CN106745835A - A kind of method for processing circulating cooling water containing sulfur - Google Patents
A kind of method for processing circulating cooling water containing sulfur Download PDFInfo
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- 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
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- 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
- C02F5/105—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 combined with inorganic substances
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/07—Alkalinity
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- 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
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Abstract
The present invention relates to water treatment field, a kind of method for processing circulating cooling water containing sulfur is disclosed, the method includes：Oxidizer containing chlorine and composite corrosion inhibitor are added toward circulating cooling water containing sulfur, and controls the total alkalinity of circulating cooling water containing sulfur to maintain in the range of 170-300mg/L；Wherein, the consumption of oxidizer containing chlorine causes that the chlorine residue in circulating cooling water containing sulfur is 0.1-0.6mg/L, and the composite corrosion inhibitor contains water-soluble zinc salt and organic polymer type water treatment agent.The present invention adds particular kind of composite corrosion inhibitor by controlling total alkalinity and chlorine residue to coordinate, and the corrosion of circulating cooling water containing sulfur can be effectively controlled in the case where phosphorus content is relatively low, and corrosion of carbon steel speed meets the technical requirements less than 0.1mm/a；And carbon steel test tube adhesion speed is met less than 20mg/ (cm2Month) technical requirements, although still using the composite corrosion inhibitor of containing water-soluble zinc salt, but be not compromised by deposition of zinc salt and make adhesion speed exceeded.So that reducing energy consumption without thoroughly being replaced to system after there is sulphur-containing substance leakage.
Description
Technical field
The invention belongs to water treatment field, in particular it relates to a kind of method for processing circulating cooling water containing sulfur.
Background technology
Oil refining apparatus can cause the corrosion failure of equipment because of the strong high-sulphur crude of processing corrosivity, send out often
Biology material leaks into the phenomenon in recirculated water；The sulfurous gas (such as hydrogen sulfide) that other device is produced is such as
It is really poorly sealed or process bad, in leaking into air, cause further by neighbouring cooling tower in it is cold
But water dissolves absorb.After sulphur-containing substance enters recirculating cooling water system, make water quality deterioration, conventional water treatment
Medicament fails, and aggravates the corrosion and fouling of circulation cold exchange device, and then the leakiness of material adds
Play, forms vicious circle.In recent years as China's processing import sour crude amount is increasing, equipment is rotten
Erosion and material from leakage enter recirculated water phenomenon and become increasingly conspicuous, to production equipment safety, the threat of long-term operation
There is increased trend.Therefore, the method for research and development treatment sulfur-containing anion recirculated cooling water is very necessary.
Current oil plant mainly has three kinds to the treatment measures of the recirculated water of sulfur compound, and one is to add big agent
To increase corrosion mitigating effect, two are a large amount of blowdowns and supplement fresh water to reduce sulphur in recirculated water the corrosion inhibiter of amount
The concentration of compound, three is to add NaOH, Na2CO3、NaHCO3Recirculated water is improved Deng basic agent
Basicity.Though these measures have certain effect, because sulfur-bearing Circulating Water Corrosion speed is fast, there is certain
Limitation.One is that most of corrosion inhibiter are phosphorous, for the conditional recirculated water of phosphorus content in recirculated water
, heavy dose is added and can be then restricted containing phosphor corrosion inhibitor.Two be most oil plants water system receive blowdown
The limitation of amount, it is impossible to thoroughly replace sulfur-bearing recirculated water in time, causes the corrosion rate of equipment still higher,
Meanwhile, the consumption of the consumption, fresh water of water treatment agent and quantity of wastewater effluent rise by a relatively large margin.Three
It is to add basic agent excess, the basicity of recirculated water can be made too high, causes fouling exceeded.
CN1338434A discloses a kind of method for processing sulfur compound recirculated cooling water, in recirculated water
Adding alkaline matter makes its pH reach 9.5-14, this so as to greatly reduce the corrosivity of recirculated water
Method can cause serious fouling in hardness recirculated water high.The method that CN1137056C is related to be
The oxidizing biocides of 2-15 times of addition leakage sulphion weight concentration in sulfur-bearing recirculated water, such as chlorine,
Dichloride sodium isocyanurate, chlorine dioxide etc., by the reaction of oxidizing sulphion, so as to solve
Sulfide is to corrosion of metal problem, but these strong oxidizers inevitably make organic phosphine water in water
Inorganic agent is decomposed, while exacerbating corrosion, limits its application；In addition, if same in recirculated water
Shi Hanyou other reducing substanceses, the oxidizing bactericide for also resulting in addition is consumed and can not abundant oxygen
Change sulphion, so as to corrosion can not effectively be suppressed.CN103420493A describes a kind of sulfur-containing anion
The processing method of recirculated cooling water, the recirculated cooling water of sulfur-containing anion and precipitating reagent copper sulphate and inhibition are hindered
Dirty agent mixing contact, corrosion inhibiting and descaling agent is selected from vanadate, organic phospho acid, organic polymer and water-soluble zinc
At least one in salt, the corrosion and scaling trend of the recirculated water obtained after treatment is substantially reduced, but due to making
It is copper ion, if the excessive corrosion that can aggravate carbon steel equipment.CN103572297A discloses one
The processing method of circulating cooling water containing sulfur is planted, to addition ferrous iron and/or ferric iron in circulating cooling water containing sulfur
Water soluble chelate compound, the quality with the sulphion in recirculated cooling water is 1, the water soluble chelate compound of iron
Consumption 5-20 is calculated as with iron, although the method can effectively suppress circulating cooling water containing sulfur to hardware
With the corrosion of pipeline, but processing cost is higher.
Treatment process of circulating cooling water is broadly divided into two kinds：One kind is nature pH operation process, general suitable
Soft supplement water water quality, controls Ca in conjunction in recirculated water2+With total alkalinity (with CaCO3Meter, below
Sum is less than 1000mg/L together), because recirculated water can control basicity higher in this technique, leaks into
Sulfide post-etching is relatively easy to control, and the document reported is substantially for this kind of water quality.Another kind is
Acid adding adjusts pH techniques, and this technique is adapted to high rigidity, high alkalinity supplement water water quality, in this process recycled water
Ca2+Typically in 700-1500mg/L, but in order to suppress fouling, basicity control is relatively low, in recirculated water
The more difficult control of sulfide post-etching is leak into, is typically rarely reported, therefore urgently further research and development.
The content of the invention
The purpose of the present invention is to overcome the high hardness and low basicity in the prior art to having revealed sulphur-containing substance to follow
The deficiency that the research of ring cooling water is still short of, there is provided a kind of height for being particularly well-suited to reveal sulphur-containing substance is hard
Spend low-phosphorous (or without phosphorus) processing method of low alkalinity recirculated cooling water.
To achieve these goals, the present invention provides a kind of method for processing circulating cooling water containing sulfur, the party
Method includes：
Oxidizer containing chlorine and composite corrosion inhibitor are added toward circulating cooling water containing sulfur, and is controlled cold containing sulfur cycle
But the total alkalinity of water is maintained in the range of 170-300mg/L；Wherein, the consumption of the oxidizer containing chlorine makes
The chlorine residue obtained in circulating cooling water containing sulfur is 0.1-0.6mg/L, and the composite corrosion inhibitor contains water-soluble zinc
Salt and organic polymer type water treatment agent.
The present invention adds particular kind of composite corrosion inhibitor, Neng Gou by controlling total alkalinity and chlorine residue to coordinate
The effectively corrosion of control circulating cooling water containing sulfur in the case of phosphorus content relatively low (or not phosphorous), carbon steel is rotten
Technical requirements and carbon steel test tube the adhesion speed satisfaction that erosion speed meets less than 0.1mm/a are less than 20
mg/(cm2Month) technical requirements, although still using the composite corrosion inhibitor of containing water-soluble zinc salt, but simultaneously
Adhesion speed will not be made exceeded due to deposition of zinc salt.So that without right after there is sulphur-containing substance leakage
System is thoroughly replaced, and has saved medicament expense, fresh water rate and charges for disposing pollutants, reduces energy consumption.And
The method of the present invention can be carried out in the case where live original dosing state is not changed, simple to operate, convenient
Fast, safely and effectively.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated 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 opposite explanation is not made, during the term " basicity " for using refers to water
Can be H with strong acid+There is the total amount of the material of neutralization, generally by highly basic, weak base, strong base weak acid
Salt is constituted, and " total alkalinity " is methyl orange alkalinity, is by titrating with methyl orange (methyl red) to indicate
The titration end-point (pH=4.5) of agent determines the basicity in water at random, to determine bicarbonate, carbonic acid in water
The concentration of salt and hydroxide, can represent that unit is with the amount of energy binding hydrogen ions in 1L water
Mmol/L, it is also possible to use the quality representation of the suitable calcium carbonate of the material of energy binding hydrogen ions in 1L water,
Unit is mg/L, and 1mmol/L=50.05mg/L；" chlorine residue (total chlorine) " is with free chlorine, chemical combination
The content (in terms of chlorine element) of the chlorine that chlorine or both and the form deposited are present, combined chlorine refer to chloramines and
The chlorine that organic chloramines form is present, free chlorine is with hypochlorous acid, hypochlorite or dissolubility simple substance chlorine form
The chlorine of presence, the chlorine residue being related in the present invention each means containing for free chlorine in the case of no specified otherwise
Amount；The material (particularly organic polymer type water treatment agent and copper material corrosion inhibitor) being related in the present invention
Weight (is dried to (more than 4h) during constant weight with butt (or weight of contained solid) at 120 DEG C
Weight) meter.
The method of the treatment circulating cooling water containing sulfur that the present invention is provided includes：
(preferably in the case where live original dosing state is not changed) is toward circulating cooling water containing sulfur (containing original
Water treatment agent) in add oxidizer containing chlorine and composite corrosion inhibitor, and control the total alkali of circulating cooling water containing sulfur
Degree is maintained in the range of 170-300mg/L (preferably in 200-250mg/L)；Wherein, the chloride oxygen
The consumption of agent causes that the chlorine residue in circulating cooling water containing sulfur is 0.1-0.6mg/L (preferably 0.1-0.4
Mg/L), the composite corrosion inhibitor contains water-soluble zinc salt and organic polymer type water treatment agent.
According to the present invention, the oxidizer containing chlorine can be the conventional chlorine-bearing compound with strong oxidizing property.
Preferably, the oxidizer containing chlorine is by chlorine, calcium hypochlorite, sodium hypochlorite, bleaching powder, dichloro isocyanide
Monosodium urate, sym-closene, chlorine dioxide, bromine chloride, bromochlorodimethyl hydanton and bromine chloromethane ethyl
At least one offer in glycolylurea.
According to the present invention, the circulating cooling water containing sulfur relative to every liter, total consumption of the composite corrosion inhibitor
(in terms of butt) can be as 3-50mg.
According to the present invention, the consumption to water-soluble zinc salt is not required particularly.It is described in terms of zinc ion
Ratio in the consumption and circulating cooling water containing sulfur of water-soluble zinc salt between the content of sulphion is preferably
2.5-5:1, more preferably 3-4:1.In terms of zinc ion, the consumption of the water-soluble zinc salt is preferably 2-8
mg/L。
According to the present invention, the water-soluble zinc salt can for this area is conventionally used as the various of corrosion inhibiter can
It is dissolved in the zinc salt of aquatic products tutanag ion.Preferably, the water-soluble zinc salt be selected from zinc chloride, zinc nitrate and
At least one of zinc sulfate (a kind of, two or three).
According to the present invention, the organic polymer type water treatment agent can be used according to conventional consumption.It is excellent
In the case of choosing, the circulating cooling water containing sulfur relative to every liter, the organic polymer type water treatment agent is with dry
The consumption of base meter is 3-9mg, more preferably 4.5-7.5mg.
According to the present invention, the number-average molecular weight of the organic polymer type water treatment agent is 300-10000.
The organic polymer type water treatment agent can be conventionally used as the various organic polymers of corrosion inhibiter for this area
Thing.The organic polymer can be for poly-aspartic-acid, poly-epoxy succinic acid and by selected from unsaturation
The copolymer that at least one polymerization in organic acid, unsaturated organic acid ester and unsaturated organic acid acid anhydride is obtained
And/or at least one in homopolymers.The unsaturated organic acid is preferably (methyl) acrylic acid, maleic acid
With at least one in the unsaturated sulfonic acid of C2-C10.The unsaturated sulfonic acid of the C2-C10 can be
Various conventional unsaturated sulfonic acids, and in addition to alkyl, alkenyl and sulfonic group, benzene can also be contained
Base, amide groups etc., the unsaturated sulfonic acid of the C2-C10 for example can be styrene sulfonic acid, pi-allyl
Sulfonic acid, vinyl sulfonic acid, 2- methyl -2'- acrylamido propane sulfonic acids etc..The unsaturated organic acid ester is
The ester (such as acrylate, such as methyl acrylate or hydroxypropyl acrylate) 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.
Preferably, the organic polymer type water treatment agent be selected from poly- (methyl) acrylic acid, HPMA,
Poly-aspartic-acid, poly-epoxy succinic acid, (methyl) acrylic acid/(methyl) hydroxypropyl acrylate copolymer, (first
Base) acrylic acid/(methyl) hydroxypropyl acrylate/(methyl) methyl acrylate copolymer, maleic acid/styrene sulphur
Acid copolymer, maleic anhydride/Styrene Sulfonic Acid Copolymer, (methyl) acrylic/styrene sulfonic acid copolymer,
(methyl) acrylate/Styrene Sulfonic Acid Copolymer, maleic acid/allyl sulphonic acid copolymer, maleic anhydride/
Allyl sulphonic acid copolymer, (methyl) acrylic acid/allyl sulphonic acid copolymer, (methyl) acrylic acid/ethene sulphur
Acid copolymer, (methyl) acrylic acid/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) propylene
Acid/acrylamide/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/(methyl) third
Olefin(e) acid ester/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/maleic acid/2- methyl
- 2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/maleic anhydride/2- methyl -2'- acrylamides
Base propane sulfonic acid copolymer and (methyl) acrylic acid/2- acrylamidos -2- methylpropanephosphonic acids/2- methyl -2'- third
At least one in acrylamide base propane sulfonic acid copolymer.
It is highly preferred that the organic polymer type water treatment agent be selected from maleic acid/Styrene Sulfonic Acid Copolymer,
Maleic anhydride/Styrene Sulfonic Acid Copolymer, (methyl) acrylic/styrene sulfonic acid copolymer, (methyl) propylene
Acid esters/Styrene Sulfonic Acid Copolymer, maleic acid/allyl sulphonic acid copolymer, maleic anhydride/allyl sulphonic acid
Copolymer, (methyl) acrylic acid/allyl sulphonic acid copolymer, (methyl) acrylic acid/vinyl sulfonic acid copolymer,
(methyl) acrylic acid/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/acrylamide
/ 2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/(methyl) acrylate/2- methyl
- 2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/maleic acid/2- methyl -2'- acrylamidos
Propane sulfonic acid copolymer, (methyl) acrylic acid/maleic anhydride/2- methyl -2'- acrylamidos propane sulfonic acid are total to
Polymers and (methyl) acrylic acid/2- acrylamidos -2- methylpropanephosphonic acids/2- methyl -2'- acrylamido propane
At least one in sulfonic acid copolymer.
In the present invention, when when containing equipment made of copper in system, the composite corrosion inhibitor can also be slow containing copper material
Erosion agent.The copper material corrosion inhibitor can be BTA (BTA), methyl benzotriazazole and sulfydryl
Benzothiazole etc..Usually, the circulating cooling water containing sulfur relative to every liter, the copper material corrosion inhibitor is with dry
The consumption of base meter is 0.5-1.5mg.
The composite corrosion inhibitor used in the present invention can be obtained by existing various methods, for example can be by
The raw material for forming the composite corrosion inhibitor is well mixed and is obtained according to foregoing consumption, and the present invention is to described mixed
The step of conjunction and condition are without particular/special requirement.Use and promote each component to be well mixed for convenience, by each
After component mixes according to above-mentioned consumption, a certain amount of solvent (preferably water) can also be added, will be compound
It is standby that corrosion inhibiter is configured to certain density medicament.
The composite corrosion inhibitor phosphorus content that the present invention is used is relatively low, it might even be possible to not phosphorous, in other words, described
The total phosphorus content that composite corrosion inhibitor is provided recirculated water is (with PO4 3-Meter) can be in below 0.7mg/L.
In the present invention, the method for the total alkalinity of control circulating cooling water containing sulfur can be according to the reality of recirculated water
Situation is selected, and such as uses alkaline matter or acidic materials, i.e. when the basicity of recirculated cooling water can not
When meeting above-mentioned requirements, total alkalinity is adjusted using alkaline matter or acidic materials.The alkaline matter can be with
It is alkali commonly used in the art, such as NaOH, KOH, Na2CO3、K2CO3、NaHCO3And KHCO3
In at least one (or two or more).Preferably, the alkaline matter is NaHCO3。
The acidic materials can be acid commonly used in the art, such as at least one in sulfuric acid, nitric acid and hydrochloric acid.
Preferably, the acidic materials are sulfuric acid.
It is described in order to further control the adhesion speed caused due to zinc sulphide precipitation to increase in the present invention
Method also includes the other drainage amount of appropriate increase circulation.Side filter refers to draw from global cycle aqueous systems
Go out a part of recirculated water to be filtered, with the impurity in removing system, this part quantity of circulating water of extraction is
It is other drainage amount.In a preferred embodiment of the invention, the other drainage amount of circulation is controlled to follow
The 4-5% (other drainage amount/quantity of circulating water × 100%) of ring water.
Circulating cooling water containing sulfur in the present invention be revealed sulphur-containing substance (such as hydrogen sulfide) circulation it is cold
But water.The content of sulphion can be 0.1-2mg/L in the circulating cooling water containing sulfur.
According to the present invention, with CaCO3Meter, the content of calcium ion preferably exists in the circulating cooling water containing sulfur
More than 700 (such as 700-1300mg/L).Usually, the total hardness of the circulating cooling water containing sulfur is
1000-2000mg/L, total alkalinity is 50-400mg/L, and chloride ion content is 50-700mg/L.
Below will the present invention will be described in detail by embodiment.In following examples, the measure of chlorine residue
Method is GB/T 14424-2008 " measure of chlorine residue in industrial circulating cooling water "；(dichloro is different for Babysafe
NaDCC) the strong Yilong Industry Co., Ltd. in Luoyang is purchased from, article No. is SS122 (114) MS, solid
Grain；Strong chlorine oil (sym-closene) is purchased from the strong Yilong Industry Co., Ltd. in Luoyang, and article No. is SS121 (116)
MS；Rotary hanging plate corrosion test is with reference to GB/T 18175-2000 " the measure rotations of water treatment agent corrosion inhibition
Turn hanging slice method " carry out, test temperature is 45 DEG C, and test piece rotating speed is 75 revs/min (rpm), test period
It is 72h, lacing film material is 20# carbon steels, keeps water constant in experiment, if any evaporation deionized water
Supplement；Dynamic analog test is carried out with reference to HG/T 2160-2008 " dynamic analogue test of cooling water method ",
220# carbon steels test tube carry out parallel test, test water walks tube side, outside test tube
Heated with saturated vapor, 32 ± 1 DEG C of water inflow temperature of Control experiment, 8-10 DEG C of exit port water temperature difference,
Experiment is run continuously for about 16 days, and experiment supplement water is live fresh water, recirculated water simulated field water quality；
The weight of copolymer and BTA is in terms of butt.
Embodiment 1
The present embodiment is used for the corrosion mitigating effect for illustrating to process circulating cooling water containing sulfur using the inventive method.
Test water is certain Circulating Water, and water quality is：Calcium ion 1070mg/L, total hardness is 1550
Mg/L, total alkalinity 100mg/L, Cl-450mg/L, S2-1mg/L, chlorine residue is not detected.
Rotary hanging plate corrosion test is carried out after adding medicament in such a way toward test water：
Do not changing the former feelings using medicament YSW105A (purchased from Beijing Yan Hua set associatives company) of oil plant
Under condition, add sodium acid carbonate its total alkalinity is reached 200mg/L, add sodium hypochlorite to reach chlorine residue
0.2mg/L, adds the composite corrosion inhibitor (water containing maleic anhydride/Styrene Sulfonic Acid Copolymer and zinc chloride
Solution, wherein maleic anhydride/Styrene Sulfonic Acid Copolymer are to develop limited public affairs purchased from Langfang gold promise biotechnology
The JNH-406 of department) so that in every liter of pending test water, corresponding maleic anhydride/styrene sulphur
The amount of acid copolymer is 4.5mg, and zinc chloride makes the concentration of corresponding zinc ion be 4mg/L, is sulphion
4 times of concentration.The results are shown in Table 1.
Embodiment 2
The present embodiment is used for the corrosion mitigating effect for illustrating to process circulating cooling water containing sulfur using the inventive method.
Test water is certain Circulating Water, and water quality is：Calcium ion 1250mg/L, total hardness is 1810
Mg/L, total alkalinity 100mg/L, Cl-530mg/L, S2-1mg/L, chlorine residue is not detected.
Rotary hanging plate corrosion test is carried out after adding medicament in such a way toward test water：
Do not changing the former feelings using medicament YSW105A (purchased from Beijing Yan Hua set associatives company) of oil plant
Under condition, add sodium hypochlorite to make its chlorine residue up to 0.4mg/L, add sodium acid carbonate to reach its total alkalinity
200mg/L, adds composite corrosion inhibitor (water-soluble containing acrylic/styrene sulfonic acid copolymer and zinc nitrate
Liquid, wherein acrylic/styrene sulfonic acid copolymer are purchased from Hubei giant dragon hall biotechnology Development Co., Ltd
AA-SSA) so that in every liter of pending test water, corresponding acrylic/styrene sulfonic acid be total to
The amount of polymers is 3.6mg, and zinc nitrate makes the concentration of corresponding zinc ion be 3mg/L, is sulphion concentration
3 times.The results are shown in Table 1.
Embodiment 3
The present embodiment is used for the corrosion mitigating effect for illustrating to process circulating cooling water containing sulfur using the inventive method.
Test water is certain Circulating Water, and water quality is：Calcium ion 850mg/L, total hardness is 1230
Mg/L, total alkalinity 180mg/L, Cl-360mg/L, S2-1mg/L, chlorine residue is not detected.
Rotary hanging plate corrosion test is carried out after adding medicament in such a way toward test water：
Do not changing the former feelings using medicament YSW105A (purchased from Beijing Yan Hua set associatives company) of oil plant
Under condition, add sodium acid carbonate its total alkalinity is reached 200mg/L, add sodium hypochlorite to reach its chlorine residue
0.5mg/L, adds the composite corrosion inhibitor (water containing maleic anhydride/allyl sulphonic acid copolymer and zinc sulfate
Solution, wherein maleic anhydride/allyl sulphonic acid copolymer are to develop limited public affairs purchased from the water process of Lianyun Harbour 31
The SY-414 of company of department) so that in every liter of pending test water, corresponding maleic anhydride/pi-allyl
The amount of sulfonic acid copolymer is 7.5mg, and zinc sulfate makes corresponding zinc ion concentration for 5mg/L, is sulphion
5 times of concentration.The results are shown in Table 1.
Embodiment 4
The present embodiment is used for the corrosion mitigating effect for illustrating to process circulating cooling water containing sulfur using the inventive method.
Rotary hanging plate corruption is carried out after adding medicament in such a way toward test water (with embodiment 1)
Corrosion test：
Do not changing the former feelings using medicament YSW105A (purchased from Beijing Yan Hua set associatives company) of oil plant
Under condition, vulcanized sodium is added to make S2-1.8mg/L is reached, adds sodium acid carbonate to reach its total alkalinity
250mg/L, adds Babysafe to make its chlorine residue up to 0.1mg/L, adds composite corrosion inhibitor (to contain acrylic acid/2-
The aqueous solution of methyl -2'- acrylamido propane sulfonic acid copolymers and zinc sulfate, wherein acrylic acid/2- methyl
- 2'- acrylamido propane sulfonic acid copolymers are purchased from Jiangsu Jing Kexia peaks Fine Chemical Co., Ltd
JC-3211) so that in every liter of pending test water, corresponding acrylic acid/2- methyl -2'- acryloyls
The amount of amido propane sulfonic acid copolymer is 6mg, and zinc sulfate makes corresponding zinc ion concentration for 4.5mg/L,
It is 2.5 times of sulphion concentration.The results are shown in Table 1.
Embodiment 5
The present embodiment is used for the corrosion mitigating effect for illustrating to process circulating cooling water containing sulfur using the inventive method.
Test water is certain Circulating Water, and water quality is：Calcium ion 750mg/L, total hardness is 1090
Mg/L, total alkalinity 200mg/L, Cl-320mg/L, S2-0.5mg/L, chlorine residue is not detected.
Rotary hanging plate corrosion test is carried out after adding medicament in such a way toward test water：
Do not changing the former feelings using medicament YSW105A (purchased from Beijing Yan Hua set associatives company) of oil plant
Under condition, vulcanized sodium is added to make S2-1.8mg/L is reached, adds sodium acid carbonate to reach its total alkalinity
250mg/L, adds Babysafe to make its chlorine residue up to 0.3mg/L, add composite corrosion inhibitor (containing acrylic acid/
The aqueous solution of methyl acrylate/hydroxypropyl acrylate copolymer and zinc nitrate, wherein acrylic acid/acrylic acid first
Ester/hydroxypropyl acrylate copolymer is the ZF-311 purchased from Beijing Yan Hua set associatives company) so that wait for every liter to locate
In the test water of reason, the amount of corresponding acrylic acid/methyl acrylate/hydroxypropyl acrylate copolymer is 7.5
Mg, zinc nitrate makes corresponding zinc ion concentration for 6mg/L, is 3.3 times of sulphion concentration.Result is shown in
Table 1.
Embodiment 6
The present embodiment is used for the corrosion mitigating effect for illustrating to process circulating cooling water containing sulfur using the inventive method.
Test water is certain Circulating Water, and water quality is：Calcium ion 1300mg/L, total hardness is 1890
Mg/L, total alkalinity 110mg/L, Cl-550mg/L, S2-0.5mg/L, chlorine residue is not detected.
Rotary hanging plate corrosion test is carried out after adding medicament in such a way toward test water：
Do not changing the former feelings using medicament YSW105A (purchased from Beijing Yan Hua set associatives company) of oil plant
Under condition, vulcanized sodium is added to make S2-1.8mg/L is reached, adds sodium acid carbonate to reach its total alkalinity
250mg/L, adds Babysafe to make its chlorine residue up to 0.6mg/L, adds composite corrosion inhibitor (to contain acrylic acid/2-
The aqueous solution of methyl -2'- acrylamidos propane sulfonic acid/hydroxypropyl acrylate copolymer and zinc chloride, wherein
Acrylic acid/2- methyl -2'- acrylamidos propane sulfonic acid/hydroxypropyl acrylate copolymer is imperial by force purchased from Luoyang
The YSW301 of Chemical Co., Ltd.'s production) so that in every liter of pending test water, corresponding third
The amount of olefin(e) acid/2- methyl -2'- acrylamidos propane sulfonic acid/hydroxypropyl acrylate copolymer is 8.4mg, chlorine
Changing zinc makes corresponding zinc ion concentration for 7mg/L, is 3.9 times of sulphion concentration.The results are shown in Table 1.
Comparative example 1
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, except original uses medicament
Outward, any other medicament is not added.The results are shown in Table 1.
Comparative example 2
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, do not changing oil refining
Factory is former using in the case of medicament, only uses NaHCO3The total alkalinity of Adjustment Tests water is 200mg/L.
The results are shown in Table 1.
Comparative example 3
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, do not changing oil refining
Factory is former using in the case of medicament, only its chlorine residue is reached 0.2 to addition sodium hypochlorite in test water
mg/L.The results are shown in Table 1.
Comparative example 4
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, do not changing oil refining
Factory is former using in the case of medicament, only to added in test water composite corrosion inhibitor (containing maleic anhydride/
The aqueous solution of Styrene Sulfonic Acid Copolymer and zinc chloride, wherein maleic anhydride/Styrene Sulfonic Acid Copolymer are purchase
From the JNH-406 of Langfang Jin Nuo biotechnologies development corporation, Ltd.) so that every liter of pending experiment is used
In water, the amount of corresponding maleic anhydride/Styrene Sulfonic Acid Copolymer is 4.5mg, and zinc chloride makes corresponding zinc
The concentration of ion is 4mg/L, is 4 times of sulphion concentration.The results are shown in Table 1.
Comparative example 5
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, do not changing oil refining
Factory is former using in the case of medicament, uses NaHCO3The total alkalinity of Adjustment Tests water be 200mg/L and to
Sodium hypochlorite is added in test water makes its chlorine residue reach 0.2mg/L, without adding composite corrosion inhibitor.Knot
Fruit is shown in Table 1.
Comparative example 6
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, do not changing oil refining
Factory is former using in the case of medicament, uses NaHCO3The total alkalinity of Adjustment Tests water be 200mg/L and to
Composite corrosion inhibitor (the water containing maleic anhydride/Styrene Sulfonic Acid Copolymer and zinc chloride is added in test water
Solution, wherein maleic anhydride/Styrene Sulfonic Acid Copolymer are to develop limited public affairs purchased from Langfang gold promise biotechnology
The JNH-406 of department) so that in every liter of pending test water, corresponding maleic anhydride/styrene sulphur
The amount of acid copolymer is 4.5mg, and zinc chloride makes the concentration of corresponding zinc ion be 4mg/L, is sulphion
4 times of concentration, without adding sodium hypochlorite.The results are shown in Table 1.
Comparative example 7
Mode according to embodiment 1 carries out rotary hanging plate corrosion test, unlike, add vulcanized sodium to make
S2-1.8mg/L is reached, in the case where oil plant original is not changed using medicament, is added in test water
Sodium hypochlorite makes its chlorine residue reach 0.2mg/L and adds composite corrosion inhibitor (to contain maleic anhydride/styrene sulphur
The aqueous solution of acid copolymer and zinc chloride, wherein maleic anhydride/Styrene Sulfonic Acid Copolymer are purchased from Langfang gold
The JNH-406 of promise biotechnology development corporation, Ltd.) so that in every liter of pending test water, phase
The amount of the maleic anhydride/Styrene Sulfonic Acid Copolymer answered is 6mg, and zinc chloride makes the dense of corresponding zinc ion
It is 6mg/L to spend, and is 3.3 times of sulphion concentration, and without NaHCO3Adjustment total alkalinity.Result is shown in
Table 1.
The rotary hanging plate corrosion test result of table 1
Embodiment 7
This example demonstrates that process circulating cooling water containing sulfur using the inventive method being surveyed through dynamic analog test
Corrosion mitigating effect, scale inhibition effect and the bactericidal effect for obtaining.
It is the 5% of quantity of circulating water to set other drainage amount.Experiment supplement water is live fresh water, to recirculated water
In continuously fill into vulcanized sodium, make corresponding S2-It is 1mg/L relative to the concentration of circulation water inventory.Recirculated water
Add original using medicament YSW105A (being purchased from Beijing Yan Hua set associatives company), main water quality is：Calcium ion
1150mg/L, total hardness is 1670mg/L, total alkalinity 200mg/L, Cl-435mg/L。
Do not change it is former using medicament in the case of, test water sulfuric acid controls the total alkalinity to be
200mg/L, adds strong chlorine oil its chlorine residue is reached 0.2mg/L, while adding composite corrosion inhibitor (propylene
The aqueous solution of acid/2- methyl -2'- acrylamido propane sulfonic acids copolymer, BTA and zinc chloride,
Wherein acrylic acid/2- methyl -2'- acrylamido propane sulfonic acid copolymers are fine purchased from Jiangsu Jing Kexia peaks
The JC-3211 of Chemical Co., Ltd.) so that in every liter of pending test water, corresponding acrylic acid/2-
The amount of methyl -2'- acrylamido propane sulfonic acid copolymers and BTA is respectively 6mg and 1mg,
Zinc chloride makes the concentration of corresponding zinc ion be 3mg/L, is 3 times of sulphion concentration.Corrosion of carbon steel speed
Degree and adhesion speed are respectively 0.071mm/a and 14mg/ (cm2Month), the total heterotrophic bacteria count of recirculated water
1 × 10 is less than after testing5Individual/ml.
Comparative example 8
Method according to embodiment 9 carries out dynamic analog test, unlike, control the total alkali of recirculated water
It is 350mg/L to spend.Corrosion of carbon steel speed and adhesion speed are respectively 0.054mm/a and 27
mg/(cm2Month), the total heterotrophic bacteria count of recirculated water is less than 1 × 10 after testing5Individual/ml.
Embodiment 8
This example demonstrates that process circulating cooling water containing sulfur using the inventive method being surveyed through dynamic analog test
Corrosion mitigating effect, scale inhibition effect and the bactericidal effect for obtaining.
It is the 5% of quantity of circulating water to set other drainage amount.Experiment supplement water is live fresh water, to recirculated water
In continuously fill into vulcanized sodium, make corresponding S2-It is 0.4mg/L relative to the concentration of circulation water inventory.Circulation
Water adds original using medicament YSW105A (being purchased from Beijing Yan Hua set associatives company), and main water quality is：Calcium from
Sub- 900mg/L, total hardness is 1300mg/L, total alkalinity 220mg/L, Cl-380mg/L。
Do not change it is former using medicament in the case of, test water sulfuric acid controls the total alkalinity to be
220mg/L, adds bromine chloride its chlorine residue is reached 0.3mg/L, while adding composite corrosion inhibitor (propylene
The aqueous solution of acid/2- methyl -2'- acrylamidos propane sulfonic acid/hydroxypropyl acrylate copolymer and zinc sulfate,
Wherein acrylic acid/2- methyl -2'- acrylamidos propane sulfonic acid/hydroxypropyl acrylate copolymer is purchased from Luoyang
The YSW301 of Qiang Long Chemical Co., Ltd.s production) so that in every liter of pending test water, accordingly
Acrylic acid/2- methyl -2'- acrylamidos propane sulfonic acid/hydroxypropyl acrylate copolymer amount be 4.5
Mg, zinc sulfate makes the concentration of corresponding zinc ion be 2mg/L, is 5 times of sulphion concentration.Carbon steel is rotten
Erosion speed and adhesion speed are respectively 0.039mm/a and 7.5mg/ (cm2Month), the heterotroph of recirculated water
Sum is less than 1 × 10 after testing5Individual/ml.
Be can be seen that by the data of above-described embodiment and comparative example：The corrosivity of circulating cooling water containing sulfur is strong,
Original corrosion inhibiting and descaling agent corrosion rate can be caused exceeded；Even with the portion of techniques in the inventive method
Step, corrosion rate is also more difficult up to standard；Take control higher alkalisation (>300mg/L, comparative example 8)
Method, though corrosion rate can be reduced, test tube adhesion speed is still exceeded, i.e. need to coordinate control total alkali
The species of degree and chlorine residue and the composite corrosion inhibitor for adding can realize the purpose of the present invention.Using this hair
Bright processing method, it is not necessary to change the medicament of scene application, disclosure satisfy that corrosion of carbon steel speed is less than
0.1mm/a, carbon steel test tube adhesion speed are less than 20mg/ (cm2Month) technical requirements, illustrate the present invention
Method be suitable for the treatment of sulfur-bearing high rigidity recirculated cooling water.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. it is a kind of process circulating cooling water containing sulfur method, it is characterised in that the method includes：
Oxidizer containing chlorine and composite corrosion inhibitor are added toward circulating cooling water containing sulfur, and is controlled cold containing sulfur cycle
But the total alkalinity of water is maintained in the range of 170-300mg/L；Wherein, the consumption of the oxidizer containing chlorine makes
The chlorine residue in circulating cooling water containing sulfur is obtained for 0.1-0.6mg/L, preferably 0.1-0.4mg/L, it is described compound
Corrosion inhibiter contains water-soluble zinc salt and organic polymer type water treatment agent.
2. method according to claim 1, wherein, the oxidizer containing chlorine is by chlorine, secondary chlorine
Sour calcium, sodium hypochlorite, bleaching powder, sodium dichloro cyanurate, sym-closene, chlorine dioxide, chlorine
At least one offer in bromine, bromochlorodimethyl hydanton and bromine chloromethane ethylhydantoin is provided.
3. method according to claim 1, wherein, in terms of zinc ion, the water-soluble zinc salt
Consumption and circulating cooling water containing sulfur in sulphion content between ratio be 2.5-5:1, preferably
3-4:1。
4. the method according to claim 1 or 3, wherein, the water-soluble zinc salt is selected from chlorination
At least one of zinc, zinc nitrate and zinc sulfate.
5. method according to claim 1, wherein, the circulating cooling water containing sulfur relative to every liter,
The consumption that the organic polymer type water treatment agent is counted with butt as 3-9mg, preferably 4.5-7.5mg.
6. method according to claim 1 or 5, wherein, the organic polymer type water process
The number-average molecular weight of agent is 300-10000.
7. method according to claim 1 or 5, wherein, the organic polymer type water process
Agent is selected from poly- (methyl) acrylic acid, HPMA, poly-aspartic-acid, poly-epoxy succinic acid, (methyl)
Acrylic acid/(methyl) hydroxypropyl acrylate copolymer, (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/(methyl)
Methyl acrylate copolymer, maleic acid/Styrene Sulfonic Acid Copolymer, maleic anhydride/styrene sulfonic acid copolymerization
Thing, (methyl) acrylic/styrene sulfonic acid copolymer, (methyl) acrylate/Styrene Sulfonic Acid Copolymer,
Maleic acid/allyl sulphonic acid copolymer, maleic anhydride/allyl sulphonic acid copolymer, (methyl) acrylic acid/alkene
Propyl sulfonic acid copolymer, (methyl) acrylic acid/vinyl sulfonic acid copolymer, (methyl) acrylic acid/2- methyl -2'-
Acrylamido propane sulfonic acid copolymer, (methyl) acrylic acid/acrylamide/2- methyl -2'- acrylamidos
Propane sulfonic acid copolymer, (methyl) acrylic acid/(methyl) acrylate/2- methyl -2'- acrylamido propane sulphurs
Acid copolymer, (methyl) acrylic acid/maleic acid/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (first
Base) acrylic acid/maleic anhydride/2- methyl -2'- acrylamido propane sulfonic acid copolymers and (methyl) acrylic acid
In/2- acrylamidos -2- methylpropanephosphonic acids/2- methyl -2'- acrylamido propane sulfonic acid copolymers at least
It is a kind of.
8. method according to claim 7, wherein, the organic polymer type water treatment agent choosing
From maleic acid/Styrene Sulfonic Acid Copolymer, maleic anhydride/Styrene Sulfonic Acid Copolymer, (methyl) acrylic acid/
Styrene Sulfonic Acid Copolymer, (methyl) acrylate/Styrene Sulfonic Acid Copolymer, maleic acid/allyl sulphonic acid
Copolymer, maleic anhydride/allyl sulphonic acid copolymer, (methyl) acrylic acid/allyl sulphonic acid copolymer, (first
Base) acrylic acid/vinyl sulfonic acid copolymer, (methyl) acrylic acid/2- methyl -2'- acrylamidos propane sulfonic acid be total to
Polymers, (methyl) acrylic acid/acrylamide/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl)
Acrylic acid/(methyl) acrylate/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid
/ maleic acid/2- methyl -2'- acrylamido propane sulfonic acids copolymer, (methyl) acrylic acid/maleic anhydride/2- first
Base -2'- acrylamido propane sulfonic acid copolymers and (methyl) acrylic acid/2- acrylamido -2- methyl propyl-phosphines
At least one in acid/2- methyl -2'- acrylamido propane sulfonic acid copolymers.
9. the method according to any one in claim 1-8, wherein, control circulation
Other drainage amount for quantity of circulating water 4-5%.
10. the method according to any one in claim 1-8, wherein, it is described cold containing sulfur cycle
But the content of sulphion is 0.1-2mg/L in water；Preferably, with CaCO3Meter, it is described cold containing sulfur cycle
But in water the content of calcium ion in more than 700mg/L.
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| CN110803781A (en) * | 2018-08-06 | 2020-02-18 | 中国石油化工股份有限公司 | Composite corrosion and scale inhibitor containing polyphosphate, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur |
| CN116657128A (en) * | 2023-07-31 | 2023-08-29 | 杭州尚善若水环保科技有限公司 | Phosphorus-free prefilming combined reagent and circulating water phosphorus-free combined prefilming treatment method |
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| CN116657128A (en) * | 2023-07-31 | 2023-08-29 | 杭州尚善若水环保科技有限公司 | Phosphorus-free prefilming combined reagent and circulating water phosphorus-free combined prefilming treatment method |
| CN116657128B (en) * | 2023-07-31 | 2023-10-03 | 杭州尚善若水环保科技有限公司 | Phosphorus-free prefilming combined reagent and circulating water phosphorus-free combined prefilming treatment method |
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