CN103030239A - Circulating water treatment method adopting deionized water as supplement water - Google Patents
Circulating water treatment method adopting deionized water as supplement water Download PDFInfo
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Abstract
The invention relates to a circulating water treatment method adopting deionized water as supplement water. The method comprises a) controlling pH of circulating water at 9-11.5; b) adding a corrosion inhibitor, wherein the corrosion inhibitor is at least a natural high-molecular polymer and a compound of borate and/or silicate; and c) employing ultraviolet ray irradiation for sterilization, wherein the natural macromolecular compound is selected from tannic acid and lignin natural macromolecular compounds. The inventive circulating water treatment method is suitable for treatment of a circulating cooling water system with sewage subjected to secondary treatment firstly and then to double membrane process so as to serve as supplement water, and can effectively control corrosion and microorganism growth.
Description
Technical field
The present invention relates to a kind of circulating water treatment method, relate in particular to a kind of circulating water treatment method of doing moisturizing with deionized water.
Background technology
As everyone knows, in industries such as petrochemical complex, thermal power generation, metallurgy, need to use large water gaging, wherein water coolant accounts for significant proportion, accounts for more than 80% of water of productive use such as petroleum chemical enterprise's water coolant water.Nowadays water resources shortage, water saving has become world theme.Sewage and Zhong Shui are back to recirculated water will greatly reduce the consumption of fresh water, even realize the spot patch fresh water.
The U.S. has realized discharging urban sewage recycling in the power generation cycle water system in the sixties in 20th century, and the nineties has realized qualified discharge Waste Water Reuse and petrochemical equipment circulating water system.The method of taking is that sewage is carried out advanced treatment, reduces COD, suspended substance and microorganism concn in the qualified discharge sewage, uses corrosion and scaling and the microorganism of water conditioner operating device again.
The method that sewage and Zhong Shui are back to recirculated water has two kinds.A kind of is advanced treatment, is about to sewage reuse after passing through again coagulation, precipitation, filtration, sterilization after the second-stage treatment.Another kind is two embrane methods, soon passes into ultrafiltration reverse osmosis device after the water process coagulation after the second-stage treatment, precipitation, the filtration, and water outlet is deionized water.Two embrane method investment costs are large, still, because there is not the fouling factor in the deionized water, be applied to circulating cooling make-up water, scale problems can be ignored, and therefore can greatly improve cycles of concentration, but also the expense of having saved Scale inhibitors, in addition can also extension device working life, save the overhaul of the equipments expense.As seen adopt deionized water can reduce the later stage expense.It is corrosion and microbiological manipulation that deionized water is done the problem that circulating cooling make-up water need to solve.
Add inhibiter and sterilant for controlling most employing of corrosion and microorganism growth in the recirculated water.The domestic formula of corrosion and scale inhibitor that is usually used in the circulating cooling water treatment mostly is phosphine system prescription at present, and its advantage is that consumption is low, and anticorrosion-antiscaling effect is good, and shortcoming is that the discharging meeting of phosphorus pollutes water body.Sterilant adopts strong chlorine oil more, and its advantage is that bactericidal property is good, but after the strong chlorine oil hydrolysis, residual tricarbimide can cause organism increase in the water in water, at the more difficult self degradation of occurring in nature, can produce environmental issue.Adopt the uv irradiating sterilization, without chemical residual, safety and environmental protection.
CN1338433A discloses in the sewage of qualified discharge and to have added sterilant and carry out disinfection, and adds alkaline matter and makes the pH value be controlled at 9.5-14 to carry out inhibition.Its shortcoming is: because have dissolved oxygen in the water, depend merely on adjusting pH value and can not effectively control corrosion.
CN1524806A discloses the water of high oily(waste)water after oil removal, sedimentation has been introduced circulating water system, simultaneously, adds inorganic base substance and makes the pH value reach 7-11, adds sterilant and corrosion inhibiting and descaling agent.Sterilant selects chlorine series bactericidal agent, the corrosion inhibiting and descaling agents such as clorox, trichloroisocyanuric acid to select organophosphorus, Sodium hexametaphosphate 99, Sodium orthomolybdate etc.Its shortcoming is: the chlorine series bactericidal agent can lose efficacy under alkaline condition, if the phosphorus containg substances such as organophosphorus, Sodium hexametaphosphate 99 are with sewage discharge meeting eutrophication.
CN1393411A has studied a kind of composite corrosion inhibitor for deionized water, and composition is comprised of deionized water, polyetheramides, silicate.Different from inhibiter composition of the present invention, and the present invention is the circulating water treatment method.
Summary of the invention
The object of the present invention is to provide a kind of deionized water to do the circulating water treatment method of moisturizing.
For reaching above purpose, the invention provides a kind ofly with the circulating water treatment method of deionized water as moisturizing, may further comprise the steps: a) the pH value of controlled circulation water is at 9-11.5; B) add inhibiter, described inhibiter is the mixture of at least a natural polymers and borate and/or silicate; C) adopt the uviolizing sterilization, wherein said natural high moleculer eompound is selected from Weibull and lignin natural high moleculer eompound.
The present invention is preferably with the pH value of alkaline matter controlled circulation water, and described alkaline matter is a kind of in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood preferably.
Consider price factor, in the situation that effect is close, the general particular certain cancers inhibiter of the present invention.
Lignin natural polymers of the present invention is selected from xylogen, sodium lignosulfonate and calcium lignin sulphonate; Borate is selected from Sodium Tetraborate and potassium borate, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees; Silicate is selected from sodium metasilicate, Starso, positive potassium silicate and potassium metasilicate, preferably from Starso, more preferably from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate, anhydrous sodium metasilicate.
The working concentration of natural polymers of the present invention is 150-300mg/L, and borate is (with B
4O
7 2-Meter) concentration is 20-40 mg/L, and silicate is (with SiO
2Meter) concentration is 20-40 mg/L.
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.
The water of the total amount 20 volume %-50 volume % of preferred cycle water coolant of the present invention is through ultraviolet-sterilization.
B of the present invention) going on foot described inhibiter can add in the mode of single dose, also can be mixed with first composite corrosion inhibitor, composite scale-inhibiting corrosion inhibitor is once added in the recirculated water again, preferably carries out in the latter's mode.Available ordinary method prepares composite corrosion inhibitor of the present invention, and the reinforced order of each component is unimportant, for example borate, silicate, natural polymers and water can be mixed by predetermined concentration, can make required composite corrosion inhibitor.
Sewage recirculating cooling water system as moisturizing after two embrane methods are processed that method of the present invention is applicable to after the second-stage treatment is processed, and can effectively control corrosion and microorganism growth.Used inhibiter toxicity is low, generates oxygen G﹠W environmentally safe after the used sterilant degraded.
Embodiment
Following corrosion inhibitor formula embodiment will help to illustrate the present invention, but not limit to its scope.Test water is deionized water, and the carbon steel test piece is the 20# steel.Test water water quality sees Table 1.
Table 1 quality of de-ionized water
| Specific conductivity/(us/cm) | The pH value | Total molten solid/ppb |
| 2 | 6.0 | 300 |
The measuring method of water quality is with reference to as follows:
PH value: GB/T 6920-1986 " the mensuration glass electrode method of water pH value "
Specific conductivity: GB/T 6908-2008 " mensuration of boiler feed water river water coolant analytical procedure specific conductivity "
Total molten solid: GB/T 14415-2007 " mensuration of solid matter in industrial circulating cooling water and the boiler feed water ".
The corrosion inhibition of following embodiment gained and bactericidal property assessment method are as follows:
Corrosion inhibitionThe test piece of 20# qualitative carbon steel is fixed on the lacing film instrument, puts into the test water that is added with the drug concentration that adds by embodiment, 45 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72h, and the weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is: F=(C * △ W)/(A * T * ρ)
C: computational constant, take mm/a (millimeter/year) during as unit, C=8.76 * 10
7
△ W: the corrosion weight loss of test specimen (g)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3).
The mensuration of heterotrophic bacterium:Get test water, in sterilisable chamber, adopt 10 times of dilution technologies of former water, test water is diluted to suitable multiple, and the water sample of corresponding extension rate is inoculated in the 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.
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).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 '.
F’=7.2×10
5×(W
1-W
2)/（A×t）
A: the area (cm of test specimen
2)
T: corrosion test time (h).
Embodiment 1
Take by weighing the 200.0g xylogen and the 93.4g sodium borate decahydrate (contains B
4O
7 2-38.0g) to join the 206.6g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and xylogen and sodium borate decahydrate are (with B in the water
4O
7 2-Meter) the concentration that effectively adds is respectively 200 mg/L, 38mg/L, 11.2, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0331mm/a.
Embodiment 2
Take by weighing the 240.0g calcium lignin sulphonate and the 77.7g metasilicate pentahydrate sodium (contains SiO
222.0g) to join the 182.3g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and calcium lignin sulphonate and metasilicate pentahydrate sodium are (with SiO in the water
2Meter) the concentration that effectively adds is respectively 240mg/L, 22mg/L, 10.5, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0404mm/a.
Embodiment 3
Take by weighing the 200.0g sodium lignosulfonate and 56.3g five hydration sodium tetraborates (contain B
4O
7 2-30.0g) to join the 243.7g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and sodium lignosulfonate and five hydration sodium tetraborates are (with B in the water
4O
7 2-Meter) the concentration that effectively adds is respectively 200 mg/L, 30mg/L, 10.5, is 45 ℃ in temperature with potassium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0398mm/a.
Embodiment 4
Take by weighing the 200.0g sodium lignosulfonate and the 142.2g non-hydrate sodium metasilicate (contains SiO
230.0g) to join the 157.8g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and xylogen sodium sulfonate and non-hydrate sodium metasilicate are (with SiO in the water
2Meter) the concentration that effectively adds is respectively 200mg/L, 30mg/L, 10.0, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0431mm/a.
Embodiment 5
Take by weighing the 240.0g Weibull and 58.4g four hydrations eight Sodium Tetraboratees (contain B
4O
7 2-22.0g) to join the 201.6g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and Weibull and four hydrations, eight Sodium Tetraboratees are (with B in the water
4O
7 2-Meter) the concentration that effectively adds is respectively 240 mg/L, 22mg/L, 10.0, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0418mm/a.
Embodiment 6
Take by weighing the 280.0g Weibull and the 61.0g anhydrous sodium metasilicate (contains SiO
230.0g) to join the 159.0g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and Weibull and anhydrous sodium metasilicate are (with SiO in the water
2Meter) the concentration that effectively adds is respectively 280mg/L, 30mg/L, 9.5, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0456mm/a.
Embodiment 7
Take by weighing the 220.0g calcium lignin sulphonate and the 56.9g anhydrous sodium metasilicate (contains SiO
228.0g) to join the 223.1g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and calcium lignin sulphonate and anhydrous sodium metasilicate are (with SiO in the water
2Meter) the concentration that effectively adds is respectively 220mg/L, 28mg/L, 10.5, is 45 ℃ in temperature with sodium hydroxide control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0426mm/a.
Embodiment 8
Take by weighing the single xylogen of 160.0g, 62.5g five hydration potassium tetraborates (contain B
4O
7 2-30.0g) and the positive potassium silicate of 124.0g (contain SiO
230.0g) to join the 153.5g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and xylogen, five hydration potassium tetraborates are (with B in the water
4O
7 2-Meter), positive potassium silicate is (with SiO
2Meter) the concentration that effectively adds is respectively 160mg/L, 30mg/L, 30mg/L, 10.5, is 45 ℃ in temperature with salt of wormwood control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0215mm/a.
Embodiment 9
Take by weighing 100.0g sodium lignosulfonate, 100.0g Weibull and 107.4g sodium metasilicate and (contain SiO
235.0g) to join the 192.6g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and sodium lignosulfonate, Weibull, sodium metasilicate are (with SiO in the water
2Meter) the concentration that effectively adds is respectively 100mg/L, 100mg/L, 35mg/L, 10.0, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0232mm/a.
Embodiment 10
Take by weighing 140.0g sodium lignosulfonate, 140.0g Weibull, 88.3g metasilicate pentahydrate sodium and (contain SiO
225.0g) and the 61.4g sodium borate decahydrate (contain B
4O
7 2-25.0g) to join the 570.3g deionized water for stirring even, is made into inhibiter 1kg of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and sodium lignosulfonate, Weibull, metasilicate pentahydrate sodium are (with SiO in the water
2Meter), sodium borate decahydrate is (with B
4O
7 2-Meter) the concentration that effectively adds is respectively 140mg/L, 140mg/L, 25mg/L, 25mg/L, 9.2, is 45 ℃ in temperature with yellow soda ash control pH value, and rotating speed is to move under the 75r/min condition that to record erosion rate behind the 72h be 0.0203mm/a.
Comparative Examples 1
Take by weighing the 200.0g sodium lignosulfonate and the 98.3g sodium borate decahydrate (contains B
4O
7 2-40.0g) to join the 201.7g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and sodium lignosulfonate and sodium borate decahydrate are (with B in the water
4O
7 2-Meter) the concentration that effectively adds is respectively 200 mg/L, 40mg/L, and adjust pH is not 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.1056mm/a.
Comparative Examples 2
Take by weighing the 280.0g Weibull and the 106.0g metasilicate pentahydrate sodium (contains SiO
230.0g) to join the 114.0g deionized water for stirring even, is made into inhibiter 500.0g of the present invention.
Inhibiter and the deionized water of the present embodiment are rotated coupon test, and Weibull and metasilicate pentahydrate sodium are (with SiO in the water
2Meter) the concentration that effectively adds is respectively 280mg/L, 30mg/L, and adjust pH is not 45 ℃ in temperature, rotating speed be under the 75r/min condition operation to record erosion rate behind the 72h be 0.1210mm/a.
Comparative Examples 3
By controlling corrosion with the sodium hydroxide adjust pH, be 45 ℃ in temperature separately, rotating speed is to record corrosion data such as table 2 behind the operation 72h under the 75r/min condition.
Table 2 pH value is on the impact of corrosion of carbon steel
| The pH value | 10.0 | 11.0 | 12.0 |
| Erosion rate (mm/a) | 1.0345 | 0.0483 | 0.0722 |
Embodiment 11
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).Ultraviolet lamp is installed in the bypass, and drawing-off water enters in the bypass from water tank, behind ultraviolet-sterilization, returns in the water tank again.Significant parameter is as follows.
Test water quality: test water (deionized water)
Quantity of circulating water: 360t/h
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
Days running: 15 days.
A tower: add the composite corrosion inhibitor among the embodiment 1, make in the water xylogen and sodium borate decahydrate (with B
4O
7 2-Meter) effective concentration is respectively 160 mg/L, 38mg/L, and regulating the pH value with sodium hydroxide simultaneously is 11.2, will control in real time density of corrosion inhibitor afterwards and the pH value remains unchanged.The water outlet of drawing 90t/h enters bypass, through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 100W again.Analog result sees Table 3, table 4.
B tower: add the composite corrosion inhibitor among the embodiment 8, make xylogen in the water, five hydration potassium tetraborates (with B
4O
7 2-Meter), positive potassium silicate is (with SiO
2Meter) effective concentration is respectively 160mg/L, 30mg/L, 30mg/L, and regulating the pH value with salt of wormwood simultaneously is 10.5, will control in real time density of corrosion inhibitor afterwards and the pH value remains unchanged.The water outlet of drawing 108t/h enters bypass, through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 150W again.Analog result sees Table 3, table 4.
C tower: regulate pH value to 10.0 with potassium hydroxide, then add the composite corrosion inhibitor among the embodiment 5, make in the water Weibull and four hydrations, eight Sodium Tetraboratees (with B
4O
7 2-Meter) effective concentration is respectively 240 mg/L, 22mg/L, will control in real time density of corrosion inhibitor afterwards and the pH value remains unchanged.The water outlet of drawing 162t/h enters bypass, through power is to return water tank behind the low-pressure high-strength ultra violet lamp of 250W again.Analog result sees Table 3, table 4.
Table 3 dynamic analog test test tube result
Table 4 heterotrophic bacterium monitoring result
| Sample time | The 3rd day | The 6th day | The 9th day | The 12nd day | The 15th day |
| The A tower | 6.8×10 3 | 9.8×10 3 | 5.3×10 3 | 2.1×10 4 | 7.0×10 3 |
| The B tower | 3.2×10 3 | 5.6×10 3 | 2.3×10 3 | 5.1×10 3 | 2.0×10 3 |
| The C tower | 2.2×10 3 | 3.5×10 3 | 3.4×10 3 | 4.7×10 3 | 1.0×10 4 |
The heterotrophic bacterium unit of number: individual/mL.
Regulation among the standard GB/T 50050-2007 " Code for design of industrial recirculating cooling water treatment ", the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a; The corrosion speed of " the small-sized experimental analogic method of testing laboratory " regulation carbon steel is " fine " level at 0-0.028mm/a in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, 0.028-0.056mm/a between be " good " level, 0.056-0.070mm/a for " can allow " level; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.Heterotrophic bacterium is controlled at 10
5Below be qualified.
This shows, using circulating water treatment prescription of the present invention is applied to deionized water and does in the circulating cooling make-up water, the erosion rate of A, B, each tower test tube of C all is lower than 0.05mm/a, reach China Petrochemical Industry's " good level " standard, adhere to speed and all be lower than 7mcm, reach " good level " standard, heterotrophic bacterium is all less than 1.0 * 10
5In the span of control.
Claims (10)
1. one kind with the circulating water treatment method of deionized water as moisturizing, and it may further comprise the steps: a) the pH value of controlled circulation water is at 9-11.5; B) add inhibiter, described inhibiter is the mixture of at least a natural polymers and borate and/or silicate; C) adopt the uviolizing sterilization, wherein said natural high moleculer eompound is selected from Weibull and lignin natural high moleculer eompound.
2. circulating water treatment method according to claim 1 is characterized in that the pH value with alkaline matter controlled circulation water, and described alkaline matter is a kind of in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood preferably.
3. circulating water treatment method according to claim 2 is characterized in that preferably a kind of in sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood of described alkaline matter.
4. each described circulating water treatment method is characterized in that described lignin natural polymers is selected from xylogen, sodium lignosulfonate and calcium lignin sulphonate according to claim 1-3.
5. each described circulating water treatment method is characterized in that described borate is selected from Sodium Tetraborate and potassium borate according to claim 1-4; Silicate is selected from sodium metasilicate, Starso, positive potassium silicate and potassium metasilicate.
6. circulating water treatment method according to claim 5 is characterized in that described borate is selected from Sodium Tetraborate; Silicate is selected from Starso.
7. method for treating circulating cooling water according to claim 6 is characterized in that described borate is selected from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees; Silicate is selected from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate, anhydrous sodium metasilicate.
8. each described circulating water treatment method is characterized in that the working concentration of natural polymers is 150-300mg/L according to claim 1-7, and borate is (with B
4O
7 2-Meter) concentration is 20-40 mg/L, and silicate is (with SiO
2Meter) concentration is 20-40 mg/L.
9. each described method for treating circulating cooling water is characterized in that the uviolizing recirculated cooling water that adopts the ultraviolet device to produce according to claim 1-8; Described ultraviolet device is preferably the low-pressure high-strength ultraviolet lamp; The power of described ultraviolet lamp is preferably 100-300W.
10. each described circulating water treatment method is characterized in that the water process ultraviolet-sterilization based on the total amount 20 volume %-50 volume % of recirculated cooling water according to claim 1-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106011868A (en) * | 2016-05-04 | 2016-10-12 | 北京师范大学 | Non-phosphorus solid slow-release corrosion inhibitor |
| CN115140849A (en) * | 2022-06-22 | 2022-10-04 | 北京师范大学 | Linear release type long-acting phosphorus-free scale inhibitor |
| CN115140849B (en) * | 2022-06-22 | 2023-10-13 | 北京师范大学 | Linear release type long-acting phosphorus-free scale inhibitor |
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