CN109748402B - Low-phosphorus composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water - Google Patents
Low-phosphorus composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water Download PDFInfo
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Abstract
The invention relates to the field of corrosion and scale inhibition of circulating cooling water, in particular to a low-phosphorus composite corrosion and scale inhibitor, application thereof and a treatment method of circulating cooling water. The low-phosphorus composite corrosion and scale inhibitor contains hydrolyzed polymaleic anhydride, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and/or polyamino polyether methylene phosphonic acid, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor. The treatment method of the circulating cooling water comprises the step of contacting the circulating cooling water with the low-phosphorus composite corrosion and scale inhibitor. The composite corrosion and scale inhibitor has excellent corrosion inhibition performance and can well stabilize Zn in water2+Ability to and CaCO3The corrosion and scale inhibitor has less components and lower consumption, and is especially suitable for the treatment of circulating cooling water with low hardness water quality, such as the sum of calcium hardness and total alkalinity of 100 mg.L‑1The following low-hardness and low-alkali water-based circulating cooling water. Moreover, the composite corrosion and scale inhibitor has low phosphorus content, and belongs to an environment-friendly corrosion and scale inhibitor.
Description
Technical Field
The invention relates to the field of corrosion and scale inhibition of circulating cooling water, in particular to a low-phosphorus composite corrosion and scale inhibitor, application thereof and a treatment method of circulating cooling water.
Background
The circulating cooling water treatment mainly solves the problems of scaling, corrosion and microorganism hazard in a circulating water system. To achieve this goal, a water treatment formulation suitable for water quality conditions must be screened out. The common corrosion and scale inhibitor for domestic and foreign recirculated cooling water treatment is almost a phosphorus water treatment agent compound formula, although they are non-toxic, low-cost and have good corrosion and scale inhibition performance, after discharged into water, the water is easy to cause eutrophication and environmental pollution. With the improvement of global environmental protection and safety consciousness, phosphorus forbidden and limited measures are continuously taken in many countries and regions, and as far as the current limit standard for industrial enterprises in China is concerned, the total phosphorus emission (counted by P) is less than or equal to 1.0mg/L, the total zinc is less than or equal to 2.0mg/L and the chemical oxygen consumption is less than or equal to 60mg/L in the petrochemical industry pollutant emission standard GB 31570-2015; the total phosphorus of newly built plants is less than or equal to 0.3mg/L, the chemical oxygen consumption is less than or equal to 30mg/L, the total zinc is less than or equal to 1.0mg/L, the discharge requirements of phosphorus content and COD are very low, and the research and development of the corrosion and scale inhibitor without phosphorus and low phosphorus are bound to become the key research content of water treatment agents at home and abroad. Meanwhile, as the human beings enter a green age taking 'environmental protection, natural advocation and sustainable development promotion' as a core, green economy becomes the key point of the economic development strategy of the 21 st century. The method aims at environment, performance and economy, and designs and develops a low-phosphorus or phosphorus-free medicament which is easy to biodegrade and has high efficiency and a corresponding treatment scheme according to the principles and ideas of green chemistry and pollution prevention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the low-phosphorus composite corrosion and scale inhibitor which has the characteristics of less components, low phosphorus, low working concentration and environment-friendly green ring.
In order to achieve the above objects, the present invention provides a low-phosphorus composite corrosion and scale inhibitor comprising hydrolyzed polymaleic anhydride, a compound a, a sulfonate copolymer, a zinc salt and optionally a copper corrosion inhibitor; wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid.
Preferably, the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer.
Preferably, the copper corrosion inhibitor is an azole compound.
Preferably, the low-phosphorus composite corrosion and scale inhibitor further contains water in an amount of 30 to 80 parts by weight based on 100 parts by weight of the low-phosphorus composite corrosion and scale inhibitor.
In a second aspect, the invention provides an application of the low-phosphorus composite corrosion and scale inhibitor in circulating cooling water treatment.
In three aspects, the invention provides a treatment method of circulating cooling water, which comprises the step of contacting the circulating cooling water with the low-phosphorus composite corrosion and scale inhibitor.
Preferably, the circulating cooling water is low-hardness water with the sum of calcium hardness and total alkalinity below 100 mg/L.
The composite corrosion and scale inhibitor has excellent corrosion inhibiting performance and can stabilize Zn in water2+Ability to and CaCO3The corrosion and scale inhibitor has less components and lower consumption, and is especially suitable for the treatment of circulating cooling water with low hardness water quality, such as calcium hardness and total alkalinity of 100 mg.L-1The following circulating cooling water treatment of low hardness and low alkali water quality. In addition, the composite corrosion and scale inhibitor has low phosphorus content, and belongs to an environment-friendly corrosion and scale inhibitor.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the invention provides a low-phosphorus composite corrosion and scale inhibitor, which contains hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor; wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid.
Preferably, the low-phosphorus composite corrosion and scale inhibitor consists of hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, zinc salt and an optional copper corrosion inhibitor.
The inventor of the invention discovers in the process of research that the phosphorus-free agent is adopted to hydrolyze polymaleic anhydride (HPMA), the low-phosphorus agent 2-phosphonobutane-1, 2, 4-tricarboxylic acid (namely 2-phosphonobutane-1, 2, 4-tricarboxylic acid and PBTCA) and/or polyamino polyether methylene Phosphonic Acid (PAPEMP), and the compound of the phosphorus-free agent, the 2-phosphonobutane-1, 2, 4-tricarboxylic acid and the PBTCA and/or the PAPEMP and the copolymer of zinc salt and sulfonate has good corrosion and scale inhibition performance, can omit the use of other organic phosphine agents, and has low PBTCA and/or PAPEMP dosage. The hydrolyzed polymaleic anhydride and the zinc salt can play a role in corrosion inhibition, and the sulfonate copolymer can play a role in stabilizing the zinc salt in the circulating water, so that the zinc salt can be well stabilized in the water to play a role in corrosion inhibition; PBTCA and PAPEMP play roles in inhibiting scale and dispersing and preventing CaCO3Deposition of scale and suspended matter. The components are compounded for use, and each component can play a good synergistic effect. When the method is applied to circulating water treatment, the harm of a common organic phosphine agent to the environment due to high phosphorus content can be reduced.
In the invention, the hydrolyzed polymaleic anhydride (HPMA) is orange viscous liquid, the relative density is 1.2(20 ℃), the general relative molecular weight is 400-800, the average relative molecular weight is about 600, and the hydrolyzed polymaleic anhydride is acidic, can be ionized, can be dissolved in water, and has the decomposition temperature of over 330 ℃.
In the present invention, the object of the present invention can be achieved by using the above components in combination, and the content of each component is not particularly required. Preferably, in order to further improve the corrosion and scale inhibition effect, the content of the compound A is 5-300 parts by weight, the content of the sulfonate copolymer is 10-300 parts by weight, and the zinc salt is Zn based on 100 parts by weight of hydrolyzed polymaleic anhydride2+5-125 parts by weight of optional copper corrosion inhibitor, and 5-75 parts by weight of optional copper corrosion inhibitor; more preferably, the content of the compound A is 5-100 parts by weight, the content of the sulfonate copolymer is 10-180 parts by weight, and the zinc salt is Zn relative to 100 parts by weight of hydrolyzed polymaleic anhydride2+10-65 parts by weight of optional copper corrosion inhibitorThe content of (B) is 10-50 parts by weight.
The type of the sulfonate copolymer is not particularly limited in the present invention, and in order to further improve the corrosion and scale inhibition effect, it is preferable that the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer, and it is further preferable that the sulfonate copolymer is selected from the group consisting of an acrylic acid/2-acrylamide-2-methylpropanesulfonic acid copolymer, an acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer, an acrylic acid/acrylate/sulfonate copolymer, a carboxylate/sulfonate/nonionic copolymer, an acrylic acid/styrene sulfonic acid copolymer, an acrylate/styrene sulfonic acid copolymer, an acrylic acid/allyl sulfonic acid copolymer, an acrylic acid/vinyl sulfonic acid copolymer, an acrylic acid/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, a salt of a carboxylic acid/sulfonic acid/nonionic copolymer, an acrylic acid/, At least one of acrylic acid/acrylamide/2-methyl-2 ' -acrylamidopropanesulfonic acid copolymer, acrylic acid/maleic acid/2-methyl-2 ' -acrylamidopropanesulfonic acid copolymer, and acrylic acid/acrylate-2-methyl-2 ' -acrylamidopropanesulfonic acid copolymer.
In the invention. The zinc salt can be water-soluble zinc salt with corrosion inhibition performance (the solubility is more than or equal to 1g/100g water at 20 ℃) which is common in the field, and the type and the content of the zinc salt are not particularly limited. Preferably, the zinc salt is selected from zinc sulphate and/or zinc chloride.
In one embodiment of the invention, the low-phosphorous composite corrosion and scale inhibitor contains a copper corrosion inhibitor. The copper corrosion inhibitor can be various heterocyclic compounds with copper corrosion inhibition performance commonly seen in the field. The kind and content thereof are not particularly limited. Preferably, the copper corrosion inhibitor is an azole corrosion inhibitor, preferably at least one selected from benzotriazole, methylbenzotriazole and mercaptobenzotriazol.
The components of the low-phosphorus composite corrosion and scale inhibitor can be stored independently or in a mixed manner.
In a preferred embodiment, the low-phosphorus composite corrosion and scale inhibitor consists of the components. The individual components are commercially available and may be provided in the form of a solution, but the contents or weights referred to in the present invention are each in terms of an effective concentration (content or weight of solute).
According to a specific embodiment of the invention, the low-phosphorus composite corrosion and scale inhibitor further contains water, and the components of the low-phosphorus corrosion and scale inhibitor can be dissolved in water according to a proportion to prepare a corrosion and scale inhibitor solution for standby application, or can be matched with water when in use. Preferably, the water content is 30 to 80 parts by weight, more preferably 40 to 75 parts by weight, based on 100 parts by weight of the low-phosphorous composite corrosion and scale inhibitor.
The second aspect of the invention provides the application of the low-phosphorus composite corrosion and scale inhibitor in circulating cooling water treatment.
In a third aspect of the invention, there is provided a method of treating recirculated cooling water, which comprises contacting recirculated cooling water with a low-phosphorous composite corrosion and scale inhibitor as described above.
In the treatment method of the circulating cooling water of the present invention, the amount of the low-phosphorous composite corrosion and scale inhibitor is not particularly limited as long as the corrosion and scale inhibition effect on the cooling equipment is achieved. Preferably, the composite corrosion and scale inhibitor is used in an amount such that the concentration of the hydrolyzed polymaleic anhydride in the circulating cooling water is 2-10mg/L (for example, 2mg/L, 4mg/L, 6mg/L, 8mg/L, 10mg/L), the concentration of the compound A is 0.5-6mg/L (for example, 0.5mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L), the concentration of the sulfonate copolymer is 1-6mg/L (for example, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L), and Zn is used2+The concentration of zinc salt is 0.5-2.5mg/L (e.g., 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), and the concentration of optional copper corrosion inhibitor is 0.5-1.5mg/L (e.g., can be 0.5mg/L, 0.8mg/L, 1.0mg/L, 1.2mg/L, 1.5 mg/L).
The inventor of the invention finds that the low-phosphorus corrosion and scale inhibitor provided by the invention is particularly suitable for low-hardness high-corrosivity near-circulation cooling water with the sum of calcium hardness and total alkalinity below 100 mg/L. In the method for treating the circulating cooling water, the components of the low-phosphorus corrosion and scale inhibitor provided by the invention can be cooperated with each other, and the low-phosphorus corrosion and scale inhibitor has low consumption and less componentsUnder the condition, the corrosion of low-hardness water can be effectively relieved, and Zn in water can be well stabilized2+Ability of (C) and resistance of CaCO3The scale effect is obvious. Therefore, the low-phosphorus composite corrosion and scale inhibitor can obtain excellent corrosion and scale inhibition effects under the condition of low phosphorus content.
In practical application, the low-phosphorus composite corrosion and scale inhibitor can be prepared before use, for example, the components are mixed according to the formula and then added into circulating cooling water; the components can also be added directly to the recirculating cooling water in accordance with the foregoing formulation without a mixing step. When directly added, the order of addition of the respective components is not particularly limited. In addition, the components can be mixed with water to be fully dissolved and then added into circulating cooling water.
In order to control the growth of microorganisms in the circulating cooling water, a bactericide can be added into the circulating cooling water when the circulating cooling water is treated, the bactericide can be added simultaneously or not simultaneously with the components of the low-phosphorus composite corrosion and scale inhibitor, and the type and the using amount of the bactericide used are well known to those skilled in the art and are not described again.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples,
hydrolyzed polymaleic anhydride (HPMA), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), polyaminopolyether methylenephosphonic acid (PAPEMP), acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer (AA/AMPS), acrylic acid/acrylate/sulfonate copolymer (TH-2000), acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer (AA/AMPS/HPA), acrylic acid/styrenesulfonic acid copolymer, acrylic acid/vinylsulfonic acid copolymer, acrylic acid/allylsulfonic acid copolymer, carboxylate-sulfonate-nonionic copolymer (TH-3100), acrylic acid/acrylate-2-methyl-2' -acrylamidopropanesulfonic acid copolymer, both from Tai and Water treatment Co., Ltd, Shandong province.
The water quality of the test water is shown in Table 1. Wherein Ca2+And total alkalinity are all as CaCO3In which Ca is counted2+Represents calciumHardness. The water quality determination method refers to the analysis and test method of cooling water (1993, published by the information center of the general petrochemical plant in Anqing) compiled by the Ministry of production and development of the general petrochemical company of China.
TABLE 1
| Quality of water | Ca2+(mg/l) | Total alkalinity (mg/l) | Cl-(mg/l) | PH | Conductivity (μ s/cm) |
| Test Water 1 | 40 | 45 | 16 | 7.2 | 180 |
| Test Water 2 | 14 | 19 | 8 | 7.0 | 78 |
Determination of Corrosion inhibition Performance
The rotating hanging piece corrosion test is to measure the corrosion inhibition performance of the water treatment medicament composition according to the method of GB/T18175-. The specific process is as follows:
fixing a No. 20 high-quality carbon steel test piece on a coupon instrument, putting the test piece into test water added with a corrosion and scale inhibitor, keeping the temperature at 45 +/-1 ℃, keeping the rotating speed at 75rpm for 72 hours, recording the weight of the test piece before and after the test, and calculating the average corrosion speed.
The average corrosion rate is calculated by the formula: f ═ CxDeltaW/A × T × ρ
C, calculating constant, when mm/a (millimeter/year) is taken as unit, C is 8.76 multiplied by 107
Δ W: corrosion weight loss of test piece (gram)
A: area of test piece (cm)2)
T: corrosion test time (hours)
ρ: density of test piece material (kg/m)3)
Dynamic simulation test
The dynamic simulation test is to determine the effect of the water treatment medicament composition of the invention on simulating the water treatment of a circulating water field according to the method of HG/T2160-2008 cooling water dynamic simulation test method. The specific process is as follows:
in order to simulate the circulating water field condition, a dynamic simulation test is carried out. Annual corrosion rate B (mm/a) and adhesion rate mcm (mg/cm)3) The evaluation is carried out according to the following specific calculation formula:
the annual corrosion rate is calculated by the formula:
K：3.65ⅹ106
g: mass (g) reduced after tube corrosion
T: time of test run (d)
A: corrosion area of test tube (cm)2)
D: metal density (g/cm)3)
Adhesion rate calculation formula: mcm is 7.2 × 105(W1-W2)/A·t
W1: weight of test tube after test, g;
W2: weight of tube after washing, g;
a: internal surface area, cm, of test tube before test2；
t: test time, h.
Stabilization of zinc salt properties
Preparing Ca from distilled water2+The concentration is 250 mg.L-1Alkalinity of 250 mg.L-1，Zn2+Is 5 mg.L-1And 1g/L of sodium tetraborate as test water, adding a low-phosphorus corrosion and scale inhibitor, standing for 10 hours in a constant-temperature water bath at the temperature of 80 +/-1 ℃, sampling and analyzing residual Zn in the water2+And (4) simultaneously making blank samples, and calculating the zinc resistance rate.
The zinc resistance rate calculation formula is as follows: the zinc resistance rate is (C-C0)/(C1-C0). times.100%
C measured Zn2+Concentration of (2)
C0 blank Zn2+Concentration of (2)
C1 Zn in raw water2+Concentration of (2)
The higher the zinc inhibition rate, the better the stability of the zinc salt in water, which indicates that the performance of stabilizing the zinc salt is better.
Total phosphorus determination
See HG/T3540 & 2011 determination of total phosphate content in industrial circulating cooling water
Chemical oxygen consumption determination
See DL/T502.23-2006 section 23 of method for steam analysis in thermal power plants: in the determination of chemical oxygen consumption (potassium dichromate method), the solution with COD less than or equal to 30mg/L can be tested by 0.025mol/L potassium dichromate solution.
Example 1
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 5.0g of HPMA with effective content of 50%, 5.0g of PBTCA with effective content of 50%, and 15.0g of acrylic acid/acrylic acid with active component of 30%Ester/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, 7.1g of ZnSO4·7H2And O, adding 67.9g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 1 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 1 is added into test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 1 are measured according to the method, and the result is shown in Table 2.
Example 2
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 7.0g of HPMA with effective content of 50%, 2.4g of PBTCA with effective content of 50%, 8.3g of acrylic acid/vinyl sulfonic acid copolymer with active component of 30%, 8.3g of acrylic acid/2-methyl-2' -acrylamide propane sulfonic acid copolymer and 5.3g of ZnSO4·7H2And O, adding 68.7g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 2 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 2 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 2 are measured according to the method, and the result is shown in Table 2.
Example 3
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 9.0g of HPMA with effective content of 50%, 3.8g of PAPEMP with effective content of 40%, 9.3g of AA/AMPS with active component of 30%, and 3.6g of ZnCl2And adding 74.3g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 3 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 3 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 3 are measured according to the method, and the result is shown in Table 2.
Example 4
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 9.0g of HPMA with effective content of 50%, 3.6g of PBTCA with effective content of 50%, 11.1g of AA/AMPS/HPA with active component of 45%, and 10.2g of ZnSO4·7H2O, 66.1g ofAnd (3) shaking uniformly to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 4 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 4 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 4 are measured according to the method, and the result is shown in Table 2.
Example 5
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 15.0g of HPMA with effective content of 50%, 5.0g of PAPEMP with effective content of 40%, 12.2g of TH-2000 with active component of 45%, and 7.9g of ZnSO4·7H2And O, adding 59.9g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 5 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 5 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 5 are measured according to the method, and the result is shown in Table 2.
Example 6
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
16.0g of 50% effective HPMA, 4.4g of 40% effective PBTCA, 11.6g of 45% active ingredient TH-3100, 9.3g of ZnSO4·7H2And O, adding 58.7g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 6 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 6 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 6 are measured according to the method, and the result is shown in Table 2.
Example 7
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
18.0g of 50% strength HPMA, 6.3g of 40% strength PAPEMP, 11.7g of an acrylic acid/allylsulfonic acid copolymer having 30% strength as active component, 7.1g of ZnSO were weighed out4·7H2And O, adding 56.9g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 7 required to be prepared. Adding the prepared low-phosphorus corrosion and scale inhibitor 7 into the test water 1 according to the concentration of 100mg/L, and addingThe corrosion rate and zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 7 were measured in the same manner as described above, and the results are shown in Table 2.
Example 8
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 19.0g of HPMA with effective content of 50%, 1.0g of PBTCA with effective content of 50%, 1.9g of PAPEMP with effective content of 40%, 8.3g of acrylate/styrene sulfonic acid copolymer with active component of 30%, and 6.2g of ZnSO4·7H2And O, adding 63.6g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 8 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 8 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 8 are measured according to the method, and the result is shown in Table 2.
Example 9
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Weighing 15.0g of HPMA with effective content of 50%, 1.0g of PBTCA with effective content of 50%, 1.9g of PAPEMP with effective content of 40%, 8.3g of acrylate/styrene sulfonic acid copolymer with active component of 30%, and 5.1g of ZnSO4·7H2And O, adding 68.7g of water, and shaking up to obtain 100.0g of the low-phosphorus corrosion and scale inhibitor 9 required to be prepared. The prepared low-phosphorus corrosion and scale inhibitor 9 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor 9 are measured according to the method, and the result is shown in Table 2.
Example 10
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
Preparation of phosphorus-free corrosion and scale inhibitor 10 was carried out as in example 5, except that ZnSO4·7H2The dosage of O is 3.1g, and the total amount of the phosphorus-free corrosion and scale inhibitor is complemented to 100.0g by water. The prepared phosphorus-free corrosion and scale inhibitor 10 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the phosphorus-free corrosion and scale inhibitor 10 are measured according to the method, and the result is shown in Table 2.
Example 11
This example is used to illustrate the corrosion and scale inhibition performance of the low-phosphorous corrosion and scale inhibitor provided by the present invention
The formulation of the phosphorus-free corrosion and scale inhibitor 11 was carried out as in example 5, except that the amount of TH-2000 was 1.1g, and the total amount of the phosphorus-free corrosion and scale inhibitor was made up to 100.0g with water. The prepared phosphorus-free corrosion and scale inhibitor 11 is added into the test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the phosphorus-free corrosion and scale inhibitor 11 are measured according to the method, and the result is shown in Table 2.
Comparative example 1
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The low phosphorus corrosion and scale inhibitor D1 was formulated as in example 1, except that the zinc salt was not added and the total amount of low phosphorus corrosion and scale inhibitor was made up to 100.0g with water. The prepared low-phosphorus corrosion and scale inhibitor D1 is added into test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor D1 are measured according to the method, and the results are shown in Table 2.
Comparative example 2
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The low phosphorus corrosion and scale inhibitor D2 was formulated as in example 1, except that the total amount of low phosphorus corrosion and scale inhibitor was made up to 100.0g with water without adding HPMA. The prepared low-phosphorus corrosion and scale inhibitor D2 is added into test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor D2 are measured according to the method, and the results are shown in Table 2.
Comparative example 3
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The low phosphorous corrosion and scale inhibitor D3 was formulated as in example 1, except that HPMA was replaced with an equal amount of polyaspartic acid. The prepared low-phosphorus corrosion and scale inhibitor D3 is added into test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor D3 are measured according to the method, and the results are shown in Table 2.
Comparative example 4
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The low phosphorus corrosion and scale inhibitor D4 was formulated as in example 1, except that HPMA was replaced with an equal amount of a copolymer of maleic acid and acrylamide. The prepared low-phosphorus corrosion and scale inhibitor D4 is added into test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor D4 are measured according to the method, and the results are shown in Table 2.
Comparative example 5
The comparative example is used for explaining the corrosion and scale inhibition performance of the reference low-phosphorus corrosion and scale inhibitor
The formulation of the low phosphorus corrosion and scale inhibitor D1 was carried out as in example 1, except that PBTCA was not added and the total amount of low phosphorus corrosion and scale inhibitor was made up to 100.0g with water. The prepared low-phosphorus corrosion and scale inhibitor D1 is added into test water 1 according to the concentration of 100mg/L, and the corrosion rate and the zinc inhibition rate of the low-phosphorus corrosion and scale inhibitor D1 are measured according to the method, and the results are shown in Table 2.
TABLE 2
| Examples/comparative examples | Corrosion rate/mm.a-1(Water for test 1) | Zinc resistance (%) |
| Example 1 | 0.042 | 70.1 |
| Comparative example 1 | 0.259 | 47.3 |
| Comparative example 2 | 0.119 | 49.0 |
| Comparative example 3 | 0.108 | 56.8 |
| Comparative example 4 | 0.099 | 60.2 |
| Comparative example 5 | 0.221 | 63.5 |
| Example 2 | 0.053 | 62.4 |
| Example 3 | 0.043 | 76.1 |
| Example 4 | 0.017 | 78.6 |
| Example 5 | 0.014 | 82.4 |
| Example 6 | 0.012 | 80.6 |
| Example 7 | 0.021 | 75.1 |
| Example 8 | 0.027 | 69.0 |
| Example 9 | 0.023 | 64.3 |
| Example 10 | 0.183 | 79.3 |
| Example 11 | 0.114 | 56.3 |
As can be seen from the data in Table 2, the low-phosphorus composite corrosion and scale inhibitor has good comprehensive performance, good corrosion inhibition performance and Zn stabilization in water2+The ability of the cell to perform.
Simulation experiment 1
To simulate the field, dynamic simulation tests were performed. The dynamic simulation test method is carried out according to the chemical industry standard HG/T2160-2008 of the people's republic of China, and the control parameters are as follows:
water quality: experimental Water 2 in Table 1
The concentration multiple is controlled by calcium hardness and total alkalinity value:
concentrating the A tower: more than 70 and less than 100mg/L
Tower B: more than 70 and less than 100mg/L
Flow rate: 1.0m/s
Medicament: tower A: low-phosphorus composite corrosion and scale inhibitor 1 of example 1
Tower B: comparative example 1 low-phosphorus composite corrosion and scale inhibitor D1
Inlet temperature: temperature difference of 32. + -. 1 ℃: 10 deg.C
The corrosion rate and tube adhesion rate are shown in table 3.
The results of the water quality index measured after the dynamic simulation test are shown in Table 4.
TABLE 3
TABLE 4
The corrosion speed of the carbon steel pipe wall of the open system is less than or equal to 0.075mm/a as specified in national standard GB 50050-2007 design Specification for Industrial circulating Cooling Water treatment 3.1.6; in the cooling water analysis and test method compiled by the production department and the development department of the general company of petrochemical industry, the laboratory small simulation test method stipulates that the corrosion speed of carbon steel is in a good grade between 0 and 0.028mm/a, in a good grade between 0.028 and 0.056mm/a and in an allowable grade between 0.056 and 0.070 mm/a; the adhesion speed is of the order of "good" at 0-6mcm, of "good" at 6-15mcm and of "permissible" at 15-20 mcm.
Therefore, when the sum of the calcium hardness and the total alkalinity is less than 100mg/L, the corrosion rate of the test tube is 0.024mm/a, the good-grade standard of the medium petrochemical industry is achieved, the adhesion rate is 1.5 mm, the good-grade standard is achieved, and the corrosion and scale inhibition effects of the low-phosphorus composite scale and corrosion inhibitor are better than those of the formula of the comparative example. And the results of measuring the total phosphorus and COD of the circulating water after 15 days of operation show that the total phosphorus is almost absent, the COD value is lower, and the total phosphorus and the COD value meet the requirements in the discharge standard GB31570-2015 of pollutants for the petrochemical industry, namely the total phosphorus discharge (measured by P) is less than or equal to 1.0mg/L, and the chemical oxygen consumption is less than or equal to 60 mg/L.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. The low-phosphorus composite corrosion and scale inhibitor is characterized by comprising hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer and zinc salt;
wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid;
wherein, relative to 100 weight parts of hydrolyzed polymaleic anhydride, the content of the compound A is 5 to 300 weight parts, the content of the sulfonate copolymer is 10 to 300 weight parts, and the zinc salt is Zn2+The content is 5-125 weight portions.
2. The low-phosphorous composite corrosion and scale inhibitor according to claim 1, wherein the compound a is present in an amount of 5 to 100 parts by weight, the sulfonate copolymer is present in an amount of 10 to 180 parts by weight, and the zinc salt is Zn in an amount of 100 parts by weight of hydrolyzed polymaleic anhydride2+The content is 10-65 weight portions.
3. The low-phosphorous composite corrosion and scale inhibitor according to claim 1 or 2, wherein the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer.
4. The low-phosphorous composite corrosion and scale inhibitor according to claim 3, wherein the sulfonate copolymer is selected from the group consisting of acrylic acid/2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer, acrylic acid/acrylate/sulfonate copolymer, carboxylate/sulfonate/nonionic copolymer, acrylic acid/styrenesulfonic acid copolymer, acrylate/styrenesulfonic acid copolymer, acrylic acid/allylsulfonic acid copolymer, acrylic acid/vinylsulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, and mixtures thereof, At least one of acrylic acid/maleic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer and acrylic acid/acrylate-2-methyl-2' -acrylamidopropanesulfonic acid copolymer.
5. The low-phosphorous composite corrosion and scale inhibitor according to claim 1 or 2, wherein the zinc salt is selected from zinc sulfate and/or zinc chloride.
6. The low-phosphorus composite corrosion and scale inhibitor is characterized by comprising hydrolyzed polymaleic anhydride, a compound A, a sulfonate copolymer, a zinc salt and a copper corrosion inhibitor;
wherein the compound A is 2-phosphonobutane-1, 2, 4-tricarboxylic acid and/or polyaminopolyether methylene phosphonic acid;
wherein, relative to 100 weight parts of hydrolyzed polymaleic anhydride, the content of the compound A is 5 to 300 weight parts, the content of the sulfonate copolymer is 10 to 300 weight parts, and the zinc salt is Zn2+The calculated content is 5-125 weight portions, and the content of the copper corrosion inhibitor is 5-75 weight portions.
7. The low-phosphorous composite corrosion and scale inhibitor according to claim 6, wherein the compound A is present in an amount of 5 to 100 parts by weight, the sulfonate copolymer is present in an amount of 10 to 180 parts by weight, and the zinc salt is Zn based on 100 parts by weight of hydrolyzed polymaleic anhydride2+The calculated content is 10-65 weight portions, and the content of the copper corrosion inhibitor is 10-50 weight portions.
8. The low-phosphorus composite corrosion and scale inhibitor according to claim 6 or 7, wherein the sulfonate copolymer is a disulfonate copolymer or a trisulfonate copolymer.
9. The low-phosphorous composite corrosion and scale inhibitor according to claim 8, wherein the sulfonate copolymer is selected from the group consisting of acrylic acid/2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylic acid/2-acrylamide-2-methylpropanesulfonic acid/hydroxypropyl acrylate copolymer, acrylic acid/acrylate/sulfonate copolymer, carboxylate/sulfonate/nonionic copolymer, acrylic acid/styrenesulfonic acid copolymer, acrylate/styrenesulfonic acid copolymer, acrylic acid/allylsulfonic acid copolymer, acrylic acid/vinylsulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, and mixtures thereof, At least one of acrylic acid/maleic acid/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer and acrylic acid/acrylate-2-methyl-2' -acrylamidopropanesulfonic acid copolymer.
10. The low-phosphorous composite corrosion and scale inhibitor according to claim 6 or 7, wherein the zinc salt is selected from zinc sulfate and/or zinc chloride.
11. The low-phosphorous composite corrosion and scale inhibitor according to claim 6 or 7, wherein the copper corrosion inhibitor is an azole compound.
12. The low-phosphorous composite corrosion and scale inhibitor according to claim 11, wherein the copper corrosion inhibitor is at least one selected from benzotriazole, methylbenzotriazole and mercaptobenzotriazole.
13. A low-phosphorus composite corrosion and scale inhibitor solution, characterized in that the low-phosphorus composite corrosion and scale inhibitor consists of the low-phosphorus composite corrosion and scale inhibitor of any one of claims 1 to 12 and water, wherein the water content is 30 to 80 parts by weight based on 100 parts by weight of the low-phosphorus composite corrosion and scale inhibitor.
14. Use of the low-phosphorus composite corrosion and scale inhibitor according to any one of claims 1 to 12 or the low-phosphorus composite corrosion and scale inhibitor solution according to claim 13 in circulating cooling water treatment.
15. A method for treating circulating cooling water, which comprises contacting the circulating cooling water with the low-phosphorus composite corrosion and scale inhibitor according to any one of claims 1 to 12 or the solution of the low-phosphorus composite corrosion and scale inhibitor according to claim 13.
16. The method of claim 15, wherein the recirculated cooling water is a low hardness water having a calcium hardness plus total alkalinity below 100 mg/L.
17. The method according to claim 15 or 16, wherein the low-phosphorus composite corrosion and scale inhibitor or the low-phosphorus composite corrosion and scale inhibitor solution is used in an amount such that the concentration of hydrolyzed polymaleic anhydride, the concentration of compound a, and the concentration of sulfonate copolymer are 2-10mg/L, 0.5-6mg/L, and 1-6mg/L, in terms of Zn, in the circulating cooling water per liter of circulating cooling water2+The concentration of the zinc salt is 0.5-2.5 mg/L.
18. The method according to claim 15 or 16, wherein the low-phosphorus composite corrosion and scale inhibitor or the low-phosphorus composite corrosion and scale inhibitor solution is used in an amount such that the concentration of hydrolyzed polymaleic anhydride, the concentration of compound a, and the concentration of sulfonate copolymer are 2-10mg/L, 0.5-6mg/L, and 1-6mg/L, in terms of Zn, in the circulating cooling water per liter of circulating cooling water2+The concentration of the zinc salt is 0.5-2.5mg/L, and the concentration of the copper corrosion inhibitor is 0.5-1.5 mg/L.
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| CN110937699A (en) * | 2019-12-17 | 2020-03-31 | 武汉金鼎新环保科技有限公司 | Compound scale and corrosion inhibitor |
| CN112811620A (en) * | 2021-01-04 | 2021-05-18 | 山东天庆科技发展有限公司 | Low-phosphorus scale and corrosion inhibitor for circulating water |
| CN114262071B (en) * | 2021-09-18 | 2023-10-20 | 自然资源部天津海水淡化与综合利用研究所 | Application of carbon steel corrosion inhibitor in reclaimed water heating network transmission and distribution |
| CN113830905A (en) * | 2021-09-28 | 2021-12-24 | 国网河南省电力公司桐柏县供电公司 | Transformer circulating cooling water corrosion and scale inhibitor and preparation method thereof |
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