CN107304082A - A kind of corrosion-mitigation scale-inhibition sterilization composition and its application - Google Patents
A kind of corrosion-mitigation scale-inhibition sterilization composition and its application Download PDFInfo
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- CN107304082A CN107304082A CN201610248731.7A CN201610248731A CN107304082A CN 107304082 A CN107304082 A CN 107304082A CN 201610248731 A CN201610248731 A CN 201610248731A CN 107304082 A CN107304082 A CN 107304082A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
- C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The present invention relates to water treatment field, disclose a kind of corrosion-mitigation scale-inhibition sterilization composition and its application, the composition contains water-soluble pink salt, organic phospho acid, hydroxycarboxylate, nitrogen-containing heterocycle compound and copolymer, the copolymer contains the construction unit provided by the methyl propane sulfonic acid of 2 acrylamido 2, on the basis of the total amount of the copolymer, the percentage by weight of the construction unit provided by the methyl propane sulfonic acid of 2 acrylamido 2 is more than 20%, wherein, the water-soluble pink salt, organic phospho acid, hydroxycarboxylate, the weight ratio of nitrogen-containing heterocycle compound and copolymer is 1:1‑20:0.5‑6:0.5‑6:1 20, the weight of water-soluble pink salt is based on tin ion.The corrosion-mitigation scale-inhibition sterilization of the present invention has preferably inhibition, scale inhibition and bactericidal property concurrently with composition, and dosage is relatively low when using.
Description
Technical field
The present invention relates to water treatment field, in particular it relates to a kind of corrosion-mitigation scale-inhibition sterilization composition and its cold circulating
But the application in water process.
Background technology
The problem of recirculated cooling water longtime running can bring corrosion and scaling and bacterial growth, it is necessary to add respectively corrosion inhibiter,
Antisludging agent and bactericide.Nontoxic, the efficient multifunctional water treating agent of research is the direction of medicament research and development.Most petrochemical industry
Enterprise's application is all compound corrosion inhibiting and descaling agent.It is widely used formula have phosphorus system (by Quadrafos, polycarboxylic acids and
Copolymer, zinc salt etc. are constituted), full stress-strain system is (by organic phospho acid, polycarboxylic acids and copolymer, azole compounds with or without zinc salt
Composition) etc..During water treatment agent is added, the compatibility issues of anti-incrustation corrosion inhibitor and bactericide are commonly present.It is conventional at present
Chlorine series bactericidal agent have oxidation to many anti-incrustation corrosion inhibitors, so as to reduce anticorrosion-antiscaling effect.
CN102578088A discloses a kind of compound drug that there is sterilization corrosion-mitigation scale-inhibition to act on, including polyamide-based, season
Ammonium salt class, organic phospho acid polymer, inorganic salts, water, the compound drug stability is good, easy compounding, simple to operate, cost
Low, low toxicity is nuisanceless, belongs to environmental protection water treatment agent.But the large usage quantity of the medicament when in use.
CN102730851A discloses a kind of water treatment agent and preparation method thereof for having corrosion-mitigation scale-inhibition and effect of killing livestock concurrently.
The water treatment agent is poly-epoxy succinic acid/Bronopol copolymer, and the copolymer is not phosphorous, biodegradable, and due to
The presence of oxidisability bromine atoms also has certain effect of killing livestock.But the corrosion mitigating effect of the medicament is general, bactericidal effect also compared with
Difference.
Therefore, the less water treatment agent of dosage has when research and development have preferable inhibition, scale inhibition and bactericidal property, used
Important meaning.
The content of the invention
The invention aims to overcome existing water treatment agent to be difficult to be provided simultaneously with preferable inhibition, scale inhibition and bactericidal properties
Can it is not enough there is provided it is a kind of there is preferable inhibition, scale inhibition and bactericidal property, use when the relatively low water treatment agent of dosage.
The present inventor has found under study for action, water-soluble pink salt, hydroxycarboxylate and nitrogen-containing heterocycle compound three
There is obvious synergistic corrosion inhibition, copolymer can play a part of stable tin ion, in addition, water-soluble pink salt hydrolysis generation
Stannic hydroxide has bactericidal action, obtains having concurrently the medicament of corrosion-mitigation scale-inhibition bactericidal property with organic phospho acid after compounding.Therefore, use
The corrosion-mitigation scale-inhibition sterilization need not add bactericide in addition with compositions-treated recirculated cooling water, or only need to add a small amount of sterilization
Agent, with regard to good corrosion-mitigation scale-inhibition bactericidal effect can be reached.
Therefore, to achieve these goals, the invention provides a kind of corrosion-mitigation scale-inhibition sterilization composition, said composition contains
There are water-soluble pink salt, organic phospho acid, hydroxycarboxylate, nitrogen-containing heterocycle compound and copolymer, the copolymer contains by 2- third
Acrylamide base -2- methyl propane sulfonic acids provide construction unit, on the basis of the total amount of the copolymer, by 2- acrylamidos -
2- methyl propane sulfonic acids provide construction unit percentage by weight more than 20%, wherein, the water-soluble pink salt, organic phosphine
Acid, hydroxycarboxylate, the weight ratio of nitrogen-containing heterocycle compound and copolymer are 1:1-20:0.5-6:0.5-6:1-20, it is water-soluble
The weight of pink salt is based on tin ion.
In addition, the application present invention also offers above-mentioned composition in processing cycle cooling water.
The corrosion-mitigation scale-inhibition sterilization of the present invention has preferably inhibition, scale inhibition and bactericidal property concurrently with composition, is added when using
Amount is relatively low.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In the present invention, in the case where not making opposite explanation, the weight of various materials is according to effective dose (or butt
Amount) meter, such as the amount of polymer (including various homopolymers and copolymer) is with its butt gauge.
The corrosion-mitigation scale-inhibition sterilization composition that the present invention is provided contains water-soluble pink salt, organic phospho acid, hydroxycarboxylate, contained
Nitrogen heterocyclic and copolymer, the copolymer contain the construction unit provided by 2- acrylamide-2-methylpro panesulfonic acids,
On the basis of the total amount of the copolymer, the weight percent of the construction unit provided by 2- acrylamide-2-methylpro panesulfonic acids
Than more than 20%, wherein, the water-soluble pink salt, organic phospho acid, hydroxycarboxylate, nitrogen-containing heterocycle compound and copolymer
Weight ratio is 1:(1-20):(0.5-6):(0.5-6):(1-20), the weight of water-soluble pink salt is based on tin ion.
Preferably, the weight ratio of the water-soluble pink salt and organic phospho acid is 1:(4-16) (such as 1:4、1:5、1:5.5、1:
8、1:10、1:11、1:12、1:14、1:15、1:Arbitrary value between 16 or aforementioned value)；And/or the water-soluble pink salt with
The weight ratio of hydroxycarboxylate is 1:(1-4) (such as 1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:Between 4 or aforementioned value
Arbitrary value)；And/or the weight ratio of the water-soluble pink salt and nitrogen-containing heterocycle compound is 1:(1.5-5) (such as 1:1.5、1:2、
1:2.5、1:3、1:3.5、1:4、1:4.5、1:Arbitrary value between 5 or aforementioned value)；And/or the water-soluble pink salt is together
The weight of polymers than for weight ratio be 1:(4-16) (such as 1:4、1:5、1:8、1:8.5、1:10、1:11、1:12、1:14、1:
15、1:Arbitrary value between 16 or aforementioned value).
Wherein, the content between each above-mentioned composition can be with identical or different.Preferably, the composition is by mentioned component
Composition.
According to the present invention, the water-soluble pink salt can for the common water-soluble pink salt in this area (solubility at 20 DEG C >=
1g/100g water).Preferably, the water-soluble pink salt in stannic chloride, stannous chloride, STANNOUS SULPHATE CRYSTALLINE and nitric acid tin at least one
Kind.
According to the present invention, the organic phospho acid can be the common various phosphonic acids in this area (such as carbon number be 1-10 (such as
C1、C2、C3、C4、C5、C6、C7、C8、C9Or C10)) phosphonic acids).Preferably, the organic phospho acid is 1-hydroxy ethylidene-1,1-diphosphonic acid
(HEDP), ATMP (ATMP), 2- phosphonate group -1,2,4- butane tricarboxylates (PBTCA), 2- hydroxyethylidene diphosphonic acid guanidine-acetic acids
(HPAA), ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, the methylenephosphonic acid of glycine two, paddy ammonia
At least one of sour two methylenephosphonic acids, the methylenephosphonic acid of sulfamic acid two and the methylenephosphonic acid of tarine two, more preferably hydroxyl
At least one of base ethylene-diphosphonic acid, 2- phosphonate group -1,2,4- butane tricarboxylates and 2- hydroxyethylidene diphosphonic acid guanidine-acetic acids.Water-soluble tin
Salt has good synergy with organic phospho acid, and excellent anticorrosion-antiscaling effect is resulted in processing cycle cooling water.
According to the present invention, hydroxycarboxylate's (saturation) can be the metal salt of the common hydroxyl carboxylic acid in this area
(such as sodium salt and/or sylvite), such as C3-C10(such as C3、C4、C5、C6、C7、C8、C9Or C10) saturated hydroxy carboxylic acid salt.It is preferred that feelings
Under condition, the hydroxycarboxylate is selected from sodium gluconate, sodium tartrate, sodium citrate, sodium lactate, natrium malicum, gluconic acid
At least one of potassium, potassium tartrate, potassium citrate, potassium lactate and potassium malate.
According to the present invention, the nitrogen-containing heterocycle compound be hetero atom be nitrogen heterocyclic compound (hetero atom (nitrogen-atoms)
Quantity be 1,2 or 3).In the present invention, the heterocyclic compound can be the common various nitrogen heterocyclic ring chemical combination in this area
Thing, is preferably selected from (substituted or unsubstituted) five member ring heterocyclic compound, (substituted or unsubstituted) 6-membered heterocyclic compound and (takes
In generation, is unsubstituted) (such as phenyl ring condenses obtained heterocyclic compound and/or phenyl ring and six to benzene-fused heterocyclic compound with five-ring heterocycles
At least one of the obtained heterocyclic compound of circle heterocycles fusion), for example, (substituted or unsubstituted) pyrroles, (substitution does not take
Generation) benzopyrrole, (substituted or unsubstituted) imidazoles, (substituted or unsubstituted) benzimidazole, (substituted or unsubstituted)
Pyrazoles, (substituted or unsubstituted) pyridine, (substituted or unsubstituted) pyrazine, (substituted or unsubstituted) pyrimidine, (substitution or not
Substitution) benzopyrazoles, (substituted or unsubstituted) benzopyrazines, (substituted or unsubstituted) benzo pyrimidine, (substitution or do not take
At least one of generation) quinoline, (substituted or unsubstituted) isoquinolin and (substituted or unsubstituted) BTA.
Wherein, substituted group can be phenyl, hydroxyl, amino, methoxyl group, nitro and C1-C3Alkyl (such as methyl) in
At least one.
It is further preferred that the nitrogen-containing heterocycle compound is selected from benzopyrrole, 2-methylimidazole, 3,5- diphenyl pyrroles
Azoles, 2- phenylpyridines, 2- HYDROXYPYRAZINEs, 2- amino -5- methoxy pyrimidines, 4- methylquinolines, 5- nitroisoquinolines, the nitrogen of benzo three
At least one of azoles and methyl benzotriazazole.
According to the present invention, on the basis of the total amount of the copolymer, provided by 2- acrylamide-2-methylpro panesulfonic acids
The percentage by weight of construction unit (preferably 20-30%) more than 20%.The weight for the other structures unit that the copolymer contains
Measure percentage (preferably 70-80%) below 80%.
Preferably, Limiting Viscosity of the copolymer at 30 DEG C is that 0.06-0.1dl/g (is preferably 0.07-0.08dl/
g)。
According to the present invention, as long as the copolymer contains the structure list provided by 2- acrylamide-2-methylpro panesulfonic acids
Member, the other structures unit contained to it is had no particular limits, and preparation water process can be commonly used in by this area
The various monomers of agent are provided.Preferably, the other structures unit that the copolymer contains (is not 2- acrylamido -2- methyl
Propane sulfonic acid) it is organic by unsaturated organic acid, the salt of unsaturated organic acid, unsaturated organic acid acid anhydride, unsaturated amides and unsaturation
At least one of acid esters or at least two offers.
The unsaturated organic acid is preferably acrylic acid, maleic acid, C1-C10Unsaturated phosphonic acids and C2-C10Unsaturation
At least one of sulfonic acid.The C2-C10Unsaturated sulfonic acid (or C1-C10Unsaturated phosphonic acids) can for it is various it is conventional not
Saturation sulfonic acid (or phosphonic acids), and in addition to alkyl, alkenyl and sulfonic group, phenyl, amide groups etc. can also be contained.It is described
C2-C10Unsaturated sulfonic acid for example can be styrene sulfonic acid, allyl sulphonic acid, vinyl sulfonic acid and 2- methyl -2'- acrylamides
At least one of base propane sulfonic acid etc..The C1-C10Unsaturated phosphonic acids for example can be 2- acrylamido -2- methyl-props
Phosphonic acids.
The salt of the unsaturated organic acid can be the salt (such as sodium salt and/or sylvite) of above-mentioned unsaturated organic acid.
The unsaturated organic acid acid anhydride is the acid anhydrides (such as maleic anhydride) of above-mentioned unsaturated organic acid.
The acid amides that the unsaturated amides can be formed for above-mentioned unsaturated organic acid, such as acrylamide and/or methyl-prop
Acrylamide.
The unsaturated organic acid ester is ester (such as acrylate (such as acrylic acid C of above-mentioned unsaturated organic acid1-C8(C1、
C2、C3、C4、C5、C6、C7Or C8) ester), such as methyl acrylate or hydroxypropyl acrylate).
It is highly preferred that the other structures unit that the copolymer contains is by acrylic acid, maleic anhydride, acrylamide, methyl
At least one in acrylamide, styrene sulfonic acid, SSS, methyl acrylate, ethyl acrylate, hydroxypropyl acrylate
Plant or at least two provide.
It is further preferred that the other structures unit that the copolymer contains is by acrylic acid, acrylamide, acrylic acid and third
Acrylamide, acrylic acid and methyl acrylate, acrylic acid and ethyl acrylate, acrylic acid and hydroxypropyl acrylate, acrylic acid and horse
Come acid anhydrides, acrylic acid and styrene sulfonic acid, acrylic acid and SSS, acrylic acid and 2- acrylamido -2- methyl-props
Phosphonic acids or acrylamide and Methacrylamide are provided.
In practical application, can such as match somebody with somebody using the corrosion-mitigation scale-inhibition sterilization composition is preceding prepared according to foregoing
Side is added in recirculated cooling water after each component is mixed；Can also by each component according to aforementioned formula without blend step
It is directly added into recirculated cooling water.The corrosion-mitigation scale-inhibition of composition is influenceed to sterilize effect in order to prevent water-soluble pink salt from occurring hydrolysis
Really, under preferable case, first organic phospho acid, hydroxycarboxylate, nitrogen-containing heterocycle compound and copolymer are added in recirculated cooling water,
Water-soluble pink salt is added, similarly, the addition to organic phospho acid, hydroxycarboxylate, nitrogen-containing heterocycle compound and copolymer is suitable
Sequence is not limited.In actual use, effective dosage (weight in terms of butt) of the copolymer can be 2-10mg/L.
Present invention also offers application of the above-mentioned composition in processing cycle cooling water.The consumption of the composition is preferred
For 6.5-28mg/L recirculated waters, more preferably 11-21.5mg/L recirculated waters.
The present invention will be described in detail by way of examples below.
In following examples, various organic phospho acids are purchased from the strong Yilong Industry Co., Ltd. in Luoyang；It is safe that copolymer is purchased from Shandong
With water process Science and Technology Co., Ltd..
In following examples, the water quality for testing raw water is as shown in table 1.Wherein Ca2+, total alkalinity and total hardness be with CaCO3
Meter, what the assay method of water quality was write with reference to production department of China Petrochemical Corporation and development division《Cool down water analysis and experiment
Method》(1993, information centre of Anqing general petrochemical works publishes).
Table 1
Test case 1
The stability of copolymer is evaluated in accordance with the following methods.
Distilled water is taken to prepare Ca2+Concentration is 250mg/L, the test water that basicity is 250mg/L and tin ion is 5mg/L,
Copolymer (1-8) is added according to table 2, the remaining tin ion in standing 10 hours, sampling analysis water in 80 ± 1 DEG C of waters bath with thermostatic control
Concentration (is measured) by potassium dichromate method, while doing blank sample, and calculates steady tin rate.Steady tin rate is higher, illustrates pink salt in water
Stability it is better, illustrate that the performance of the stable pink salt of copolymer is more excellent.
Surely tin rate calculation formula is：Steady tin rate=(C-C0)/(C1-C0) × 100%
C：Survey the concentration (mg/L) of tin ion
C0：The concentration (mg/L) of the tin ion of blank sample
C1：The concentration (mg/L) of tin ion in raw water
Table 2
The structure that the 2- acrylamide-2-methylpro panesulfonic acids containing specified quantitative are provided it can be seen from the result of the test of table 2
The copolymer of unit has good stabilization to pink salt, far superior to other copolymers.
Embodiment 1-4
According to shown in table 3 toward adding medicament in test water and carry out scale inhibition, inhibition and bactericidal property test, specific test
Method is as follows.* mg/L described in table 3 represent effectively (butt) content, and pink salt is according to tin ion meter.
The evaluation of scale-inhibiting properties
Medicament is added into test water, is concentrated by evaporation in 80 ± 1 DEG C of waters bath with thermostatic control, to 5 times of cycles of concentration, sampling point
Residue Ca in bleed2+Concentration, while doing blank sample, and calculate scale inhibition performance.The calculation formula of scale inhibition performance is：Scale inhibition performance=(C-
C0)/(nC1-C0) × 100%, wherein,
C：Residue Ca in water2+Concentration (mg/L)
C0：The Ca of blank sample2+Concentration (mg/L)
C1：Ca in raw water2+Concentration (mg/L)
n：Cycles of concentration
The evaluation of corrosion inhibition
20# quality carbon steel test pieces are fixed on lacing film instrument, is put into and has added medicament according to each embodiment or comparative example
In test water (experiment raw water concentrates 5 times and obtained, uncomfortable pH value), steady temperature is 40 ± 1 DEG C, keeps rotating speed to be revolved for 75rpm
Turn 72h, the weight of test piece, calculates average corrosion rate (F) before and after record experiment.PH value is not adjusted in process of the test.Average corruption
Erosion speed (F) calculation formula be：F=(C × △ W)/(A × T × ρ), wherein,
C：Computational constant, during with mm/a (millimeter/year) for unit, C=8.76 × 107
△W：The corrosion weight loss (g) of test specimen
A：Area (the cm of test specimen2)
T：The corrosion test time (h)
ρ：Density (the kg/m of material for test3)
The measure of bactericidal property
The assay method of medicament disinfecting performance is worked out with reference to production department of China Petrochemical Corporation and development division《Cooling
Water analysis and test method》In《The static sterilization test of heterotroph》Regulation.
Table 3
From the results shown in Table 3 corrosion-mitigation scale-inhibition sterilization of the invention had concurrently with composition preferably inhibition, scale inhibition and
Bactericidal property.
Comparative example 1
Medicament is added in the way of embodiment 1, unlike, copolymer 1 is copolymerized thing 6 and replaced, and measures scale inhibition performance and is
62.8%, F are 0.085mm/a, the sterilizing rate of different time (1h, 4h, 8h, 12h and 24h) is respectively 81.7%, 74.1%,
58.9%th, 49.3% and 30.1%.
Comparative example 2
Medicament is added in the way of embodiment 1, unlike, copolymer 1 is copolymerized thing 7 and replaced, and measures scale inhibition performance and is
59.6%, F are 0.092mm/a, the sterilizing rate of different time (1h, 4h, 8h, 12h and 24h) is respectively 81.0%, 71.9%,
55.8%th, 41.7% and 29.1%.
Embodiment 5
For the scene of simulating, dynamic analog test has been carried out.Dynamic analog test method presses People's Republic of China's chemical industry
Professional standard HG/T2160-91 is carried out, and control parameter is as follows.
Water quality：Raw water 1 is tested, 1 is shown in Table.
Cycles of concentration：The B towers 4.0 ± 0.2 of A towers 4.0 ± 0.2
pH：A towers control 8.0 ± 0.2 B towers control 8.0 ± 0.2
Flow velocity：1.0m/s
Medicament：
A towers：Weigh HEDP, 1g grape that PBTCA, 8g effective content that 4g effective contents are 50 weight % are 50 weight %
Sodium saccharate, 1.5g BTAs, 26.7g solid contents are 30 weight % copolymer 1, are dissolved in 57.3g water, are eventually adding
1.5g Tin tetrachloride pentahydrates, make it fully dissolve, and shake up, that is, the 100g medicaments of preparation needed for obtaining.
When being added with the medicament prepared by 100mg/L drug concentration into water, PBTCA, HEDP, gluconic acid in water
Sodium, BTA, copolymer 1, the valid density of tin ion be respectively 2mg/L, 4mg/L, 1mg/L, 1.5mg/L, 8mg/L and
0.5mg/L。
B towers：Weigh ATMP, 33.3g that HPAA, 12g effective content that 8g effective contents are 50 weight % are 50 weight %
Solid content is 30 weight % copolymer 8, is dissolved in 42.6g water, is eventually adding 4.1g nitric acid tin, it is fully dissolved, shake up,
The 100g medicaments of preparation needed for obtaining.
When being added with the medicament prepared by 100mg/L drug concentration into water, HPAA in water, ATMP, copolymer 8,
The valid density of tin ion is respectively 4mg/L, 6mg/L, 10mg/L and 2mg/L.
Inlet temperature：32 ± 1 DEG C of temperature difference：10℃
Heterotroph monitoring result is shown in Table 4 during dynamic analog test, and test tube the results are shown in Table 5.
Table 4
Table 5
Standard GB/T 50050-95《Code for design of industrial recirculating cooling water treatment》3.1.6 middle regulation, open type system
Carbon steel tube wall corrosion rate be less than or equal to 0.125mm/a；Production department of China Petrochemical Corporation and development division establishment
's《Cool down water analysis and test method》In《The small-sized experimental analogic method of laboratory》Provide the corrosion rate of carbon steel in 0-
It is " fine " level between 0.028mm/a, is " good " level between 0.028-0.056mm/a, being in 0.056-0.070mm/a " can
To allow " level；It is " fine " level that speed, which is adhered to, in 0-6mcm, is " good " level in 6-15mcm, is " can allow " in 15-20mcm
Level.
As can be seen here, using the corrosion-mitigation scale-inhibition sterilization composition of the present invention, the corrosion rate of test tube is 0.021mm/a,
Sinopec " fine level " standard is reached, speed 5.1mcm is adhered to, " fine level " standard is reached, better than comparative example.Result of the test table
Composition good combination property is used in bright corrosion-mitigation scale-inhibition sterilization of the invention, with good resistance calcium carbonate scale performance and corrosion inhibition,
Also there is good bactericidal property, it is adaptable to the processing of recirculated cooling water.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of corrosion-mitigation scale-inhibition sterilization composition, it is characterised in that said composition contains water-soluble pink salt, organic phospho acid, hydroxyl
Yl carboxylic acid salt, nitrogen-containing heterocycle compound and copolymer, the copolymer contains to be provided by 2- acrylamide-2-methylpro panesulfonic acids
Construction unit, on the basis of the total amount of the copolymer, the construction unit provided by 2- acrylamide-2-methylpro panesulfonic acids
Percentage by weight more than 20%, wherein, the water-soluble pink salt, organic phospho acid, hydroxycarboxylate, nitrogen-containing heterocycle compound
Weight ratio with copolymer is 1:1-20:0.5-6:0.5-6:1-20, the weight of water-soluble pink salt is based on tin ion.
2. composition according to claim 1, wherein, it is the water-soluble pink salt, organic phospho acid, hydroxycarboxylate, nitrogenous
The weight ratio of heterocyclic compound and copolymer is 1:4-16:1-4:1.5-5:4-16.
3. composition according to claim 1 or 2, wherein, the water-soluble pink salt is selected from stannic chloride, stannous chloride, sulphur
At least one of sour tin and nitric acid tin.
4. composition according to claim 1 or 2, wherein, the organic phospho acid is C1-C10Organic phospho acid, be preferably
1-hydroxy ethylidene-1,1-diphosphonic acid, ATMP, 2- phosphonate group -1,2,4- butane tricarboxylates, 2- hydroxyethylidene diphosphonic acids guanidine-acetic acid, second two
The methylenephosphonic acid of amine four, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, the methylenephosphonic acid of glycine two, the methene phosphine of glutamic acid two
At least one of acid, the methylenephosphonic acid of sulfamic acid two and the methylenephosphonic acid of tarine two.
5. composition according to claim 1 or 2, wherein, the hydroxycarboxylate is C3-C10Saturated hydroxy carboxylic acid
Salt, it is preferable that the hydroxycarboxylate is selected from sodium gluconate, sodium tartrate, sodium citrate, sodium lactate, natrium malicum, grape
At least one of saccharic acid potassium, potassium tartrate, potassium citrate, potassium lactate and potassium malate.
6. composition according to claim 1 or 2, wherein, the nitrogen-containing heterocycle compound is selected from substituted or unsubstituted
In five member ring heterocyclic compound, substituted or unsubstituted 6-membered heterocyclic compound and substituted or unsubstituted benzene-fused heterocyclic compound
It is at least one, it is preferable that the nitrogen-containing heterocycle compound is selected from benzopyrrole, 2-methylimidazole, 3,5- diphenylpypazoles, 2- benzene
Yl pyridines, 2- HYDROXYPYRAZINEs, 2- amino -5- methoxy pyrimidines, 4- methylquinolines, 5- nitroisoquinolines, BTA and first
At least one of base BTA.
7. composition according to claim 1 or 2, wherein, Limiting Viscosity of the copolymer at 30 DEG C is 0.06-
0.1dl/g。
8. the composition according to claim 1,2 or 7, wherein, the other structures unit that the copolymer contains is by insatiable hunger
With at least one in organic acid, the salt of unsaturated organic acid, unsaturated organic acid acid anhydride, unsaturated amides and unsaturated organic acid ester
Plant or at least two provide；
Preferably, the other structures unit that the copolymer contains is by acrylic acid, maleic anhydride, acrylamide, methacryl
At least one of amine, styrene sulfonic acid, SSS, methyl acrylate, ethyl acrylate, hydroxypropyl acrylate or extremely
Few two kinds of offers；
It is highly preferred that the other structures unit that contains of the copolymer by acrylic acid, acrylamide, acrylic acid and acrylamide,
Acrylic acid and methyl acrylate, acrylic acid and ethyl acrylate, acrylic acid and hydroxypropyl acrylate, acrylic acid and maleic anhydride,
Acrylic acid and styrene sulfonic acid, acrylic acid and SSS, acrylic acid and 2- acrylamido -2- methylpropanephosphonic acids or
Acrylamide and Methacrylamide are provided.
9. application of the composition in processing cycle cooling water in claim 1-8 described in any one.
10. application according to claim 9, wherein, the consumption of the composition is 6.5-28mg/L recirculated waters, is preferably
11-21.5mg/L recirculated waters.
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| WO2023124953A1 (en) * | 2021-12-31 | 2023-07-06 | 中国石油天然气股份有限公司 | Bactericidal corrosion inhibitor as well as preparation method therefor and use thereof |
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| CN107304082B (en) | 2020-05-12 |
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