CN109748401A - The processing method of recirculated cooling water - Google Patents
The processing method of recirculated cooling water Download PDFInfo
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- CN109748401A CN109748401A CN201711070396.7A CN201711070396A CN109748401A CN 109748401 A CN109748401 A CN 109748401A CN 201711070396 A CN201711070396 A CN 201711070396A CN 109748401 A CN109748401 A CN 109748401A
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Abstract
The present invention relates to the corrosion-mitigation scale-inhibition fields of recirculated cooling water, and in particular to the processing method of recirculated cooling water, including, recirculated cooling water is contacted with without phosphorus composite slow-corrosion scale resistor；Without phosphorus composite slow-corrosion scale resistor contains compound A, co-polymer of sulfonate, zinc salt and optional copper inhibitor, and compound A is hydrolysis of polymaleic anhydride and/or maleic acid-acrylic acid copolymer；Following cooling water is the middle hardness water that the sum of calcium hardness and total alkalinity are greater than that 100mg/L is less than 900mg/L；The pH value of recirculated cooling water is 7.9-8.5.The composite slow-corrosion scale resistor has excellent corrosion inhibition, stablizes Zn in water well2+Ability and resistance CaCO3Dirty function, and the component of corrosion inhibiting and descaling agent itself is few, dosage is low, is the circulating water cooling treatment for being less than 900mg/L greater than 100mg/L particularly suitable for the sum of calcium hardness and total alkalinity.And the composite slow-corrosion scale resistor does not contain phosphorus, it is environmentally protective.
Description
Technical field
The present invention relates to the corrosion-mitigation scale-inhibition fields of recirculated cooling water, specifically, cold to recycling using the resistance of without phosphorus compound slow corrosion
But the processing method of water.
Background technique
The supply/demand of recirculated cooling water, to entire industrial enterprise's water, draining, it is water-saving have significant impact, but therewith
Bring is the rotten candle scale problems of cooling facility in recirculating cooling water system.In cooling circulating water system, addition inhibition resistance
Dirty agent is to prevent one of most important method of recirculated cooling water fouling.In addition country mentioning the continuous of environmentally friendly attention degree in recent years
Height, especially for industrial enterprise, in petro chemical industry pollutant emission standard GB31570-2015 provide total phosphorus discharge (with
P meter)≤1.0mg/L, total zinc≤2.0mg/L, chemical oxygen consumption (COC)≤60mg/L；Urban wastewater treatment firm pollution discharge standard
Total phosphorus≤the 0.3mg/L newly to found the factory, chemical oxygen consumption (COC)≤30mg/L, total zinc≤1.0mg/L are provided in DB11/890-2012.Cause
This, the content for controlling its phosphorus content, chemical oxygen consumption (COC) and total zinc from corrosion inhibiting and descaling agent itself is to reduce the important ring of disposal of pollutants
Section, corrosion inhibiting and descaling agent have been very urgent without phosphatization greenization.It the exploitation of poly-epoxy succinic acid and is applied in order to without phosphorus, raw
The direction of Biodegradable green scale corrosion inhibitor development, poly-epoxy succinic acid have inhibition, scale inhibition dual function, thermal stability concurrently
Well, the advantages that without phosphorus non-nitrogen, but in practical applications, poly-epoxy succinic acid itself belongs to alkalinity, multiple with other corrosion inhibiting and descaling agents
Timing easily precipitates, and is not easy to mix, and practical application is inconvenient.Meanwhile water resource more it is deficient now, deposited in terms of water quality
In the low hard water of more situation, soft water, demineralized water, reusing sewage water etc., these are all more harsh to test water treatment agent
Superiority in terms of inhibition.
Therefore, be badly in need of developing it is a kind of it is without phosphorus, green, application is strong, component is few, using the low corrosion inhibiting and descaling agent of concentration.
Summary of the invention
The purpose of the invention is to overcome the prior art there are defect as above, provide and a kind of use without phosphorus compound slow corrosion
The processing method to recirculated cooling water is hindered, the composite slow-corrosion scale resistor which uses is few, without phosphorus with component, work is dense
Spend low and environmentally protective characteristic.
To achieve the goals above, the present invention provides a kind of processing method of recirculated cooling water, and this method includes that will recycle
Cooling water is contacted with without phosphorus composite slow-corrosion scale resistor；
Wherein, it is slow to contain compound A, co-polymer of sulfonate, zinc salt and optional copper for the without phosphorus composite slow-corrosion scale resistor
Lose agent, wherein the compound A is hydrolysis of polymaleic anhydride and/or maleic acid-acrylic acid copolymer；
Wherein, the cooling water that follows is the middle hardness that the sum of calcium hardness and total alkalinity are greater than that 100mg/L is less than 900mg/L
Water；The pH value of the recirculated cooling water is 7.9-8.5.
Preferably, the co-polymer of sulfonate is dibasic sulfoacid salt copolymer or ternary co-polymer of sulfonate.
Preferably, the copper inhibitor is azole compounds.
Preferably, the without phosphorus composite slow-corrosion scale resistor also contains water, the without phosphorus compound slow corrosion scale inhibition based on 100 parts by weight
Agent, the content of water are 30-80 parts by weight.
Composite slow-corrosion scale resistor used in method for treating circulating cooling water of the present invention has excellent corrosion inhibition, also
Stablize Zn in water well2+Ability and resistance CaCO3Dirty function, and the component of corrosion inhibiting and descaling agent itself lacks and dosage is lower, it is special
It is not suitable for the circulating water cooling treatment of middle hard water matter, as the sum of calcium hardness and total alkalinity are greater than 100mg/L less than 900mg/L
The circulating water cooling treatment of middle hardness.Also, composite slow-corrosion scale resistor used in the method for the present invention does not contain phosphorus, belongs to green
Environment-friendly type inhibition anti-sludging agent.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first aspect of the present invention provides a kind of processing method of recirculated cooling water, and this method includes, by recirculated cooling water
It is contacted with without phosphorus composite slow-corrosion scale resistor；
Wherein, it is slow to contain compound A, co-polymer of sulfonate, zinc salt and optional copper for the without phosphorus composite slow-corrosion scale resistor
Lose agent, wherein the compound A is hydrolysis of polymaleic anhydride and/or maleic acid-acrylic acid copolymer；
Wherein, the cooling water that follows is the middle hardness that the sum of calcium hardness and total alkalinity are greater than that 100mg/L is less than 900mg/L
Water；The pH value of the recirculated cooling water is 7.9-8.5.
Preferably, the without phosphorus composite slow-corrosion scale resistor is delayed by compound A, co-polymer of sulfonate, zinc salt and optional copper
Lose agent composition.
The present inventor has found that hydrolysis of polymaleic anhydride and/or maleic-acrylic acid are copolymerized in the course of the study
Object and zinc salt can play the role of corrosion inhibition, and co-polymer of sulfonate can play zinc salt in stable recirculated water, prevent CaCO3
The effect of the deposition of dirt and suspended matter.By the way that hydrolysis of polymaleic anhydride and/or maleic acid-acrylic acid copolymer are total to sulfonate
Polymers and zinc salt and optional copper inhibitor are used cooperatively, and while guaranteeing anticorrosion-antiscaling effect, can also reduce its work
Make concentration.Thus the environmental type corrosion inhibiting and descaling agent is had developed, and is used in the sum of calcium hardness and total alkalinity and is greater than
100mg/L is less than 900mg/L and pH value is to achieve good in the processing of middle hardness water of 7.9-8.5 (running pH value naturally)
Effect.
In the present invention, hydrolysis of polymaleic anhydride (HPMA) be orange colour thick liquid, relative density be 1.2 (20 DEG C), one
As relative molecular weight be 400-800, average relative molecular mass about 600 is acid, can ionize, be dissolved in water, decomposition temperature is at 330 DEG C
More than.
In the present invention, as long as with the use of above-mentioned each component and by them in the processing of middle hardness water as above
It achieves the object of the present invention, the content of each component is not required particularly.Under preferable case, in order to further increase inhibition resistance
Dirty effect, relative to the compound A of 100 parts by weight, the content of the co-polymer of sulfonate is 18-600 parts by weight, described
Zinc salt is with Zn2+The content of meter is 3-125 parts by weight, and the content of optional copper inhibitor is 3-75 parts by weight；It is further preferred that
Relative to the compound A of 100 parts by weight, the content of the co-polymer of sulfonate is 30-270 parts by weight, the zinc salt with
Zn2+The content of meter is 4-40 parts by weight, and the content of optional copper inhibitor is 5-50 parts by weight.
The present invention is not particularly limited the type of the co-polymer of sulfonate, in order to further increase corrosion-mitigation scale-inhibition effect
Fruit, it is preferred that the co-polymer of sulfonate be dibasic sulfoacid salt copolymer or ternary co-polymer of sulfonate, it is further preferred that
The co-polymer of sulfonate is selected from acrylic acid/2- acrylamide-2-methyl propane sulfonic copolymer, acrylic acid/2- acrylamide -2-
Methyl propane sulfonic acid/hydroxypropyl acrylate copolymer, acrylic acid/esters/co-polymer of sulfonate, carboxylate/sulfonate/non-from
Sub- copolymer, acrylic/styrene sulfonic acid copolymer, acrylate/Styrene Sulfonic Acid Copolymer, acrylic acid/allyl sulphonic acid
Copolymer, acrylic acid/vinyl sulfonic acid copolymer, acrylic acid/2- methyl -2'- acrylamido propane sulfonic acid copolymer, propylene
Acid/acrylamide/2- methyl -2'- acrylamido propane sulfonic acid copolymer, acrylic acid/maleic acid/2- methyl -2'- third
In acrylamide base propane sulfonic acid copolymer and acrylic acid/esters -2- methyl -2'- acrylamido propane sulfonic acid copolymer
At least one.
In the present invention.The zinc salt can be (molten at 20 DEG C for the common water-soluble zinc salt with corrosion inhibition in this field
Xie Du >=1g/100g water), its type and content is not particularly limited.Preferably, the zinc salt is zinc sulfate and/or chlorine
Change zinc.
In one embodiment of the invention, the without phosphorus composite slow-corrosion scale resistor contains copper inhibitor.The copper is slow
Lose the various heterocyclic compounds with copper corrosion inhibition that agent can be common for this field.It is not special to its type and content
Limitation.Preferably, the copper inhibitor is Azole Corrosion Inhibitors, is preferably selected from benzotriazole, methyl benzotriazazole and sulfydryl
At least one of benzotriazole.
Each component of without phosphorus composite slow-corrosion scale resistor used in the method for the present invention can be kept separately or mix
It saves.
In the preferred embodiment, without phosphorus composite slow-corrosion scale resistor used in the method for the present invention is made of said components.
Each component can be commercially available, and can be provided in the form of a solution, but content involved in the present invention or weight are equal
In terms of effective concentration (content or weight of solute).
A kind of specific embodiment according to the present invention, the without phosphorus composite slow-corrosion scale resistor used in the method for the present invention
In also contain water, and corrosion-mitigation scale-inhibition can be configured to by phosphate-free corrosion inhibition antisludging agent each component as above is proportionally soluble in water
The form of agent solution is spare, can also Shi Zaiyu water cooperation to be used.Preferably, based on the without phosphorus compound slow corrosion of 100 parts by weight
Antisludging agent, the content of water are 30-80 parts by weight, further preferably 40-70 parts by weight.
In the processing method of recirculated cooling water of the invention, the dosage of the without phosphorus composite slow-corrosion scale resistor is not special
Restriction, as long as anticorrosion-antiscaling effect can be played to cooling equipment.Preferably, the dosage of the composite slow-corrosion scale resistor makes
In the recirculated cooling water, the concentration of compound A be 2-16mg/L (for example, can be 2mg/L, 4mg/L, 6mg/L,
8mg/L, 10mg/L, 12mg/L, 14mg/L, 16mg/L), the concentration of co-polymer of sulfonate be 3-12mg/L (for example, can be
3mg/L, 4mg/L, 6mg/L, 8mg/L, 10mg/L, 12mg/L), with Zn2+The concentration of the zinc salt of meter be 0.5-2.5mg/L (for example,
It can be 0.5mg/L, 0.8mg/L, 1.0mg/L, 1.2mg/L, 1.5mg/L, 1.8mg/L, 2.0mg/L, 2.3mg/L, 2.5mg/
L), the concentration of optional copper inhibitor be 0.5-1.5mg/L (for example, can be 0.5mg/L, 0.8mg/L, 1.0mg/L,
1.2mg/L、1.5mg/L)。
In method for treating circulating cooling water provided by the invention, the phosphate-free corrosion inhibition antisludging agent each component, which can cooperate with, matches
Cooperation is used, and in the case where the low component of dosage is few, the corrosivity of middle hardness water can be effectively relieved, stablize Zn in water well2+
Ability, and hinder CaCO3Dirty significant effect.It can be seen that without phosphorus composite slow-corrosion scale resistor as above can be without using phosphorous
Excellent scale inhibitor effect is obtained in the case where component.
In practical application, the without phosphorus composite slow-corrosion scale resistor can be prepared before use, such as according to aforementioned formula
It is added in recirculated cooling water after each component is mixed；It can also be straight without mixing step according to aforementioned formula by each component
It connects and is added in recirculated cooling water.When being directly added into, the addition sequence of each component is not particularly limited.Further, it is also possible to
Each component is mixed with water, adds it in recirculated cooling water after completely dissolution.
For the growth of microorganism in control loop cooling water, in processing cycle cooling water, fungicide can be added
Into recirculated cooling water, the fungicide can add simultaneously simultaneously or not with the component of above-mentioned without phosphorus composite slow-corrosion scale resistor,
And the type and dosage of the fungicide used are well known to the skilled person, details are not described herein.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
Hydrolysis of polymaleic anhydride (HPMA), maleic acid-acrylic acid copolymer (MA/AA), acrylic acid -2- acrylamide -2-
Methyl propane sulfonic acid copolymer (AA/AMPS), acrylic acid/esters/co-polymer of sulfonate (TH-2000), acrylic acid/ethylene sulphur
Acid copolymer, acrylic acid/2- methyl -2'- acrylamido propane sulfonic acid copolymer, acrylic acid/2- acrylamide -2- methyl-prop
Sulfonic acid/hydroxypropyl acrylate copolymer (AA/AMPS/HPA), acrylic acid/acrylamide/2- methyl -2'- acrylamido propane
Sulfonic acid copolymer, acrylate/Styrene Sulfonic Acid Copolymer, acrylic/styrene sulfonic acid copolymer, acrylic acid/allyl sulphur
Acid copolymer, carboxylate-sulfonate-non-ionic copolymer (TH-3100), acrylic acid/esters -2- methyl -2'- acryloyl
Amido propane sulfonic acid copolymer, is purchased from Shandong Taihe Water Treatment Co., Ltd..
The water quality of test water is as shown in table 1.Wherein Ca2+With total alkalinity with CaCO3Meter, wherein Ca2+It is hard to represent calcium
Degree." cooling water analysis and the test that the measuring method of water quality is write referring to production department, China Petrochemical Corporation and development division
Method " (1993, information centre, Anqing general petrochemical works publishes).
Table 1
| Water quality | Ca2+(mg/l) | Total alkalinity (mg/l) | Cl-(mg/l) | PH | Conductivity (μ s/cm) |
| Test water 1 | 430 | 450 | 121 | 8.2 | 1320 |
| Test water 2 | 140 | 165 | 34 | 7.9 | 356 |
Hinder the measurement of calcium carbonate scale performance
Hindering calcium carbonate scale performance test is according to GB/T 16632-2008 " measurement-calcium carbonate of water treatment agent scale-inhibiting properties
Sedimentation " method measure the scale-inhibiting properties of water treatment agent composition of the invention.Detailed process is as follows:
To Ca2+Concentration is 600mg/L, medicament is added in the test water that basicity is 600mg/L, then at 80 ± 1 DEG C of constant temperature
Water-bath inside holding 10h, residue Ca in sampling analysis water after cooling2+Concentration, while doing blank sample, and calculate scale inhibition performance.
Scale inhibition performance calculation formula are as follows:
C: actual measurement Ca2+Concentration
C0: the Ca of blank sample2+Concentration
The measurement of corrosion inhibition
Rotary hanging plate corrosion test is according to GB/T 18175-2000 " measurement-rotary hanging plate of water treatment agent corrosion inhibition
Method " method measure the corrosion inhibition of water treatment agent composition of the invention.Detailed process is as follows:
20# quality carbon steel test piece is fixed on lacing film instrument, is put into the test water 1 added with corrosion inhibiting and descaling agent, it is constant
45 ± 1 DEG C of temperature, revolving speed 75rpm is kept to rotate 72 hours, the weight of record test front and back test piece calculates average corrosion rate.
Average corrosion rate calculation formula are as follows: F=C × Δ W/A × T × ρ
C: computational constant, with mm/a (millimeter/year) be unit when, C=8.76 × 107
Δ W: the corrosion weight loss (gram) of test specimen
A: test specimen area (centimetre2)
T: corrosion test time (hour)
ρ: material for test density (kg/m3)
Dynamic simulation test
Dynamic simulation test is measured according to the method for HG/T 2160-2008 " dynamic analogue test of cooling water method "
The effect of water treatment agent composition of the invention for the water process at simulation loop water scene.Detailed process is as follows:
For simulation loop water field condition, dynamic simulation test has been carried out.With year corrosion rate B (mm/a) and adherency speed
Rate mcm (mg/cm3) evaluated, specific calculation formula is as follows:
Year corrosion rate calculating formula are as follows:
K:3.65 X 106
G: the quality (g) of reduction after test tube corrosion
T: the time (d) of test run
A: test tube corroded area (cm2)
D: density metal (g/cm3)
Adhere to rate calculations formula: mcm=7.2 × 105(W1-W2)/A·t
W1: the weight of test tube, g after test；
W2: the weight of test tube, g after cleaning；
A: the inner surface area before test tube examination, cm2；
T: test period, h.
Stablize zinc salt performance
Distilled water is taken to prepare Ca2+Concentration is 250mgL-1, basicity 250mgL-1, Zn2+For 5mgL-1And 1g/L
Phosphate-free corrosion inhibition antisludging agent is added in the test water of sodium tetraborate, in standing 10 hours, sampling analysis in 80 ± 1 DEG C of waters bath with thermostatic control
Residue Zn in water2+Concentration, while doing blank sample, and calculate resistance zinc rate.
Hinder zinc rate calculation formula are as follows: resistance zinc rate=(C-C0)/(C1-C0) × 100%
C: actual measurement Zn2+Concentration
C0: the Zn of blank sample2+Concentration
C1: the Zn in raw water2+Concentration
Resistance zinc rate is higher, and the stability of zinc salt in water is better, illustrates that the performance for stablizing zinc salt is better.
Total phosphorus determination
Referring to HG/T 3540-2011 " measurement of total phosphate content in industrial circulating cooling water "
Chemical oxygen consumption (COC) measurement
Referring to " the 23rd part of thermal power plant vapour analysis method: the measurement of chemical oxygen consumption (COC) DL/T 502.23-2006
(potassium dichromate method) ", wherein the solution of COD≤30mg/L can be tested with the potassium bichromate solution of 0.025mol/L.
Embodiment 1
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
It is total to weigh the acrylic/styrene sulfonic acid that HPMA, 25.0g active component that 8.0g effective content is 50% is 30%
Polymers, the ZnSO of 4.0g4·7H263.0g water is added in O, shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 1 of required preparation is arrived.
It is added by the concentration of 100mg/L into test water with prepared phosphate-free corrosion inhibition antisludging agent 1, and is measured according to method as above
The resistance CaCO of phosphate-free corrosion inhibition antisludging agent 13Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 2
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh acrylate/styrene sulfonic acid that HPMA, 8.3g active component that 16.0g effective content is 50% are 30%
Copolymer, acrylic acid/allyl sulphonic acid copolymer that 11.7g active component is 30%, the ZnSO of 4.4g4·7H2O is added
59.6g water shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 2 of required preparation is arrived.With prepared phosphate-free corrosion inhibition antisludging agent 2
It is added by the concentration of 100mg/L into test water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 2 as above3
Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 3
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh AA/AMPS, 1.7g that HPMA, 18.3g active component that 20.0g effective content is 50% is 30%
ZnCl2, 60.0g water is added, shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 3 of required preparation is arrived.With prepared without phosphorus slow
Erosion antisludging agent 3 is added by the concentration of 100mg/L into test water, and measures phosphate-free corrosion inhibition antisludging agent 3 according to method as above
Resistance CaCO3Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 4
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh acrylic acid/esters/sulphur that HPMA, 26.7g active component that 24.0g effective content is 50% are 30%
The ZnSO of hydrochlorate copolymer (TH-2000), 5.3g4·7H244.0g water is added in O, shakes up to get the 100.0g of required preparation is arrived
Phosphate-free corrosion inhibition antisludging agent 4.It is added, and pressed into test water by the concentration of 100mg/L with prepared phosphate-free corrosion inhibition antisludging agent 4
According to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 4 as above3Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 5
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
The preparation of phosphate-free corrosion inhibition antisludging agent 5 is carried out according to embodiment 4, unlike, ZnSO4·7H2The dosage of O is 1.8g,
The total amount of phosphate-free corrosion inhibition antisludging agent is complemented into 100.0g with water.With prepared phosphate-free corrosion inhibition antisludging agent 5 by the dense of 100mg/L
It spends and is added into test water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 5 as above3Dirty rate, corrosion rate
With resistance zinc rate, it the results are shown in Table 2.
Embodiment 6
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
The preparation of phosphate-free corrosion inhibition antisludging agent 6 is carried out according to embodiment 4, unlike, 30% acrylic acid-acrylic ester-
The dosage of co-polymer of sulfonate is 5.0g, and the total amount of phosphate-free corrosion inhibition antisludging agent is complemented to 100.0g with water.With prepared nothing
Phosphorus corrosion inhibiting and descaling agent 6 is added by the concentration of 100mg/L into test water, and measures no-phosphate corrosion scale inhibition according to method as above
The resistance CaCO of agent 63Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 7
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
It is total to weigh acrylic acid/vinyl sulfonic acid that HPMA, 21.7g active component that 31.0g effective content is 50% are 30%
The ZnSO of polymers, 3.1g4·7H244.2g water is added in O, shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 7 of required preparation is arrived.
It is added by the concentration of 100mg/L into test water with prepared phosphate-free corrosion inhibition antisludging agent 7, and is measured according to method as above
The resistance CaCO of phosphate-free corrosion inhibition antisludging agent 73Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 8
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh acrylic acid/2- methyl -2'- that MA/AA, 26.7g active component that 6.0g effective content is 50% are 30%
The ZnSO of acrylamido propane sulfonic acid copolymer, 4.9g4·7H262.4g water is added in O, shakes up to get required preparation is arrived
100.0g phosphate-free corrosion inhibition antisludging agent 8.It is thrown by the concentration of 100mg/L into test water with prepared phosphate-free corrosion inhibition antisludging agent 8
Add, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 8 as above3Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table
2。
Embodiment 9
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh acrylic acid/acrylamide that MA/AA, 30.0g active component that 12.0g effective content is 50% is 30%/
The ZnSO of 2- methyl -2'- acrylamido propane sulfonic acid copolymer, 5.3g4·7H252.7g water is added in O, shakes up to get to institute
The 100.0g phosphate-free corrosion inhibition antisludging agent 9 that need to be prepared.With prepared phosphate-free corrosion inhibition antisludging agent 9 by the concentration of 100mg/L to test
It is added in water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 9 as above3Dirty rate, corrosion rate and resistance zinc rate,
It the results are shown in Table 2.
Embodiment 10
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh AA/AMPS/HPA, 3.5g that MA/AA, 18.0g active component that 18.0g effective content is 50% is 30%
ZnSO4·7H260.5g water is added in O, shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 10 of required preparation is arrived.With preparing
Phosphate-free corrosion inhibition antisludging agent 10 added by the concentration of 100mg/L into test water, and it is without phosphorus slow according to method measurement as above
Lose the resistance CaCO of antisludging agent 103Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 11
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh TH-3100,2.6g that MA/AA, 10.0g active component that 24.0g effective content is 50% is 45%
ZnSO4·7H263.4g water is added in O, shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 11 of required preparation is arrived.With prepared
Phosphate-free corrosion inhibition antisludging agent 11 is added by the concentration of 100mg/L into test water, and measures no-phosphate corrosion according to method as above
The resistance CaCO of antisludging agent 113Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 12
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh MA/AA, 13.3g active component that HPMA, 9.0g effective content that 18.0g effective content is 50% is 50%
For 30% acrylic acid/esters/2- methyl -2'- acrylamido propane sulfonic acid copolymer, 3.1g ZnSO4·7H2O,
56.6g water is added, shakes up to get the 100.0g phosphate-free corrosion inhibition antisludging agent 12 of required preparation is arrived.It is hindered with prepared no-phosphate corrosion
Dirty agent 12 is added by the concentration of 100mg/L into test water, and according to method measurement phosphate-free corrosion inhibition antisludging agent 12 as above
Hinder CaCO3Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 13
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh MA/AA, 23.3g active component that HPMA, 12.0g effective content that 4.0g effective content is 50% is 50%
For 30% acrylic acid/esters/co-polymer of sulfonate, 4.9g ZnSO4·7H2O is added 55.8g water, shakes up to get arriving
The 100.0g phosphate-free corrosion inhibition antisludging agent 13 of required preparation.With prepared phosphate-free corrosion inhibition antisludging agent 13 by 100mg/L concentration to
It is added in test water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 13 as above3Dirty rate, corrosion rate and resistance
Zinc rate, the results are shown in Table 2.
Embodiment 14
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh MA/AA, 20.0g active component that HPMA, 7.0g effective content that 7.0g effective content is 50% is 50%
The ZnCl of TH-2000,4.9g that AA/AMPS/HPA, 4.4g active component for 30% is 45%2, 56.7g water is added, shakes up,
The 100.0g phosphate-free corrosion inhibition antisludging agent 14 prepared needed for obtaining.With prepared phosphate-free corrosion inhibition antisludging agent 14 by 100mg/L's
Concentration is added into test water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 14 as above3Dirty rate, corrosion speed
Rate and resistance zinc rate, the results are shown in Table 2.
Embodiment 15
The present embodiment is used to illustrate the corrosion and scale inhibition performance of phosphate-free corrosion inhibition antisludging agent provided by the invention
Weigh MA/AA, 3.3g active component that HPMA, 4.0g effective content that 16.0g effective content is 50% is 50%
The ZnSO of TH-3100,2.9g that TH-2000,5.6g active component for 45% is 45%4·7H2O is added 68.2g water, shakes
It is even to get arrive required preparation 100.0g phosphate-free corrosion inhibition antisludging agent 15.100mg/L is pressed with prepared phosphate-free corrosion inhibition antisludging agent 15
Concentration added into test water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent 15 as above3Dirty rate, corrosion
Rate and resistance zinc rate, the results are shown in Table 2.
Comparative example 1
This comparative example is used to illustrate the corrosion and scale inhibition performance of the phosphate-free corrosion inhibition antisludging agent of reference
The preparation of phosphate-free corrosion inhibition antisludging agent D1 is carried out according to embodiment 4, unlike, zinc salt and sulfonate copolymerization are not added
The total amount of phosphate-free corrosion inhibition antisludging agent is complemented to 100.0g with water by object.100mg/L is pressed with prepared phosphate-free corrosion inhibition antisludging agent D1
Concentration added into test water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent D1 as above3Dirty rate, corrosion
Rate and resistance zinc rate, the results are shown in Table 2.
Comparative example 2
This comparative example is used to illustrate the corrosion and scale inhibition performance of the phosphate-free corrosion inhibition antisludging agent of reference
The preparation of phosphate-free corrosion inhibition antisludging agent D2 is carried out according to embodiment 4, unlike, zinc salt is not added, it will be without phosphorus with water
The total amount of corrosion inhibiting and descaling agent complements to 100.0g.With prepared phosphate-free corrosion inhibition antisludging agent D2 by the concentration of 100mg/L to test
It is added in water, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent D2 as above3Dirty rate, corrosion rate and resistance zinc
Rate the results are shown in Table 2.
Comparative example 3
This comparative example is used to illustrate the corrosion and scale inhibition performance of the phosphate-free corrosion inhibition antisludging agent of reference
The preparation of phosphate-free corrosion inhibition antisludging agent D3 is carried out according to embodiment 4, unlike, HPMA is replaced with to the poly- day of equivalent
Aspartic acid.It is added by the concentration of 100mg/L into test water with prepared phosphate-free corrosion inhibition antisludging agent D3, and according to as above
The resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent D33Dirty rate, corrosion rate and resistance zinc rate, the results are shown in Table 2.
Comparative example 4
This comparative example is used to illustrate the corrosion and scale inhibition performance of the phosphate-free corrosion inhibition antisludging agent of reference
The preparation of phosphate-free corrosion inhibition antisludging agent D4 is carried out according to embodiment 4, unlike, HPMA is replaced with to the Malaysia of equivalent
The copolymer of acid and acrylamide.It is thrown by the concentration of 100mg/L into test water with prepared phosphate-free corrosion inhibition antisludging agent D4
Add, and according to the resistance CaCO of method measurement phosphate-free corrosion inhibition antisludging agent D4 as above3Dirty rate, corrosion rate and resistance zinc rate, are as a result shown in
Table 2.
Table 2
The without phosphorus composite slow-corrosion scale resistor good combination property used in the method for the present invention it can be seen from 2 data of table, has
Good resistance CaCO3Zn in dirty performance, corrosion inhibition and stable water2+Ability.
Simulated experiment 1
For the scene of simulating, dynamic simulation test has been carried out.Dynamic simulation test method presses People's Republic of China's chemical industry
Professional standard HG/T2160-2008 is carried out, and control parameter is as follows:
Water quality: experimental water 2 in table 1
Cycles of concentration control is with calcium hardness+total alkali angle value control:
A tower: greater than 750mg/L is concentrated and is less than 900mg/L
B tower: greater than 750mg/L is concentrated and is less than 900mg/L
Flow velocity: 1.0m/s
Medicament: A tower: the without phosphorus composite slow-corrosion scale resistor D2 of comparative example 2
B tower: the without phosphorus composite slow-corrosion scale resistor 4 of embodiment 4
Inlet temperature: 32 ± 1 DEG C of temperature difference: 10 DEG C
Corrosion rate and test tube adherency rate are shown in Table 3.
The water quality indicator result measured after dynamic simulation test such as table 4.
Table 3
Table 4
It is provided in standard GB/T 50050-2007 " Code for design of industrial recirculating cooling water treatment " 3.1.6, open type system
The corrosion rate of the carbon steel tube wall of system is less than or equal to 0.075mm/a；Production department, China Petrochemical Corporation and development division are compiled
The corrosion rate of " the small-sized experimental analogic method of laboratory " regulation carbon steel is in 0- in " cooling water analysis and the test method " of system
It is " fine " grade between 0.028mm/a, is " good " grade between 0.028-0.056mm/a, being in 0.056-0.070mm/a " can
To allow " grade；It is " fine " grade that speed, which is adhered to, in 0-6mcm, is " good " grade in 6-15mcm, is " can permit " in 15-20mcm
Grade.
It can be seen that being less than 900mg/ in the sum of calcium hardness and total alkalinity using non-Phosphorus composite anti incrustation eorrosion snhibiter of the invention
In the case where L, the corrosion rate of test tube is 0.020mm/a, reaches middle petrochemical industry " fine " grade standard, adheres to rate 7.6mcm, reaches
To " good " grade standard, it is better than inhibition and the scale inhibition effect of comparative formulation.And operation 15 days after measure recirculated water total phosphorus and
COD the results show that total phosphorus almost without COD value is relatively low, is all satisfied petro chemical industry pollutant emission standard GB31570-
Regulation in 2015, i.e. total phosphorus discharge (in terms of P)≤1.0mg/L, chemical oxygen consumption (COC)≤60mg/L.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of processing method of recirculated cooling water, which is characterized in that this method includes, by recirculated cooling water and without phosphorus compound slow
Lose antisludging agent contact；
Wherein, the without phosphorus composite slow-corrosion scale resistor contains compound A, co-polymer of sulfonate, zinc salt and optional copper inhibitor,
Wherein, the compound A is hydrolysis of polymaleic anhydride and/or maleic acid-acrylic acid copolymer；
Wherein, the cooling water that follows is the middle hardness water that the sum of calcium hardness and total alkalinity are greater than that 100mg/L is less than 900mg/L；Institute
The pH value for stating recirculated cooling water is 7.9-8.5.
2. according to the method described in claim 1, wherein, relative to the compound A of 100 parts by weight, the sulfonate is total
The content of polymers is 18-600 parts by weight, and the zinc salt is with Zn2+The content of meter is 3-125 parts by weight, optional copper inhibitor
Content is 3-75 parts by weight.
3. according to the method described in claim 2, wherein, relative to the compound A of 100 parts by weight, the sulfonate is total
The content of polymers is 30-270 parts by weight, and the zinc salt is with Zn2+The content of meter is 4-40 parts by weight, and optional copper inhibitor contains
Amount is 5-50 parts by weight.
4. method described in any one of -3 according to claim 1, wherein the co-polymer of sulfonate is total for dibasic sulfoacid salt
Polymers or ternary co-polymer of sulfonate.
5. according to the method described in claim 4, wherein, the co-polymer of sulfonate is selected from acrylic acid/2- acrylamide -2- first
Base sulphonic acid copolymer, acrylic acid/2- acrylamide-2-methyl propane sulfonic/hydroxypropyl acrylate copolymer, acrylic acid/propylene
Acid esters/co-polymer of sulfonate, carboxylate/sulfonate/non-ionic copolymer, acrylic/styrene sulfonic acid copolymer, acrylic acid
Ester/Styrene Sulfonic Acid Copolymer, acrylic acid/allyl sulphonic acid copolymer, acrylic acid/vinyl sulfonic acid copolymer, acrylic acid/2- first
Base -2'- acrylamido propane sulfonic acid copolymer, acrylic acid/acrylamide/2- methyl -2'- acrylamido propane sulfonic acid are total
Polymers, acrylic acid/maleic acid/2- methyl -2'- acrylamido propane sulfonic acid copolymer and acrylic acid/esters -2-
At least one of methyl -2'- acrylamido propane sulfonic acid copolymer.
6. method described in any one of -5 according to claim 1, wherein the zinc salt is zinc sulfate and/or zinc chloride.
7. method described in any one of -6 according to claim 1, wherein the copper inhibitor is azole compounds.
8. according to the method described in claim 7, wherein, the copper inhibitor is selected from benzotriazole, methyl benzotriazazole
At least one of with sulfydryl benzotriazole.
9. method described in any one of -8 according to claim 1, wherein the without phosphorus composite slow-corrosion scale resistor also contains
Water, the without phosphorus composite slow-corrosion scale resistor based on 100 parts by weight, the content of water are 30-80 parts by weight.
10. method described in any one of -9 according to claim 1, wherein described without phosphorus relative to every liter of recirculated cooling water
The dosage of composite slow-corrosion scale resistor makes in the recirculated cooling water, and the concentration of compound A is 2-16mg/L, co-polymer of sulfonate
Concentration be 3-12mg/L, with Zn2+The concentration of the zinc salt of meter is 0.5-2.5mg/L, and the concentration of optional copper inhibitor is 0.5-
1.5mg/L。
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| CN115140849A (en) * | 2022-06-22 | 2022-10-04 | 北京师范大学 | Linear release type long-acting phosphorus-free scale inhibitor |
| CN115432831A (en) * | 2022-09-21 | 2022-12-06 | 岳阳隆兴实业有限公司 | Non-phosphorus scale and corrosion inhibitor |
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