CN106477740B - Circulating water treatment composition and its processing method of application and recirculated water - Google Patents
Circulating water treatment composition and its processing method of application and recirculated water Download PDFInfo
- Publication number
- CN106477740B CN106477740B CN201510541700.6A CN201510541700A CN106477740B CN 106477740 B CN106477740 B CN 106477740B CN 201510541700 A CN201510541700 A CN 201510541700A CN 106477740 B CN106477740 B CN 106477740B
- Authority
- CN
- China
- Prior art keywords
- heterocyclic compound
- composition
- water
- concentration
- recirculated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to chemical industry to clean field, discloses a kind of circulating water treatment composition, it is 1 that the composition, which contains weight ratio,：2.5 40 heterocyclic compound and hydrophilic colloid, heterocyclic compound include the second heterocyclic compound that the first heterocyclic compound and hetero atom that hetero atom is sulphur and nitrogen are nitrogen.The composition preferably also contains without phosphorus polymer.The invention also discloses a kind of processing method of recirculated water, including：Initial period：The heterocyclic compound of 3 12mg/L and the hydrophilic colloid of 30 120mg/L are added, carries out the pre- film of room temperature；Enriching stage：The without phosphorus polymer of 6 30mg/L is added, starts thermic load and moisturizing；Stabilization sub stage：Continue moisturizing and blowdown, add a concentration of 1 4mg/L that medicament causes heterocyclic compound in recirculated water, a concentration of 10 40mg/L of hydrophilic colloid, a concentration of 2 10mg/L of without phosphorus polymer.In addition, the invention also discloses application of the composition as prefilming agent or corrosion inhibiting and descaling agent in circulating water treatment.The composition of the present invention is not phosphorous, can effectively realize pre- film and scale inhibitor.
Description
Technical field
The present invention relates to cleaning chemical fields, and in particular, to a kind of circulating water treatment composition and its application and follows
The processing method of ring water.
Background technology
Mainly corrosion and scaling and the microbial growth three major issues solved are needed in recirculated cooling water operational process.Its
Middle microorganism is mainly controlled by fungicide.It is to have two opposite trend being closely connected each other to corrode with fouling,
The balance between the two trend is grasped, is the key that solve this two large problems.Therefore, the control of corrosion and fouling is generally selected
Composite drug, often there are certain concertednesses between each single dose in composite drug, can preferably play scale inhibitor
Effect.
It is at present main corrosion inhibiter mostly using organic phospho acid in circulating water treatment composite drug, it is stronger in water quality corrosivity
When, it also needs to add in phosphate to enhance the corrosion mitigating effect of formula.Even with the zinc salt that can quickly form precipitation membrane, due to it
Film quality is soft to be easily destroyed, and still needs to be used cooperatively with phosphorous medicament.However, the discharge due to phosphorus can lead to the eutrophy of water body
Change, the use of high phosphorous reagent combination is more and more limited.Low-phosphorous, without phosphorus formula of corrosion and scale inhibitor is developed to open as water treatment agent
The direction of hair.
Before recirculating cooling water system is driven, cleaning and pre- film are carried out to system.So-called pre- film is directed to add in system
Prefilming agent generates one layer of mistake with the protective film of anti-corrosion effect by physics chemical action in the metal surface cleaned up
Journey.Pre-film plan can be divided into two major class：One kind is the pre-film plan of proprietary formula, composition and matching during day-to-day operation later
Direct contact is had no between Fang Zucheng, the row's of increasing rate of water make-up is needed after pre- film, to system into line replacement, in operation and management compared with
It is cumbersome.At present, the pre-film plan of domestic widely used proprietary formula is mainly the compound prescription of Quadrafos and zinc salt.Though
Right pre-film effect is good, but added amount of chemical is big, and the phosphorus and Zn content after pre- film in waste water are high, exists to environment water potential
Pollution risk.Another kind of is the pre-film plan for improving concentration, the characteristics of this kind of pre-film plan be pre- film formulation composition with it is normal
Running between the composition of formula has a close contact, and after the completion of pre- film, prefilming agent is replaced naturally in the process of running, normal operation
When need to only keep the corrosion inhibiter of low concentration that protective film can be made to be maintained and repair, it is relatively simple in operation and management.
Therefore, exploitation has more Practical significance suitable for improving the low-phosphorous medicament of the pre-film plan of concentration.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide it is a kind of it is new can be used for it is without phosphorus in circulating water treatment
Composition and its processing method of application and recirculated water.
The hydrophilic colloids such as xanthans, guar gum and Arabic gum (natural polysaecharides hydrophilic colloid) are big due to having
Molecule special construction and colloid property, and with multiple functions, can be used as emulsifier, stabilizer, gelling thickener, size,
Film forming agent etc., is widely used in all fields of national economy, and for it, as corrosion inhibiter, research in this area has not yet been reported.So
And the present inventor the study found that by be used cooperatively hydrophilic colloid and heterocyclic compound can effectively realize pre- film and
Corrosion-mitigation scale-inhibition.
It therefore, to achieve these goals, should in a first aspect, the present invention provides a kind of circulating water treatment composition
Composition contains heterocyclic compound and hydrophilic colloid, and the weight ratio of the heterocyclic compound and hydrophilic colloid is 1：2.5-
40, the heterocyclic compound includes the second jeterocyclic chemistry that the first heterocyclic compound and hetero atom that hetero atom is sulphur and nitrogen are nitrogen
Close object.Preferably, the composition also contains without phosphorus polymer.
Second aspect, the present invention provides the sides that a kind of composition using described in first aspect carries out circulating water treatment
Method, this method include the following steps：
(1) water running initial period is recycled：Add the heterocyclic compound of 3-12mg/L recirculated waters and 30-120mg/L cycles
The hydrophilic colloid of water carries out the pre- film of room temperature；
(2) water running enriching stage is recycled：The without phosphorus polymer of 6-30mg/L recirculated waters is added, start thermic load and is mended
Water；
(3) the recirculated water stable stage：Continue moisturizing and blowdown, when concentration of the hydrophilic colloid in recirculated water reaches
During 10-40mg/L recirculated waters, heterocyclic compound, hydrophilic colloid and without phosphorus polymer are added so that heterocyclic compound in recirculated water
A concentration of 1-4mg/L recirculated waters of object, a concentration of 10-40mg/L recirculated waters of hydrophilic colloid, without phosphorus polymer it is a concentration of
2-10mg/L recirculated waters.
The third aspect, the present invention provides the composition as prefilming agent or corrosion inhibiting and descaling agent in circulating water treatment
Using.
The composition of the present invention is not phosphorous, environmentally friendly.Moreover, the composition of the present invention is used for circulating water treatment
When, it can effectively realize pre- film and/or scale inhibitor.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, term " heterocyclic compound " refers to the object of cyclic structure being made of carbon atom and hetero atom
Matter, however it is not limited to the definition of compound (pure substance), it is a variety of different with the cyclic structure being made of carbon atom and hetero atom
The mixture of compound be also contained in the range of the heterocyclic compound that defines of the present invention, also referred to as " heterocyclic type inhibition
Agent ", " heterocycle type organic " or " heterocyclic substance " etc..
(without phosphorus) circulating water treatment composition provided by the invention contains heterocyclic compound and hydrophilic colloid, described miscellaneous
The weight ratio of cycle compound and hydrophilic colloid is 1：2.5-40 preferably 1：4-40, the heterocyclic compound include hetero atom
The first heterocyclic compound and hetero atom for sulphur and nitrogen are the second heterocyclic compound of nitrogen.
In the present invention, first heterocyclic compound can be the common various heterocyclic compounds in this field, preferably
(substituted or unsubstituted) five member ring heterocyclic compound and/or (substituted or unsubstituted) benzene-fused heterocyclic compound (such as phenyl ring and five
The heterocyclic compound that circle heterocyclic ring condenses), for example, (substituted or unsubstituted) thiazole and/or (substituted or unsubstituted) benzene
And thiazole.In first heterocyclic compound, substituted group can be sulfydryl, amino and C1-C3Alkyl (such as methyl) at least
One.It is highly preferred that first heterocyclic compound is selected from 2-mercaptobenzothiazole, thiazolamine, 2- amino -4- methyl thiazoliums
At least one of azoles, 2- amino -4- methylbenzothiazoles and 2- aminobenzothiazoles.
In the present invention, second heterocyclic compound can be that the common various nitrogen-containing heterocycle compounds in this field are (miscellaneous
The quantity of atom (nitrogen-atoms) be 1,2 or 3), be preferably selected from (substituted or unsubstituted) five member ring heterocyclic compound, (substitution or not
Substitution) (such as phenyl ring and five-ring heterocycles condense for 6-membered heterocyclic compound and (substituted or unsubstituted) benzene-fused heterocyclic compound
To the heterocyclic compound that condenses of heterocyclic compound and/or phenyl ring and hexa-member heterocycle) at least one of, for example, (substitution
Or it is unsubstituted) pyrroles, (substituted or unsubstituted) benzopyrrole, (substituted or unsubstituted) imidazoles, (substitution or it is unsubstituted
) benzimidazole, (substituted or unsubstituted) pyrazoles, (substituted or unsubstituted) pyridine, (substituted or unsubstituted) pyrazine,
(substituted or unsubstituted) pyrimidine, (substituted or unsubstituted) benzopyrazoles, (substituted or unsubstituted) benzopyrazines, (substitution
Or it is unsubstituted) benzo pyrimidine, (substituted or unsubstituted) quinoline, (substituted or unsubstituted) isoquinolin and (substitution or do not take
At least one of generation) benzotriazole.In second heterocyclic compound, substituted group can be phenyl, hydroxyl, amino,
Nitro and C1-C3At least one of alkyl (such as methyl).
It is highly preferred that second heterocyclic compound is selected from benzopyrrole, 2-methylimidazole, 2- phenylpyridines, 2- hydroxyls
In pyrazine, 2- amino -5- methoxy pyrimidines, 4- methylquinolines, 5- nitroisoquinolines, benzotriazole and methyl benzotriazazole
At least one.
Weight ratio between first heterocyclic compound and the second heterocyclic compound does not require particularly, Ke Yiwei
1：0.25-4 (preferably 1:1).
In the present invention, the hydrophilic colloid be natural polysaecharides hydrophilic colloid, such as natural gum (water can be dissolved in and formed
The heteroglycan of sticky solution, referring to Wang Jingyan etc.,《Biochemistry》The third edition first volume page 51).Under preferable case, the parent
Aqueous colloidal is selected from least one of xanthans, guar gum and Arabic gum.
By being used cooperatively heterocyclic compound and hydrophilic colloid, composition of the invention is especially suitable for circulating water treatment
In pre- film step.Therefore, the present invention also provides the above-mentioned composition for containing heterocyclic compound and hydrophilic colloid as pre-
Application of the film in circulating water treatment.The composition of the present invention is as prefilming agent in use, dosage is preferably 30-135mg/L
Recirculated water.
In the present invention, the composition can also contain without phosphorus polymer further to realize the corrosion-mitigation scale-inhibition of recirculated water.
The weight ratio of the heterocyclic compound and without phosphorus polymer is preferably 1：0.5-10, more preferably 1：1-10.
Preferably, the limit of the without phosphorus polymer sticks number as 0.03-0.1dl/g.
It is highly preferred that the without phosphorus polymer is without phosphorus homopolymer (such as C3-C10(C3、C4、C5、C6、C7、C8、C9Or C10) no
The without phosphorus homopolymer of saturated carboxylic acid), it is further preferably poly- selected from poly-aspartate, poly-epoxy succinic acid, polyacrylic acid and hydrolysis
At least one of maleic anhydride.
In a preferred embodiment of the invention, the without phosphorus polymer and the heterocyclic compound and the hydrophilic gel
Body is retained separately, so as to be particularly convenient for the different phase of circulating water treatment.Wherein, the heterocyclic compound with it is described hydrophilic
Property colloid can be retained separately, and can also mix preservation.
By being further used cooperatively without phosphorus polymer, composition of the invention is hindered especially suitable for the inhibition of recirculated water
Dirt.Therefore, the present invention also provides the above-mentioned composition for containing heterocyclic compound, hydrophilic colloid and without phosphorus polymer as slow
Lose application of the antisludging agent in circulating water treatment.The composition of the present invention is as corrosion inhibiting and descaling agent in use, dosage is preferably 10-
55mg/L recirculated waters.
According to the preferred embodiment of the present invention, the composition is by mentioned component (the first heterocyclic compound, the second heterocycle
Compound and hydrophilic colloid or the first heterocyclic compound, the second heterocyclic compound, hydrophilic colloid and without phosphorus polymer)
Composition.
The present invention composition can be widely used for using basic, normal, high hardness, the water quality of basicity as moisturizing circulating water treatment
In, that is, being less than (low hardness, basicity water quality) recirculated water of 100mg/L suitable for processing the sum of calcium hardness and total alkalinity
(natural ph technique is used in processing)；It is the (medium hard of 100-300mg/L to be also applied for processing the sum of calcium hardness and total alkalinity
Degree, basicity water quality) (natural ph technique is used) in circulating water treatment；It is big to apply also for processing the sum of calcium hardness and total alkalinity
(control ph 7.8-8.2 adjusts acid used in pH value in (high hardness, basicity water quality) circulating water treatment of 300mg/L
Can be various acid commonly used in the art, such as sulfuric acid and/or nitric acid).
In practical application, the composition can be prepared before use, such as each component is mixed according to aforementioned formula
After add in recirculated cooling water；It is cold can also each component to be directly added into according to aforementioned formula to cycle without mixing step
But in water.When being directly added into, the addition sequence of each component is not particularly limited.Further, it is also possible to by each component with
Water mixes, it is made to be added in recirculated cooling water after fully dissolving.
In addition, the method provided by the invention for carrying out circulating water treatment using above-mentioned composition includes the following steps：
(1) water running initial period is recycled：Add the heterocyclic compound of 3-12mg/L recirculated waters and 30-120mg/L cycles
The hydrophilic colloid of water carries out the pre- film of room temperature；
(2) water running enriching stage is recycled：The without phosphorus polymer of 6-30mg/L recirculated waters is added, start thermic load and is mended
Water；
(3) the recirculated water stable stage：Continue moisturizing and blowdown, when concentration of the hydrophilic colloid in recirculated water reaches
During 10-40mg/L recirculated waters, heterocyclic compound, hydrophilic colloid and without phosphorus polymer are added so that heterocyclic compound in recirculated water
A concentration of 1-4mg/L recirculated waters of object, a concentration of 10-40mg/L recirculated waters of hydrophilic colloid, without phosphorus polymer it is a concentration of
2-10mg/L recirculated waters.
In the circulating water treatment method of the present invention, the concrete operations in each stage are not required particularly, according to routine
Mode carries out, and those skilled in the art can select the concrete operations in each stage, no longer go to live in the household of one's in-laws on getting married one by one herein
It states.
Wherein, the run time of cycle water running initial period is usually more than for 24 hours (such as 24-35h).Water running is recycled to rise
In stage beginning, the pre- film of room temperature refers to carry out pre- film under conditions of not actuated thermic load, and temperature is usually 20-25 DEG C.
In cycle water running enriching stage, the cycles of concentration of recirculated water is usually 3-5 times.
It, can also be using heterocyclic compound or without phosphorus polymer as when judging to add medicament in the recirculated water stable stage
The benchmark of machine, that is, can when concentration of the heterocyclic compound in recirculated water reach 1-4mg/L recirculated waters when, add heterocyclic compound,
Hydrophilic colloid and without phosphorus polymer；Alternatively, when concentration of the without phosphorus polymer in recirculated water reaches 2-10mg/L recirculated waters, throw
Add heterocyclic compound, hydrophilic colloid and without phosphorus polymer.Due to heterocyclic compound, hydrophilic colloid and without phosphorus polymer be in than
Example adds, skilled artisans appreciate that aforesaid operations mode is also within the scope of the present invention.
For the growth of microorganism in control loop water, method of the invention can also include fungicide being added to cycle
Step in water, the fungicide can add in the recirculated water stable stage, can be with heterocyclic compound, hydrophilic colloid
It is added simultaneously or asynchronously with without phosphorus polymer.The type and amount of the fungicide used all can be those skilled in the art it is each
Kind conventional selection, details are not described herein.
The present invention will be described in detail by way of examples below.
In following embodiment, xanthans, guar gum and Arabic gum are purchased from Zhengzhou feudal dynasty chemical products Co., Ltd；Poly- day
Winter propylhomoserin (it is 0.089dl/g that the limit, which sticks number), poly-epoxy succinic acid (it is 0.032dl/g that the limit, which sticks number), (limit sticks polyacrylic acid
Number is 0.071dl/g) and hydrolysis of polymaleic anhydride (it is 0.068dl/g that the limit, which sticks number) to be purchased from the calm and peaceful water process in Shandong Province limited
Company；The water quality of test water is as shown in table 1, wherein Ca2+, total alkalinity and total hardness be with CaCO3Meter.Ca2+Detection is with reference to mark
Quasi- GB/T6910-2006；Total alkalinity detection reference standard GB/T 15451-2006；Total hardness detection reference standard GB/T
6909-2008；Cl-Detect reference standard GB/T 15453-2008；Conductivity detection reference standard GB/T 6908-2008；pH
Value detection reference standard GB/T 6920-1986.
Table 1
The evaluation of scale-inhibiting properties
Preparation calcium and total alkali are the test water of 600mg/L, and medicine is added by embodiment and comparative example into test water
Agent, it is 9.0 then to add in sodium tetraborate and adjust pH, is transferred in 500mL volumetric flasks.In standing in 80 ± 1 DEG C of waters bath with thermostatic control
10h, after cooling residue Ca in sampling analysis water2+Concentration, while do blank sample, and calculate scale inhibition performance.
Scale inhibition efficiency of the definition of scale inhibition performance for corrosion inhibiting and descaling agent, the calculation formula of scale inhibition performance are：Scale inhibition performance=(C-C0)/
(nC1-C0) × 100%, wherein,
C：Residue Ca in water after cooling2+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 pre- film medicine according to each embodiment and comparative example
In the test water of agent, holding rotating speed is 75rmp, and rotation carries out pre- film in 24 hours.It is put by the lacing film of pre- film according to each reality
It applies example and comparative example has been added in the test water of corrosion inhibiting and descaling agent, steady temperature is 45 ± 1 DEG C, and rotating speed is kept to be revolved for 75rpm
Turn 72h, the weight of test piece, calculates average corrosion rate (F) before and after record experiment.During low, middle hardness, basicity quality test of water
Do not adjust pH value.Control ph is 7.8-8.2 during high rigidity, basicity quality test of water.
The calculation formula of average corrosion rate (F) is：F=(C × △ W)/(A × T × ρ), wherein,
C：Computational constant, with mm/a (millimeter/year) be unit when, 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)
Embodiment 1
Xanthans, benzopyrrole and 2-mercaptobenzothiazole are added into test water, makes it dense in test water
Degree is respectively 75mg/L, 3.75mg/L and 3.75mg/L, and pre- film is carried out to lacing film with this.
Xanthans, benzopyrrole, 2-mercaptobenzothiazole and hydrolysis of polymaleic anhydride are added into test water, make its
Concentration in test water is respectively 25mg/L, 1.25mg/L, 1.25mg/L and 6mg/L, and recirculating cooling water system is carried out with this
Corrosion inhibition evaluation test.
According to method for evaluation of antisludging performance test preparation water, and xanthans, benzopyrrole, 2- sulfydryl benzos are added thereto
Thiazole and hydrolysis of polymaleic anhydride, make its concentration in test water be respectively 25mg/L, 1.25mg/L, 1.25mg/L and
6mg/L carries out evaluation of antisludging performance experiment with this.
Result of the test is shown in Table 2.
Embodiment 2
Guar gum, 2-methylimidazole and thiazolamine are added into test water, makes its concentration in test water
Respectively 90mg/L, 3.6mg/L and 2.4mg/L carry out pre- film with this to lacing film.
Guar gum, 2-methylimidazole, thiazolamine and poly-epoxy succinic acid are added into test water, is testing it
It is respectively 30mg/L, 1.2mg/L, 0.8mg/L and 5mg/L with the concentration in water, recirculating cooling water system rust inhibition is carried out with this
It can evaluation test.
According to method for evaluation of antisludging performance test preparation water, and guar gum, 2-methylimidazole, 2- amino thiophenes are added thereto
Azoles and poly-epoxy succinic acid make its concentration in test water be respectively 30mg/L, 1.2mg/L, 0.8mg/L and 5mg/L, with
This carries out evaluation of antisludging performance experiment.
Result of the test is shown in Table 2.
Embodiment 3
Arabic gum, methyl benzotriazazole and 2- amino -4- methylthiazols are added into test water, is testing it
It is respectively 60mg/L, 3.6mg/L and 5.4mg/L with the concentration in water, pre- film is carried out to lacing film with this.
Arabic gum, methyl benzotriazazole, 2- amino -4- methylthiazols and polyacrylic acid are added into test water,
It is respectively 20mg/L, 1.2mg/L, 1.8mg/L and 7mg/L to make its concentration in test water, and recirculated cooling water is carried out with this
System corrosion inhibition evaluation test.
According to method for evaluation of antisludging performance test preparation water, and Arabic gum, methyl benzotriazazole, 2- are added thereto
Amino -4- methylthiazols and polyacrylic acid, it is respectively 20mg/L, 1.2mg/L, 1.8mg/L to make its concentration in test water
And 7mg/L, evaluation of antisludging performance experiment is carried out with this.
Result of the test is shown in Table 2.
Embodiment 4
Xanthans, 2- phenylpyridines and 2- aminobenzothiazoles are added into test water, makes it in test water
Concentration is respectively 105mg/L, 2.7mg/L and 1.8mg/L, and pre- film is carried out to lacing film with this.
Xanthans, 2- phenylpyridines, 2- aminobenzothiazoles and poly-aspartate are added into test water, is trying it
It is respectively 35mg/L, 0.9mg/L, 0.6mg/L and 8mg/L to test with the concentration in water, and recirculating cooling water system inhibition is carried out with this
Benchmark test.
According to method for evaluation of antisludging performance test preparation water, and xanthans, 2- phenylpyridines, 2- aminobenzenes are added thereto
And thiazole and poly-aspartate, its concentration in test water is made to be respectively 35mg/L, 0.9mg/L, 0.6mg/L and 8mg/L,
Evaluation of antisludging performance experiment is carried out with this.
Result of the test is shown in Table 2.
Embodiment 5
Guar gum, 2- hydroxypyrazine and 2- amino -4- methylbenzothiazoles are added into test water, it is made to be used in experiment
Concentration in water is respectively 45mg/L, 7.5mg/L and 3mg/L, and pre- film is carried out to lacing film with this.
Guar gum, 2- hydroxypyrazine, 2- amino -4- methylbenzothiazoles and poly- epoxy succinic are added into test water
Acid, it is respectively 15mg/L, 2.5mg/L, 1mg/L and 4mg/L to make its concentration in test water, and recirculated cooling water is carried out with this
System corrosion inhibition evaluation test.
According to method for evaluation of antisludging performance test preparation water, and add thereto guar gum, 2- hydroxypyrazine, 2- amino-
4- methylbenzothiazoles and poly-epoxy succinic acid, it is respectively 15mg/L, 2.5mg/L, 1mg/L to make its concentration in test water
And 4mg/L, evaluation of antisludging performance experiment is carried out with this.
Result of the test is shown in Table 2.
Embodiment 6
Arabic gum, 2- amino -5- methoxy pyrimidines, thiazolamine and 2- amino benzo thiophenes are added into test water
Azoles makes its concentration in test water be respectively 120mg/L, 0.6mg/L, 1.2mg/L and 1.2mg/L, with this to lacing film into
The pre- film of row.
Arabic gum, 2- amino -5- methoxy pyrimidines, thiazolamine, 2- amino benzo thiophenes are added into test water
Azoles and polyacrylic acid, make its concentration in test water be respectively 40mg/L, 0.2mg/L, 0.4mg/L, 0.4mg/L and
10mg/L carries out recirculating cooling water system corrosion inhibition evaluation test with this.
According to method for evaluation of antisludging performance test preparation water, and it is phonetic to add Arabic gum, 2- amino -5- methoxyl groups thereto
Pyridine, thiazolamine, 2- aminobenzothiazoles and polyacrylic acid, make its concentration in test water be respectively 40mg/L,
0.2mg/L, 0.4mg/L, 0.4mg/L and 10mg/L carry out evaluation of antisludging performance experiment with this.
Result of the test is shown in Table 2.
Embodiment 7
Xanthans, guar gum, benzotriazole and 2- amino -4- methylthiazols are added into test water, is trying it
It is respectively 30mg/L, 30mg/L, 9.6mg/L and 2.4mg/L to test with the concentration in water, and pre- film is carried out to lacing film with this.
Xanthans, guar gum, benzotriazole, 2- amino -4- methylthiazols, poly-aspartate are added into test water
And hydrolysis of polymaleic anhydride, make its concentration in test water be respectively 10mg/L, 10mg/L, 3.2mg/L, 0.8mg/L,
2mg/L and 2mg/L carries out recirculating cooling water system corrosion inhibition evaluation test with this.
According to method for evaluation of antisludging performance test preparation water, and add thereto xanthans, guar gum, benzotriazole,
2- amino -4- methylthiazols, poly-aspartate and hydrolysis of polymaleic anhydride, make its concentration in test water be respectively
10mg/L, 10mg/L, 3.2mg/L, 0.8mg/L, 2mg/L and 2mg/L carry out evaluation of antisludging performance experiment with this.
Result of the test is shown in Table 2.
Comparative example 1
Xanthans is added into test water, makes its a concentration of 82.5mg/L in test water, with this to lacing film into
The pre- film of row.
Xanthans and hydrolysis of polymaleic anhydride are added into test water, makes its concentration in test water be respectively
27.5mg/L and 6mg/L carries out recirculating cooling water system corrosion inhibition evaluation test with this.
According to method for evaluation of antisludging performance test preparation water, and xanthans and hydrolysis of polymaleic anhydride are added thereto, make
Its concentration in test water is respectively 31mg/L and 6mg/L, and evaluation of antisludging performance experiment is carried out with this.
Result of the test is shown in Table 2.
Comparative example 2
Benzopyrrole is added into test water, makes its a concentration of 82.5mg/L in test water, with this to lacing film
Carry out pre- film.
Benzopyrrole and hydrolysis of polymaleic anhydride are added into test water, makes its concentration in test water be respectively
27.5mg/L and 6mg/L carries out recirculating cooling water system corrosion inhibition evaluation test with this.
According to method for evaluation of antisludging performance test preparation water, and benzopyrrole and hydrolysis of polymaleic anhydride are added thereto,
It is respectively 27.5mg/L and 6mg/L to make its concentration in test water, and evaluation of antisludging performance experiment is carried out with this.
Result of the test is shown in Table 2.
Comparative example 3
2-mercaptobenzothiazole is added into test water, makes its a concentration of 82.5mg/L in test water, with this
Pre- film is carried out to lacing film.
2-mercaptobenzothiazole and hydrolysis of polymaleic anhydride are added into test water, makes its concentration in test water
Respectively 27.5mg/L and 6mg/L carries out recirculating cooling water system corrosion inhibition evaluation test with this.
According to method for evaluation of antisludging performance test preparation water, and 2-mercaptobenzothiazole is added thereto and hydrolyzes poly- Malaysia
Acid anhydrides, it is respectively 27.5mg/L and 6mg/L to make its concentration in test water, and evaluation of antisludging performance experiment is carried out with this.
Result of the test is shown in Table 2.
Embodiment 8
Pre- film is not carried out to lacing film.
Xanthans, benzopyrrole, 2-mercaptobenzothiazole and hydrolysis of polymaleic anhydride are added into test water, make its
Concentration in test water is respectively 25mg/L, 1.25mg/L, 1.25mg/L and 6mg/L, and recirculating cooling water system is carried out with this
Corrosion inhibition evaluation test.
Result of the test is shown in Table 2.
Table 2
Note："/" represents undetermined
From the results shown in Table 2, circulating water treatment provided by the invention composition (embodiment 1-7) comprehensive performance
Well, there is excellent corrosion mitigating effect and scale inhibition effect.
Particularly, comparative example 1-3 be can be seen that into hydrophilic colloid compared with embodiment 1-7 and heterocyclic compound is common
It uses, just with good synergy.By embodiment 8 as can be seen that pre-filming treatment can be carried significantly compared with embodiment 1-7
High corrosion mitigating effect, illustrate the circulating water treatment of the present invention has preferable pre-film effect by the use of composition as prefilming agent.
Embodiment 9
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/T2160-91 is carried out, and test piece and test tube material are 20# carbon steels.Control parameter is as follows.
Water quality：Test water 1-3 in table 1.
Recycle water running initial period：The dosage of xanthans is 75mg/L, and the dosage of benzopyrrole is 3.75mg/L,
The dosage of 2-mercaptobenzothiazole is 3.75mg/L, is continuously run for 24 hours in no thermic load.
Recycle water running enriching stage：The dosage of hydrolysis of polymaleic anhydride is 18mg/L, starts thermic load, does not adjust pH
Value does not simultaneously adjust in without sewage discharge concentration 6 times (test waters 1) or pH value and is concentrated into the case that without sewage discharge
In recirculated water the sum of calcium ion content and total alkalinity for 1000mg/L (test water 2) or adjust pH value to 8.0 ± 0.2 simultaneously
It is 1100mg/L (test water 3) in the without sewage discharge calcium ion content that is concentrated into recirculated water.
The recirculated water stable stage：Blowdown and moisturizing when concentration of the xanthans in recirculated water reaches 25mg/L, add
Composite drug keeps a concentration of 25mg/L of xanthans in recirculated water, a concentration of 1.25mg/L of benzopyrrole, 2- sulfydryl benzos
A concentration of 1.25mg/L of thiazole, a concentration of 6mg/L of hydrolysis of polymaleic anhydride.
Flow velocity：1.0m/s
Inlet temperature of the recirculated water at heat exchanger entrance：32±1℃
Recycle the water entrance temperature difference：8-10℃
Run time：16 days
Dynamic simulation test the results are shown in Table 3.
Adherency rate calculation formula be：Adhere to rate=3 × (W1-W2)/(A × t), wherein,
W1：Test tube weight (g) after examination
W2：Test tube weight (g) after pickling
A：Test tube internal surface area (m2/ root)
t：Test period (my god)
Table 3
| Lacing film corrosion rate (mm/a) | Test tube adherency rate (mcm) | |
| Test water 1 | 0.027 | 5.6 |
| Test water 2 | 0.017 | 7.4 |
| Test water 3 | 0.038 | 4.7 |
It is shown in table 3 the result shows that, by the circulating water treatment of the present invention with composition in circulating water treatment, lacing film
Corrosion rate is worked out better than production department of China Petrochemical Corporation and development division《Cool down water analysis and test method》In《Examination
Test the small-sized experimental analogic method in room》" fine grade " standard；Adherency rate reaches production department of China Petrochemical Corporation and development division
Establishment《Cool down water analysis and test method》In《The small-sized experimental analogic method of laboratory》In " fine grade " standard.
By using the present invention circulating water treatment composition, it is ensured that recirculated cooling water (basic, normal, high hardness and
Basicity water quality is the recirculated cooling water of moisturizing) stable operation, there is good inhibition, scale effect, and medicament is not phosphorous,
The risk of body eutrophication can be caused to avoid Circulating water effluent.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, 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 also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of without phosphorus circulating water treatment composition, which is characterized in that the composition contains heterocyclic compound and hydrophilic gel
The weight ratio of body, the heterocyclic compound and hydrophilic colloid is 1：2.5-40, it is sulphur that the heterocyclic compound, which includes hetero atom,
The first heterocyclic compound and hetero atom with nitrogen are the second heterocyclic compound of nitrogen；
First heterocyclic compound be substituted or unsubstituted thiazole and/or substituted or unsubstituted benzothiazole, wherein, take
The group in generation can be sulfydryl, amino and C1-C3At least one of alkyl；
Second heterocyclic compound is selected from benzopyrrole, 2-methylimidazole, 2- phenylpyridines, 2- hydroxypyrazine, 2- amino -5-
At least one of methoxy pyrimidine, 4- methylquinolines, 5- nitroisoquinolines, benzotriazole and methyl benzotriazazole；
The hydrophilic colloid is natural polysaecharides hydrophilic colloid.
2. composition according to claim 1, wherein, first heterocyclic compound is selected from 2-mercaptobenzothiazole, 2-
At least one of aminothiazole, 2- amino -4- methylthiazols, 2- amino -4- methylbenzothiazoles and 2- aminobenzothiazoles.
3. composition according to claim 1, wherein, the hydrophilic colloid is selected from xanthans, guar gum and Arab
At least one of glue.
4. according to the composition described in any one in claim 1-3, wherein, the composition also contains without phosphorus polymer,
The weight ratio of the heterocyclic compound and without phosphorus polymer is 1：0.5-10.
5. composition according to claim 4, wherein, the limit of the without phosphorus polymer sticks number as 0.03-0.1dl/g.
6. composition according to claim 4, wherein, the without phosphorus polymer is C3-C10Unsaturated carboxylic acid it is without phosphorus
Polymers.
7. composition according to claim 4, wherein, the without phosphorus polymer is selected from poly-aspartate, poly- epoxy succinic
At least one of acid, polyacrylic acid and hydrolysis of polymaleic anhydride.
8. composition according to claim 4, wherein, the without phosphorus polymer and the heterocyclic compound and described hydrophilic
Property colloid is retained separately.
9. the method that the composition in a kind of 4-8 using claim described in any one carries out circulating water treatment, feature exist
In this method includes the following steps：
（1）Recycle water running initial period：Add the heterocyclic compound of 3-12mg/L recirculated waters and 30-120mg/L recirculated waters
Hydrophilic colloid carries out the pre- film of room temperature；
（2）Recycle water running enriching stage：The without phosphorus polymer of 6-30mg/L recirculated waters is added, starts thermic load and moisturizing；
（3）The recirculated water stable stage：Continue moisturizing and blowdown, when concentration of the hydrophilic colloid in recirculated water reaches 10-
During 40mg/L recirculated waters, heterocyclic compound, hydrophilic colloid and without phosphorus polymer are added so that heterocyclic compound in recirculated water
A concentration of 1-4mg/L recirculated waters, a concentration of 10-40mg/L recirculated waters of hydrophilic colloid, a concentration of 2- of without phosphorus polymer
10mg/L recirculated waters.
10. application of the composition as prefilming agent in circulating water treatment in claim 1-3 described in any one.
11. application according to claim 10, wherein, the dosage of the composition is 30-135mg/L recirculated waters.
12. application of the composition as corrosion inhibiting and descaling agent in circulating water treatment in claim 4-8 described in any one.
13. application according to claim 12, wherein, the dosage of the composition is 10-55mg/L recirculated waters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541700.6A CN106477740B (en) | 2015-08-28 | 2015-08-28 | Circulating water treatment composition and its processing method of application and recirculated water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541700.6A CN106477740B (en) | 2015-08-28 | 2015-08-28 | Circulating water treatment composition and its processing method of application and recirculated water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106477740A CN106477740A (en) | 2017-03-08 |
| CN106477740B true CN106477740B (en) | 2018-06-15 |
Family
ID=58236141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510541700.6A Active CN106477740B (en) | 2015-08-28 | 2015-08-28 | Circulating water treatment composition and its processing method of application and recirculated water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106477740B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819992B (en) * | 2019-11-27 | 2020-09-11 | 济南鼎隆化工科技有限公司 | Environment-friendly organic metal corrosion inhibitor and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20204720U1 (en) * | 2002-03-25 | 2002-06-13 | Reckitt Benckiser Nv | Thickened aqueous compositions |
| CN1511791A (en) * | 2002-12-30 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Method for utiliznig sterilizing agent in circular cooling water |
| CN104743685A (en) * | 2015-03-21 | 2015-07-01 | 威海翔宇环保科技股份有限公司 | Long-acting sustained-release scale and corrosion inhibitor for circulating water |
-
2015
- 2015-08-28 CN CN201510541700.6A patent/CN106477740B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE20204720U1 (en) * | 2002-03-25 | 2002-06-13 | Reckitt Benckiser Nv | Thickened aqueous compositions |
| CN1511791A (en) * | 2002-12-30 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Method for utiliznig sterilizing agent in circular cooling water |
| CN104743685A (en) * | 2015-03-21 | 2015-07-01 | 威海翔宇环保科技股份有限公司 | Long-acting sustained-release scale and corrosion inhibitor for circulating water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106477740A (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509652C (en) | No-phosphate corrosion and scale inhibitor and application thereof | |
| CN100545313C (en) | A kind of compound prefilming agent of environment-friendly type and using method thereof that is used for the pre-film processing of recirculating cooling water system | |
| CN104891684B (en) | Without phosphorus composite slow-corrosion scale resistor for bitter recirculated water and preparation method thereof | |
| CN102730848A (en) | Composite anti-incrustation corrosion inhibiter and its application in water treatment | |
| CN102452725B (en) | Composite scale and corrosion inhibitor and its application | |
| CN103191646B (en) | A kind of without phosphorus Treated sewage reusing reverse osmosis membrane antisludging agent and preparation method thereof | |
| CN102328979B (en) | Cationic flocculant based on collagen modification and preparation method thereof | |
| CN101230260B (en) | Compound inhibitor for exploitation of oil-gas field and preparation method thereof | |
| CN107777789A (en) | Low-phosphor efficient anti-incrustation corrosion inhibitor for circulating water treatment and preparation method thereof | |
| CN103771596A (en) | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water | |
| CN102730847A (en) | Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment | |
| CN106495294B (en) | A kind of corrosion-mitigation scale-inhibition fungicide and preparation method thereof | |
| CN106745847B (en) | Composite corrosion and scale inhibitor and preparation method thereof | |
| CN106477738B (en) | Circulating water treatment composition and its processing method of application and recirculated water | |
| CN101519244B (en) | Compound scale inhibitor for treating recirculated cooling water and preparation method thereof | |
| CN103030225A (en) | Treatment process of circulating cooling water with leaked ammonia nitrogen | |
| CN106430653A (en) | Composite corrosion and scale inhibitor, and application thereof | |
| CN104891682B (en) | Environment-friendly and efficient water treatment agent applicable to Cu-Fe sharing system | |
| CN106430645B (en) | A kind of composite slow-corrosion scale resistor and its application | |
| CN106477740B (en) | Circulating water treatment composition and its processing method of application and recirculated water | |
| CN107304077B (en) | Corrosion-inhibition, scale-inhibition and sterilization composition and application thereof | |
| CN103030230B (en) | A kind for the treatment of process of circulating cooling water leaking ammonia nitrogen | |
| CN106477741B (en) | Circulating water treatment composition and its processing method of application and recirculated water | |
| CN106477739B (en) | Circulating water treatment composition and its processing method of application and recirculated water | |
| CN103803739A (en) | Method for recycling of reclaimed water in circulating cooling water system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |