage problem just, be the effective way that realizes municipal sewage as a resource, operate proper good social benefit, environmental benefit, economic benefit and the economy of resources of obtaining.
Industry is the rich and influential family of town water, industrial circulating cooling water account for wherein more than 50%.If with the moisturizing as industrial circulating cooling water of the middle water that obtains after sanitary sewage and the Industrial Wastewater Treatment, significant, be the most important thing of saving town water work.In the water sanitary sewage, the trade effluent that refer to discharge after reclaiming, handling, reach the water of certain water quality standard, i.e. secondary biochemical treatment water outlet is the undrinkable water that can reuse within the specific limits.China does not still have municipal middle water to directly apply to the successful example of big-and-middle-sized manufacturing enterprise industrial circulating cooling water at present.
Industrial circulating cooling water is widely used in all kinds of enterprises such as oil, metallurgy, electric power, chemical industry as industrial main heat transferring medium.Be water saving, generally adopt Recycle design, the circular flow of water coolant will bring three big problems such as burn into fouling, microbial reproduction to system.Compare with fresh water, the stability that middle olighydria is relative, its water quality is complicated and changeable.Middle water is back to industrial circulating cooling water, also will solve the problem of burn into fouling, microbial reproduction, and is difficult to control more owing to the complicacy of middle water, and especially the microbial reproduction problem is more outstanding, the turbidity height, and the corrosion situation is comparatively serious.In addition, have certain density positive phosphorus in the middle water, positive phosphorus very easily forms the phosphoric acid salt crust with calcium, magnesium plasma in water, and this type of dirt is easy-clear not, can influence the heat transfer efficiency of circulating water system, influences ordinary production.
CN1916304A discloses a kind of middle water method for reusing synthesized, the other high-order ecological purification pond that arranges in middle water treatment plant, resident living sewage carries out purifying treatment by pipe-line transportation to middle water treatment plant, a middle water part that obtains after the processing is delivered to the Residential areas and does the undrinkable water use, another part mixes with Chi Shui by discharge of pipes to high-order ecological purification pond, simultaneously, Chi Shui in the high-order ecological purification pond is delivered to middle water treatment plant by overflow spout, is carrying out the sewage purification processing with back, resident living sewage interflow.Water was back to cultivate during this method only related to has in the high-order ecological purification pond of aquatic animals and plants and water microorganisms, with the method for the treatment of pond as " viewing and admiring the lake ".
CN101423300A discloses the anti-incrustation corrosion inhibitor of water reuse system in a kind of being applicable to, this anti-incrustation corrosion inhibitor mainly comprises poly-epoxy succinic acid, 2-phosphonic acids butane-1,2,4-tricarboxylic acid, C
6-C
24Aliphatic amide and nonionic surface active agent, different with the anti-incrustation corrosion inhibitor that the present invention uses.
Summary of the invention
The object of the present invention is to provide a kind of method that middle water can be back to recirculated cooling water.
Water was not back to the method for circulating cooling system during the CN1916304A disclosed method did not relate to, and the corrosion inhibiting and descaling agent that uses in the CN101423300A disclosed method is different with the present invention.
Positive phosphorus is a kind of anodic corrosion inhibitor, can suppress the electrochemistry anodic reaction.It can form oxide compound or oxyhydroxide in positive column, metallic surface and metal ion effect, and deposition covers and forms protective membrane on the anode.Positive phosphorus also is a kind of cathode type inhibiter simultaneously, can suppress the electrochemistry cathodic reaction.Cathodic corrosion inhibitor can with relevant ionic reaction in the water, reaction product is in the cathodic area of metallic surface precipitation film forming.Be example with the zinc salt, it produces Zn (OH) at the negative electrode position
2Precipitation plays protective membrane.In addition, positive phosphorus and the compound use of zinc salt can play the synergistic slow corrosion effect, when having positive phosphorus to exist, Zn are arranged
3(PO
4)
2Or Fe
3(PO
4)
2Be precipitated out and tightly adhere to the metallic surface, corrosion mitigating effect is better.
The present inventor finds, just because of positive phosphorus easily with water in calcium ion generate the very little calcium phosphate scale of solubility product, so seldom emphasize the independent corrosion inhibition of positive phosphorus in the past and it be used as the water coolant inhibiter.The inventor's contriver also finds, positive phosphorus is united use with the without phosphorus multipolymer that contains the carboxylic acid group, the positive phosphorus that contains in the water in can utilizing is as inhibiter, and play the synergistic slow corrosion effect by adding a certain amount of zinc salt, use the without phosphorus multipolymer that contains the carboxylic acid group simultaneously and can prevent PO in the recirculated water by regulating its effective concentration
4 3-, Zn
2+, Ca
2+, Mg
2+The fouling Deng producing precipitation.The described carboxylic acid group's of containing without phosphorus multipolymer can be to Ca in the water because containing a large amount of carboxylic groups in its molecular chain
2+, Mg
2+, Zn
2+Plasma plays sequestering action and lattice distortion effect, so show scale-inhibiting properties.Positive phosphorus in the utilization in the water can reduce the add-on of water treatment agent and reduce cost of water treatment as inhibiter when guaranteeing corrosion mitigating effect.
The tensio-active agent 1427 (tetradecyl dimethyl benzyl ammonium chloride) that the control biological clay uses in the circulating water treatment at present etc. is cats product, use compatibleness poor with the without phosphorus multipolymer that contains the carboxylic acid group, can reduce the scale inhibition dispersion effect of without phosphorus multipolymer.Nonionogenic tenside has good biological clay control action kou equally, and uses compatibleness good with the without phosphorus multipolymer that contains the carboxylic acid group, can not influence the scale inhibition dispersion effect of without phosphorus multipolymer.
The invention provides the method that a kind of middle water is back to recirculated cooling water, wherein, this method may further comprise the steps:
(1) with after the middle water filtration as the moisturizing of recirculated cooling water;
(2) add anti-incrustation corrosion inhibitor in the recirculated cooling water of step (1), described anti-incrustation corrosion inhibitor contains: A) poly aspartic acid and/or poly-epoxy succinic acid; B) contain carboxylic acid group's without phosphorus multipolymer; C) zinc salt and optional D) copper inhibitor;
Wherein, in the ortho-phosphoric acid root, positive phosphorus concentration is 2.5mg/L-5mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is for being not less than 6mg; Positive phosphorus concentration is greater than 5mg/L to 10mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 10mg; Positive phosphorus concentration is greater than 10mg/L to 15mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 16mg;
(3) in the recirculated cooling water of step (1), add anti-incrustation corrosion inhibitor before and/or in recirculated cooling water, add sterilant and nonionogenic tenside simultaneously and/or afterwards.
By method of the present invention middle water is back to recirculated cooling water, simple to operate, and the positive phosphorus in can effectively utilizing in the water, reduce water treatment agent add-on and cost of water treatment, prevent the formation of calcium phosphate scale, preventing from corroding the generation with biological clay, is effective with its moisturizing as recirculated cooling water therefore.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The method according to this invention, contain the without phosphorus multipolymer of carboxylic acid group according to what different positive phosphorus contents added appropriate amount in the recirculated cooling water, thereby make the two combined action, under the preferable case, in the ortho-phosphoric acid root, positive phosphorus concentration is 2.5mg/L-5mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is for being not less than 6mg; Positive phosphorus concentration is greater than 5mg/L to 10mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 10mg; Positive phosphorus concentration is greater than 10mg/L to 15mg/L in recirculated cooling water, is benchmark with every liter of recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 16mg; More preferably, in the ortho-phosphoric acid root, positive phosphorus concentration is 2.5mg/L-5mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is 6-10mg; Positive phosphorus concentration is greater than 5mg/L to 10mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 10mg to 16mg; Positive phosphorus concentration is greater than 10mg/L to 15mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 16mg to 22mg.
The method according to this invention, the described carboxylic acid group's of containing without phosphorus multipolymer is preferably copolymer and/or terpolymer, the described limit viscosity number that contains carboxylic acid group's without phosphorus multipolymer (30 ℃, the limit viscosity number described in the present invention is all measured under the temperature for this reason) is 0.065-0.095dl/g.Preferably, the described carboxylic acid group's of containing without phosphorus multipolymer is selected from vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid/styrene sulfonic acid multipolymer, maleic anhydride/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid/allyl sulphonic acid multipolymer, maleic anhydride/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/toxilic acid/2-methyl-2 '-in the acrylamido propane sulfonic acid multipolymer one or more.Wherein, preferred one or more in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid heptyl ester and Octyl acrylate of described acrylate; More preferably, described acrylate is selected from one or more in methyl acrylate, ethyl propenoate, the Propylene glycol monoacrylate.
The method according to this invention, add-on for described poly aspartic acid and/or poly-epoxy succinic acid has no particular limits, and can be this area amount commonly used, for example, be benchmark with every liter of recirculated cooling water, the add-on of described poly aspartic acid and/or poly-epoxy succinic acid is 2-20mg.Limit viscosity number for described poly aspartic acid and poly-epoxy succinic acid has no particular limits, it can be this area limit viscosity number commonly used, under the preferable case, the limit viscosity number that described poly aspartic acid is 30 ℃ is 0.055-0.090dl/g, and the limit viscosity number that described poly-epoxy succinic acid is 30 ℃ is 0.030-0.060dl/g.
The method according to this invention has no particular limits for described zinc salt, can be various zinc salts commonly used in this area, and preferred, described zinc salt is selected from one or more in zinc nitrate, zinc sulfate, zinc chloride and the zinc carbonate; More preferably, described zinc salt is selected from zinc sulfate and/or zinc chloride; Under the preferable case, be benchmark with every liter of recirculated cooling water, in zine ion, the add-on of zinc salt is 1.5-5mg.
The method according to this invention has no particular limits for described copper inhibitor, can be this area various copper inhibitors commonly used, preferably contains the compound of heterocycle as copper inhibitor; More preferably, one or more in described copper inhibitor selected from mercapto benzothiazole, methyl benzotriazazole and the benzotriazole (BTA).Under the preferable case, be benchmark with every liter of recirculated cooling water, the add-on of described copper inhibitor is 0.5-1.5mg.
The method according to this invention in described step (1), has no particular limits for the method for described filtration, as long as preferably can make turbidity and suspension content after the filtration all be not more than 5mg/L; More preferably, both all are not more than 3mg/L.Described filter method can be various filter method known in the art, and for example, described method with middle water filtration comprises that at least a centering water that adopts in fabric filter, quartz sand filtration device or the more medium filter filters.In order further to obtain better filter effect, preferred, the filtering velocity of described filtration is 10-40m/h.The filtration water yield of the described filtering velocity unit's of referring to filtration area in the unit time.The filtrate of described fabric filter is fibrous bundle or fibrous nodules, and the filtrate of quartz sand filtration device is quartz sand, and the filtrate of more medium filter can be quartz sand and hard coal etc.When suspended substance trickle in the sewage and colloidalmaterial during by strainer, can be dammed.Described fabric filter has the filtration efficiency height, floor space is little, back flushing is easy and water loss is little, be easy to realize advantages such as operation of equipment and convenient management, therefore, can preferably use fabric filter.
The method according to this invention, in described step (3), kind and content for described sterilant have no particular limits, and can be the various sterilant for recirculating cooling water system, and described sterilant can be oxidative bactericide and/or non-oxidative bactericide.Described oxidative bactericide is selected from chlorine, Surchlor GR 60 (one or more in Puritabs, trichloroisocyanuric acid (strong chlorine oil), clorox, dioxide peroxide and the bromine series bactericidal agent; Wherein, described bromine series bactericidal agent is selected from one or more in bromine Chlorodimethyl glycolylurea, dibromo dimethyl hydantoin, bromine chloromethane ethylhydantoin, active bromide (be generally in Sodium Bromide and the tensio-active agent and add auxiliary agent) and the bromine chloride.Under the preferable case, be benchmark with every liter of described recirculated cooling water, the consumption of described oxidative bactericide is 5-200mg; 10-100mg more preferably.Described non-oxidative bactericide is selected from one or more in isothiazolinone, glutaraldehyde and the dithiocyano-methane, under the preferable case, is benchmark with every liter of described recirculated cooling water, and the consumption of described non-oxidative bactericide is 5-300mg; 30-150mg more preferably; Especially be preferably 50-100mg.
The method according to this invention, described nonionogenic tenside is selected from fatty amide and/or alkylolamide.
The method according to this invention, described fatty amide are selected from the straight chain fatty acid acid amides that carbonatoms is 12-24; Preferably, described fatty amide is selected from one or more in laurylamide, myristoyl amine, palmitoyl amine, stearylamide, 20 carboxamides, 22 carboxamides and the tetracosa carbon acid amides; More preferably, described fatty amide is selected from one or more in laurylamide, stearylamide and the tetracosa carbon acid amides.
The method according to this invention, described alkylolamide are the condensation product of lipid acid and thanomin.Described lipid acid is selected from the lipid acid that carbonatoms is 12-24; Preferably, described lipid acid is selected from one or more in lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, arachic acid, docosoic acid and the Lignoceric acid, and described thanomin is monoethanolamine and/or diethanolamine; Wherein, the wideer and those skilled in the art of the selectable range of the mol ratio of described lipid acid and thanomin can select with reference to prior art.More preferably, described alkylolamide is selected from one or more in lauric acid diethyl amide, Stearic acid diethanolamine salt, palmitinic acid diglycollic amide, tetradecanoic acid single ethanol amide, lauric monoethanolamide, palmitic monoethanolamide and the stearic acid monoethanolamide.
The method according to this invention is benchmark with every liter of recirculated cooling water, and the add-on of described nonionogenic tenside can be 2-100mg, takes all factors into consideration cost and effect, and the add-on of described nonionogenic tenside is preferably 5-30mg.
The method according to this invention, have no particular limits for described sterilant and nonionogenic tenside adding mode, can be various adding modes commonly used in this area, for example: disposablely every three days add a kind of medicament, be one with fortnight and add the cycle that order of adding is: oxidative bactericide-non-oxidative bactericide-oxidative bactericide-nonionogenic tenside.
" limit viscosity number " is called intrinsic viscosity again described in the present invention, refers to the size of polymer shared volume in solution of unit mass.
According to the present invention, " middle water " refer to will discharging sanitary sewage, trade effluent reclaim, water that after treatment can recycling also claims reuse water.Water after the treated facility deep purifying of municipal effluent is handled (comprise water and the bathing water of building, living community, the vegetable washing water etc. of sewage work after second-stage treatment is deepened processing again concentrate after treatment water) general designation " middle water ".Its water quality is between tap water (going up water) and enter between the sewage in the pipeline (following water) also event " middle water " by name.It refers to that mainly municipal effluent or sanitary sewage reach certain water quality standard after treatment, within the specific limits reusable undrinkable water.The COD value of water generally below 100mg/L, is generally 15-100mg/L in described.In industrial cycle cooling water standard, middle water COD of the present invention answers≤60mg/L according to reclaimed water reuse.
Method of the present invention is applicable to that the various middle water that will satisfy above-mentioned COD value is back to recirculated cooling water.
Through provided by the invention described in the water method that is back to recirculated cooling water can satisfy recirculated cooling water well requirement (for example, carbon steel equipment heat-transfer surface water side corrosion speed<0.075mm/a, equipment heat-transfer surface water side adheres to speed<15mcm, heterotrophic bacterium number<1 * 10
5Individual/mL etc.), thus realize middle water is back in the recirculating cooling water system as moisturizing.
To further describe in detail the present invention by specific embodiment below.
The used test raw water quality of following embodiment 1-15 and Comparative Examples 1-14 sees Table 1 in (with middle water as the former water of test).The measuring method of water quality is measured according to standard of chemical industry HG/T 3609-2000 " industrial circulating cooling water water quality analysis method rule ".
Table 1
Project | Test former water 1 | Test former water 2 | Test former water 3 |
Ca 2+/(mg/L) | 215.9 | 232.7 | 269.4 |
Total hardness/(mg/L) | 311.6 | 347.1 | 407.8 |
Total alkalinity/(mg/L) | 195.7 | 206.5 | 255.4 |
Cl -/(mg/L) | 84.4 | 135.2 | 133.5 |
SO 4 2-/(mg/L) | 70.8 | 122 | 183 |
Total phosphorus/(mg/L) | 0.69 | 1.39 | 2.87 |
Positive phosphorus/(mg/L) | 0.58 | 1.33 | 2.72 |
Specific conductivity/(μ s/cm) | 938 | 1041 | 1439 |
pH | 7.63 | 7.31 | 7.18 |
Turbidity/(mg/L) | 5.2 | 7.5 | 9.6 |
COD/(mg/L) | 17.3 | 26.8 | 32.5 |
Suspended substance/(mg/L) | 8.6 | 10.2 | 13.8 |
Annotate: Ca
2+, total alkalinity, total hardness be all with CaCO
3Meter, total phosphorus, positive phosphorus are all with PO
4 3-Meter, as follows.
In the filtration step of following embodiment 1-15 and Comparative Examples 1-14, with the former water 1 of above-mentioned test, test former water 2 and test former water 3 and use high-efficiency fiber beam filter device (available from Yixing Tong Zhou environment-friendly materials equipment company limited respectively, model is GSG-1000), the quartz sand filtration device is (available from Beijing Chunqiu Dingsheng Environmental Science and Technology Co., Ltd., model is GLQ-600) and quartz sand and anthracitic more medium filter (available from the U.S. water utilities in source Science and Technology Ltd., model is YMJX-400) filter, suspended substance and turbidity are as shown in table 2 below in the middle water that obtains after the filtration.
Table 2
Project | Filtrate 1 | Filtrate 2 | Filtrate 3 |
Turbidity/(mg/L) | 1.7 | 2.3 | 2.5 |
Suspended substance/(mg/L) | 2.1 | 2.7 | 3.0 |
Wherein, the turbidity of described middle water adopts turbidimeter (the permanent instrument electronics technology in Kunshan company limited, model is 2100AN) to measure, and suspension content adopts GB 11901-89 gravimetric determination.
Embodiment 1-12 and Comparative Examples 1-9
Embodiment 1-12 and Comparative Examples 1-9 are used for corrosion mitigating effect and the resistance calcium phosphate scale effect of explanation method of the present invention and reference method of the present invention.
In table 2, replenish Ca in filtrate 1, filtrate 2 and the filtrate 3 respectively
2+And PO
4 3-To cycles of concentration be 5 times amount, the recirculated cooling water when water is as the moisturizing of recirculated cooling water in being equivalent to, as corrosion mitigating effect and resistance calcium phosphate scale measure of merit test water, the positive phosphorus concentration difference in each test water is as follows with the water after handling:
Table 3
Project | Test water 1 | Test water 2 | Test water 3 |
Positive phosphorus/(mg/L) | 2.92 | 6.68 | 13.65 |
The benchmark test method of anti-incrustation corrosion inhibitor is as follows:
1) corrosion inhibition test:
With 20
#The carbon steel test piece (embodiment 3,6,10 and Comparative Examples 2,4,6,7,8 increase the brass test pieces) be fixed on the lacing film instrument, put into the test water that is added with the medicament that adds by the embodiment 1-12 shown in the table 4 and Comparative Examples 1-9 respectively, control pH value is 8.0 ± 0.2 in the process of the test, 45 ± 1 ℃ of steady temperatures, keep rotating speed 75r/min rotation 72h at the rotary hanging plate instrument, the weight of test piece is calculated average corrosion rate before and after the record test, and its result is shown in the table 6.
The average corrosion rate calculation formula is:
F=(C×ΔW)/(A×T×ρ)
C: computational constant, when being unit with mm/a, C=8.76 * 10
7
Δ W: the corrosion weight loss of test piece (g)
A: the area (cm of test piece
2)
T: corrosion test time (h)
ρ: the density (kg/m of test piece material
3)
2) resistance calcium phosphate scale performance test:
Adding sodium tetraborate adjusting pH in the test water of table 3 is 9.0, transfers in the 500mL volumetric flask, adds certain density medicament by the embodiment 1-12 shown in the table 4 and Comparative Examples 1-9 then, is settled to scale, shakes up.In 80 ± 1 ℃ of waters bath with thermostatic control, leave standstill 10h, remain PO in the sampling analysis water after cooling
4 3-Concentration, make blank sample with the corresponding test water that does not add anti-incrustation corrosion inhibitor simultaneously, and calculate scale inhibition performance, its result is shown in the table 6.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: the test water test back PO that adds corrosion inhibiting and descaling agent
4 3-Concentration (mg/L)
C
0: the test water test back PO that does not add corrosion inhibiting and descaling agent
4 3-Concentration (mg/L)
C
1: PO in the test water before the test
4 3-Concentration (mg/L)
Table 4
Following medicament used in the embodiment of the invention and the Comparative Examples is respectively available from following producer.
Table 5
Table 6
By The above results as can be seen, utilize the method (embodiment 1-12) that middle water is back to recirculated cooling water of the present invention to compare with the reference method (Comparative Examples 1-6) that middle water is back to recirculated cooling water, the scale inhibition performance of calcium phosphate obviously improves, and corrosion of carbon steel speed and copper material corrosion speed obviously reduce.Illustrate and adopt middle water of the present invention to be back to the method for recirculated cooling water, can reduce the formation of calcium phosphate scale effectively, prevent the corrosion of steel and copper material.Result by embodiment and Comparative Examples 7-9 it can also be seen that relatively the adding of sterilant and nonionogenic tenside does not have influence substantially to resistance calcium phosphate scale and the corrosion mitigating effect of anti-incrustation corrosion inhibitor.
Embodiment 13-15 and Comparative Examples 10-13
Present embodiment and Comparative Examples are used for the scale inhibitor effect of explanation method of the present invention and reference method and to the inhibition of heterotrophic bacterium.
Carry out dynamic analog test according to the chemical industry standard HG/T 2160-91 of the People's Republic of China (PRC), test control parameter is as follows:
Cycles of concentration (ratio of saltiness and the make up water saltiness of recirculated cooling water is described): 5.0 ± 0.2
The system flow rate of recirculated water: 1.0m/s
Recirculated water is in the temperature at heat exchanger entrance place: 32 ± 1 ℃
Recirculated water is imported and exported the temperature difference: 10 ℃
The pH value of recirculated water: 8.0.
Embodiment 13
Present embodiment is used for the method that explanation water provided by the invention is back to recirculated cooling water.
(1) will join in the circulating cooling system as moisturizing according to the filtrate 1 in the table 2, after the cycles of concentration of recirculated cooling water reaches 5, positive phosphorus concentration in the recirculated water is 2.95mg/L, add poly aspartic acid (limit viscosity number is 0.059dl/g) respectively in the recirculated cooling water, (weight ratio is 7: 3 to vinylformic acid/styrene sulfonic acid multipolymer, limit viscosity number is 0.081dl/g) and Zinc vitriol, effective concentration is respectively 6mg/L, 8mg/L, 2mg/L;
(2) added Surchlor GR 60, isothiazolinone, Surchlor GR 60 and laurylamide respectively every three days in the recirculated water that obtains to step (1), add concentration and be respectively 50mg/L, 70mg/L, 50mg/L and 10mg/L.
(3) test run is after 15 days, and " water coolant analysis and the test method " of writing with reference to production department of China PetroChemical Corporation and development division measured impurity and suspended substance in test tube erosion rate and the water and sticked to adhesion speed on the tube wall; Measure the quantity of heterotrophic bacteria respectively with reference to the method for GB GB/T 14643.1-2009, the result is shown in table 7 and the table 8.
Embodiment 14
Present embodiment is used for the method that explanation water provided by the invention is back to recirculated cooling water.
(1) will join in the circulating cooling system as moisturizing according to the filtrate 2 in the table 2, after the cycles of concentration of recirculated cooling water reaches 5, positive phosphorus concentration in the recirculated water is 6.70mg/L, add poly-epoxy succinic acid (limit viscosity number is 0.035dl/g) respectively in the recirculated cooling water, (weight ratio is 4: 1 to toxilic acid/styrene sulfonic acid multipolymer, limit viscosity number is 0.092dl/g) and zinc chloride, add concentration and be respectively 12mg/L, 14mg/L, 2mg/L;
(2) added trichloroisocyanuric acid, glutaraldehyde, trichloroisocyanuric acid and 1: 1 type lauric monoethanolamide (synthetic product of 1mol lauric acid and 1mol monoethanolamine) respectively every three days in the recirculated water that obtains to step (1), add concentration and be respectively 30mg/L, 60mg/L, 30mg/L and 20mg/L;
(3) test run is after 15 days, and " water coolant analysis and the test method " of writing with reference to production department of China PetroChemical Corporation and development division measured impurity and suspended substance in test tube erosion rate and the water and sticked to adhesion speed on the tube wall; Measure the quantity of heterotrophic bacteria respectively with reference to the method for GB GB/T 14643.1-2009, the result is shown in table 7 and the table 8.
Embodiment 15
Present embodiment is used for the method that explanation water provided by the invention is back to recirculated cooling water
(1) will join in the circulating cooling system as moisturizing according to the filtrate 3 in the table 2, after the cycles of concentration of recirculated cooling water reaches 5, positive phosphorus concentration in the recirculated water is 13.67mg/L, add respectively in the recirculated cooling water poly-epoxy succinic acid (limit viscosity number is 0.056dl/g), acrylic acid/esters/2-methyl-2 '-(weight ratio is 3: 1: 1 to acrylamido propane sulfonic acid multipolymer, limit viscosity number is 0.069dl/g) and zinc chloride, add concentration and be respectively 16mg/L, 18mg/L, 3mg/L;
(2) added bromine Chlorodimethyl glycolylurea, dithiocyano-methane, bromine Chlorodimethyl glycolylurea and 1: 1 type Stearic acid diethanolamine salt (synthetic product of 1mol stearic acid and 1mol diethanolamine) respectively every three days in the recirculated water that obtains to step (1), add concentration and be respectively 25mg/L, 100mg/L, 25mg/L and 15mg/L;
(3) test run is after 15 days, and " water coolant analysis and the test method " of writing with reference to production department of China PetroChemical Corporation and development division measured impurity and suspended substance in test tube erosion rate and the water and sticked to adhesion speed on the tube wall; Measure the quantity of heterotrophic bacteria respectively with reference to the method for GB GB/T 14643.1-2009, the result is shown in table 7 and the table 8.
Comparative Examples 10
This Comparative Examples is used for the reference method that explanation water is back to recirculated cooling water.
According to the method identical with embodiment 13, different is, the vinylformic acid/concentration of styrene sulfonic acid multipolymer in recirculated water is 2mg/L, and erosion rate and the measurement result that adheres to speed are shown in table 7 and the table 8.
Comparative Examples 11
This Comparative Examples is used for the reference method that explanation water is back to recirculated cooling water.
According to the method identical with embodiment 14, different is, the toxilic acid/concentration of styrene sulfonic acid multipolymer in recirculated water is 8mg/L, and erosion rate and the measurement result that adheres to speed are shown in table 7 and the table 8.
Comparative Examples 12
This Comparative Examples is used for the reference method that explanation water is back to recirculated cooling water.
According to the method identical with embodiment 15, different is, acrylic acid/esters/2-methyl-2 '-concentration of acrylamido propane sulfonic acid multipolymer in recirculated water is 12mg/L, erosion rate and the measurement result that adheres to speed are shown in table 7 and the table 8.
Comparative Examples 13
This Comparative Examples is used for the reference method that explanation water is back to recirculated cooling water.
According to the method identical with embodiment 15, different is, use cats product 1427 to substitute 1: 1 type Stearic acid diethanolamine salt of nonionogenic tenside in the step (2), concentration is 15mg/L, and the measurement result of erosion rate and adhesion speed is shown in table 7 and the table 8.
The measuring method of erosion rate and adhesion speed is specific as follows:
The mensuration of erosion rate: (W will weigh
0) after the carbon steel test tube be positioned in the bypass of interchanger, take out test tube after the off-test, clean then, dry, take by weighing the heavy (W of test tube
2), calculate average corrosion rate F.
F=[C×(W
0-W
2)]/(A×T×ρ)
C: computational constant, when every year, (mm/a) was unit with millimeter, C=8.76 * 10
7
W
0: the weight (g) of test tube before the test
W
2: the weight (g) of cleaning the back test tube
A: the internal surface area (cm before the test tube test
2)
T: test period (h)
ρ: the density (kg/m of tube material
3)
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)
W
1: the weight (g) of band bur test tube
W
2: the weight (g) of cleaning the back test tube
A: the internal surface area (cm before the test tube test
2)
T: test period (h)
Table 7
Erosion rate (mm/a) | Adhere to speed (mg/ (cm 2Month)) | |
Embodiment 13 | 0.029 | 6.5 |
Embodiment 14 | 0.032 | 7.3 |
Embodiment 15 | 0.035 | 8.1 |
Comparative Examples 10 | 0.047 | 14.6 |
Comparative Examples 11 | 0.038 | 13.8 |
Comparative Examples 12 | 0.040 | 14.3 |
Comparative Examples 13 | 0.051 | 12.7 |
The measuring method of heterotrophic bacterium is specific as follows:
The mensuration of heterotrophic bacterium forms mensuration-plate count of bacterium with reference to mucus in the GB GB/T 14643.1-2009 industrial circulating cooling water, be specially the recirculated water in the water collecting basin is taken a sample according to the described different time sections of table 8, get the recirculated water of 1ml then respectively and according to different embodiment and Comparative Examples and different steps, look bacterial number in the sampling water and how much select different extension rates such as 10 times, 100 times, 1000 times to dilute, and the recirculated water after will diluting is inoculated in the culture dish.Then aseptic culture medium (beef-protein medium) is poured in the culture dish, mix with recirculated water after the dilution, cultivate 72 ± 4h etc. being inverted after the culture medium solidifying in the incubator be placed on 29 ± 1 ℃.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 extension rate is this water sample.
Table 8
Regulation among the standard GB 50050-2007 " Code for design of industrial recirculating cooling water treatment ", a cold opened system recirculated cooling water heat exchange carbon steel equipment heat-transfer surface water side corrosion speed should be less than 0.075mm/a; Equipment heat-transfer surface water side adheres to speed should be greater than 15mg/ (cm
2Month); Total heterotrophic bacteria count is not more than 1 * 10
5Individual/mL.
By table 7 and table 8 as can be seen, the erosion rate of embodiment 13-15 is between 0.029-0.035mm/a; Adhere to speed at 6.5-8.1mg/ (cm
2Month) between; Total heterotrophic bacteria count also all obviously is less than 1 * 10
5Individual/as below the mL, all to be better than the treatment effect of Comparative Examples 10-13.Illustrate that using method of the present invention can be back to circulating cooling system as moisturizing with middle water, and method of the present invention prevents that the effect of local corrosion and inhibition microorganism growth is all fine under the higher middle water condition of water quality of more, the positive phosphorus concentration of suspended substance.
Claims (14)
1. water is back to the method for recirculated cooling water in one kind, it is characterized in that this method may further comprise the steps:
(1) with after the middle water filtration as the moisturizing of recirculated cooling water;
(2) add anti-incrustation corrosion inhibitor in the recirculated cooling water of step (1), described anti-incrustation corrosion inhibitor contains: A) poly aspartic acid and/or poly-epoxy succinic acid; B) contain carboxylic acid group's without phosphorus multipolymer; C) zinc salt and optional D) copper inhibitor;
Wherein, in the ortho-phosphoric acid root, positive phosphorus concentration is 2.5mg/L-5mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is for being not less than 6mg; Positive phosphorus concentration is greater than 5mg/L to 10mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 10mg; Positive phosphorus concentration is greater than 10mg/L to 15mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 16mg;
(3) in the recirculated cooling water of step (1), add anti-incrustation corrosion inhibitor before and/or in recirculated cooling water, add sterilant and nonionogenic tenside simultaneously and/or afterwards.
2. method according to claim 1, wherein, in described step (2), in the ortho-phosphoric acid root, positive phosphorus concentration is 2.5mg/L-5mg/L in described recirculated cooling water, be benchmark with every liter of described recirculated cooling water, the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is 6-10mg; Positive phosphorus concentration is greater than 5mg/L to 10mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 10mg to 16mg; Positive phosphorus concentration is greater than 10mg/L to 15mg/L in described recirculated cooling water, is benchmark with every liter of described recirculated cooling water, and the content of the without phosphorus multipolymer that contains the carboxylic acid group in the anti-incrustation corrosion inhibitor that adds is greater than 16mg to 22mg.
3. method according to claim 1 and 2, wherein, the described carboxylic acid group's of containing without phosphorus multipolymer is copolymer and/or terpolymer, the limit viscosity number in the time of 30 ℃ is 0.065-0.095dl/g.
4. method according to claim 3, wherein, the described carboxylic acid group's of containing without phosphorus multipolymer is selected from vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid/styrene sulfonic acid multipolymer, maleic anhydride/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid/allyl sulphonic acid multipolymer, maleic anhydride/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/toxilic acid/2-methyl-2 '-in the acrylamido propane sulfonic acid multipolymer one or more.
5. method according to claim 4, wherein, described acrylate is selected from one or more in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinylformic acid heptyl ester and the Octyl acrylate.
6. method according to claim 1 wherein, in the step (2), is benchmark with every liter of described recirculated cooling water, and the add-on of described poly aspartic acid and/or poly-epoxy succinic acid is 2-20mg.
7. according to claim 1 or 6 described methods, wherein, the limit viscosity number during 30 ℃ of described poly aspartic acids is 0.055-0.090dl/g, and the limit viscosity number during 30 ℃ of described poly-epoxy succinic acids is 0.030-0.060dl/g.
8. method according to claim 1, wherein, in the step (2), described zinc salt is selected from one or more in zinc sulfate, zinc chloride, zinc nitrate and the zinc carbonate; Be benchmark with every liter of described recirculated cooling water, in zine ion, the add-on of described zinc salt is 1.5-5mg.
9. method according to claim 1, wherein, in the step (2), one or more in described copper inhibitor selected from mercapto benzothiazole, methyl benzotriazazole and the benzotriazole; Be benchmark with every liter of described recirculated cooling water, the add-on of described copper inhibitor is 0.5-1.5mg.
10. method according to claim 1, wherein, in the step (1), the condition of filtration makes turbidity and the suspension content of the middle water after filtering all be not more than 5mg/L.
11. method according to claim 1, wherein, described sterilant is oxidative bactericide and/or non-oxidative bactericide.
12. method according to claim 11, wherein, described oxidative bactericide is selected from one or more in chlorine, Surchlor GR 60, trichloroisocyanuric acid, clorox, dioxide peroxide and the bromine series bactericidal agent; Be benchmark with every liter of described recirculated cooling water, the add-on of described oxidative bactericide is 5-200mg.
13. method according to claim 11, wherein, described non-oxidative bactericide is selected from one or more in isothiazolinone, glutaraldehyde and the dithiocyano-methane, is benchmark with every liter of described recirculated cooling water, and the add-on of described non-oxidative bactericide is 5-300mg.
14. method according to claim 1, wherein, described nonionogenic tenside is fatty amide and/or alkylolamide; Described fatty amide is selected from one or more in laurylamide, myristoyl amine, palmitoyl amine, stearylamide, 20 carboxamides, 22 carboxamides and the tetracosa carbon acid amides; Described alkylolamide is selected from one or more in lauric acid diethyl amide, Stearic acid diethanolamine salt, palmitinic acid diglycollic amide, tetradecanoic acid single ethanol amide, lauric monoethanolamide, palmitic monoethanolamide and the stearic acid monoethanolamide; Be benchmark with every liter of described recirculated cooling water, the add-on of described nonionogenic tenside is 2-100mg.
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