CN106745838A - 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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- CN106745838A CN106745838A CN201510811150.5A CN201510811150A CN106745838A CN 106745838 A CN106745838 A CN 106745838A CN 201510811150 A CN201510811150 A CN 201510811150A CN 106745838 A CN106745838 A CN 106745838A
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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 0.2-1mg/L, and the composite corrosion inhibitor contains water-soluble zinc salt and organophosphorus-type corrosion inhibiter.The present invention adds particular kind of composite corrosion inhibitor by controlling total alkalinity and chlorine residue to coordinate, and can effectively control the corrosion of circulating cooling water containing sulfur, 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 sulphion life of the zinc ion easily and in water for the corrosion inhibitor formula containing zinc ion
Being precipitated into zinc sulphide and failed, therefore add the corrosion inhibiter of heavy dose has the danger of aggravation fouling.Two is many
The water system of number oil plant is limited by blowdown flow rate, it is impossible to is thoroughly replaced sulfur-bearing recirculated water in time, is caused
The corrosion rate of equipment is still higher, meanwhile, the consumption of the consumption, fresh water of water treatment agent and sewage
Discharge capacity rises by a relatively large margin.Three is to add basic agent excess, and the basicity of recirculated water can be made too high,
Cause 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 the 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 0.2-1mg/L, and the composite corrosion inhibitor contains water-soluble zinc salt
With organophosphorus-type corrosion inhibiter.
The present invention adds particular kind of composite corrosion inhibitor, Neng Gouyou by controlling total alkalinity and chlorine residue to coordinate
The corrosion of effect control circulating cooling water containing sulfur, 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 aqueous
The composite corrosion inhibitor of soluble zinc salt, but be not compromised by deposition of zinc salt and make adhesion speed exceeded.So as to
So that having saved medicament expense, fresh water without thoroughly being replaced to system after there is sulphur-containing substance leakage
Take and charges for disposing pollutants, reduce energy consumption.And, the method for the present invention can not change live original dosing shape
Carried out in the case of state, it is simple to operate, it is convenient and swift, 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；Material (particularly organophosphorus-type corrosion inhibiter, the organic polymer type water treatment agent being related in the present invention
And copper material corrosion inhibitor) weight (dried to perseverance at 120 DEG C with butt (or weight of contained solid)
The weight of (more than 4h) during 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 0.2-1mg/L (preferably 0.4-0.8
Mg/L), the composite corrosion inhibitor contains water-soluble zinc salt and organophosphorus-type corrosion inhibiter.
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 2-20mg, preferably 4.5-8.5mg.
According to the present invention, the consumption to water-soluble zinc salt and organophosphorus-type corrosion inhibiter is not required particularly.
Under preferable case, the ratio between the weight of the weight of the water-soluble zinc salt and the organophosphorus-type corrosion inhibiter
Be worth is 1:1-15, preferably 1:1.8-8, wherein, the weight of the organophosphorus-type corrosion inhibiter (has with butt
Effect content) meter.
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 organophosphorus-type corrosion inhibiter can be conventionally used as the various of corrosion inhibiter for this area
Organic phosphoric acid and/or its salt (ester).Preferably, the organophosphorus-type corrosion inhibiter is selected from hydroxyethylidene diphosphonic acid base
Acetic acid (HPAA), 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), ATMP (ATMP), second
The methylenephosphonic acid of diamines four (EDTMP), 2- phosphonic acid butane -1,2,4- tricarboxylic acids (PBTCA), hydroxyl phosphine
Acidic group sodium acetate, 1-hydroxy ethylidene-1,1-diphosphonic acid sodium, ATMP sodium, ethylene diamine tetra methylene phosphonic acid sodium,
2- phosphonic acid butane -1,2,4- sodium tricarboxylates, hydroxyethylidene diphosphonic acid guanidine-acetic acid potassium, 1-hydroxy ethylidene-1,1-diphosphonic acid potassium, ammonia
The methylenephosphonic acid potassium of base three, ethylene diamine tetra methylene phosphonic acid potassium, 2- phosphonic acid butanes -1,2,4- tricarboxylic acids potassium and many
At least one (or two or more) in first alcohol phosphate (PAPE).Wherein, polyalcohol phosphorus
Acid esters can be the material for meeting standard HG/T 2228-2006 " water treatment agent PAPE ".
According to the present invention, methods described can also include adding organic polymer toward circulating cooling water containing sulfur
Type water treatment agent.Circulating cooling water containing sulfur relative to every liter, the organic polymer type water treatment agent
Consumption (in terms of butt) can be as 0-6mg.
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.
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 use of the copper material corrosion inhibitor
Amount is (in terms of butt) as 0.5-5mg.
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.
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.
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 0.1-1mg/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, preferably 750-1250mg/L).Usually, the sulfur-bearing is followed
The total hardness of ring cooling water is 1000-2000mg/L, and total alkalinity is 50-400mg/L, chloride ion content
It 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；
Organophosphorus-type corrosion inhibiter (HEDP, HPAA, PBTCA, ATMP and PAPE etc.) and compound slow corrosion
The weight of agent is in terms of butt (effective content), for example, " adding the composite corrosion inhibitor of 4.8mg/L "
Represent circulating cooling water containing sulfur relative to every liter, the addition that composite corrosion inhibitor is counted with butt as 4.8mg,
The rest may be inferred.
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 785mg/L, total hardness is 1150
Mg/L, total alkalinity 120mg/L, Cl-290mg/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 situation using medicament YSW105 (purchased from Beijing Yan Hua set associatives company) of oil plant
Under, use NaHCO3The total alkalinity of Adjustment Tests water is 250mg/L, adds sodium hypochlorite to reach chlorine residue
0.4mg/L, the composite corrosion inhibitor for adding 4.8mg/L (is 5 containing weight ratio:1 HEDP and zinc chloride).
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 1200mg/L, total hardness is 1750
Mg/L, total alkalinity 80mg/L, Cl-450mg/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 situation using medicament YSW105 (purchased from Beijing Yan Hua set associatives company) of oil plant
Under, use NaHCO3The total alkalinity of Adjustment Tests water is 200mg/L, adds sodium hypochlorite to make its chlorine residue
Up to 0.6mg/L, the composite corrosion inhibitor for adding 6.2mg/L (is 25 containing weight ratio:6 HPAA and nitre
Sour zinc).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 1250
Mg/L, total alkalinity 180mg/L, Cl-360mg/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 situation using medicament YSW105 (purchased from Beijing Yan Hua set associatives company) of oil plant
Under, use NaHCO3The total alkalinity of Adjustment Tests water is 200mg/L, adds sodium hypochlorite to make its chlorine residue
Up to 0.8mg/L, the composite corrosion inhibitor for adding 4.6mg/L (is 10 containing weight ratio:5:8 HEDP,
ATMP and zinc sulfate).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 situation using medicament YSW105 (purchased from Beijing Yan Hua set associatives company) of oil plant
Under, add vulcanized sodium to make S2-1mg/L is reached, NaHCO is used3The total alkalinity of Adjustment Tests water is
250mg/L, adds Babysafe to make its chlorine residue up to 0.2mg/L, adds the composite corrosion inhibitor of 5.4mg/L (to contain
It is 4 to have weight ratio:4:1 HEDP, PBTCA and zinc sulfate).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 1100
Mg/L, total alkalinity 200mg/L, Cl-300mg/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 situation using medicament YSW105 (purchased from Beijing Yan Hua set associatives company) of oil plant
Under, add vulcanized sodium to make S2-1mg/L is reached, NaHCO is used3The total alkalinity of Adjustment Tests water is
250mg/L, adds Babysafe to make its chlorine residue up to 0.5mg/L, adds the composite corrosion inhibitor of 6.4mg/L (to contain
It is 3 to have weight ratio:3:2 ATMP, HPAA and zinc nitrate).The results are 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 1000mg/L, total hardness is 1500
Mg/L, total alkalinity 110mg/L, Cl-370mg/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 situation using medicament YSW105 (purchased from Beijing Yan Hua set associatives company) of oil plant
Under, add vulcanized sodium to make S2-1mg/L is reached, NaHCO is used3The total alkalinity of Adjustment Tests water is
210mg/L, adds Babysafe to make its chlorine residue up to 0.9mg/L, adds the composite corrosion inhibitor of 8.4mg/L (to contain
It is 2.5 to have weight ratio:1 PAPE (being purchased from Luoyang Qiang Long Chemical Co., Ltd.s, article No. is ZF151MS)
And zinc chloride).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 250mg/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 reaches its chlorine residue to addition sodium hypochlorite in test water
0.4mg/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 (contains to the composite corrosion inhibitor of addition 4.8mg/L in test water
Weight ratio is 5:1 HEDP and zinc chloride).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 250mg/L and to
Sodium hypochlorite is added in test water makes its chlorine residue reach 0.4mg/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 250mg/L and to
The composite corrosion inhibitor that 4.8mg/L is added in test water (is 5 containing weight ratio:1 HEDP and chlorination
Zinc), 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, do not changing oil refining
Factory is former using in the case of medicament, its chlorine residue is reached 0.4mg/L to sodium hypochlorite is added in test water
And add 4.8mg/L composite corrosion inhibitor (containing weight ratio be 5:1 HEDP and zinc chloride), and
Without NaHCO3Adjustment total alkalinity.The results are 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.
Experiment supplement water is live fresh water, and continuously vulcanized sodium is filled into in recirculated water, makes corresponding S2-
It is 0.6mg/L relative to the concentration of circulation water inventory.Recirculated water adds original to use medicament YSW105 (purchases
From Beijing Yan Hua set associatives company), main water quality is：Calcium ion 1250mg/L, total hardness is 1850mg/L,
Total alkalinity 200mg/L, Cl-550mg/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 0.5mg/L, while adding the compound slow corrosion of 5.4mg/L
Agent (is 5 containing weight ratio:1 HEDP and zinc chloride).Corrosion of carbon steel speed and adhesion speed difference
It is 0.046mm/a and 11mg/ (cm2Month), the total heterotrophic bacteria count of recirculated water is less than 1 × 10 after testing5
Individual/ml.
Comparative example 8
Method according to embodiment 7 carries out dynamic analog test, unlike, test water sulfuric acid control
Total alkalinity processed is 350mg/L.Corrosion of carbon steel speed and adhesion speed are respectively 0.035mm/a and 25
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.
Experiment supplement water is live fresh water, and continuously vulcanized sodium is filled into in recirculated water, makes corresponding S2-
It is 0.4mg/L relative to the concentration of circulation water inventory.Recirculated water adds original to use medicament YSW105 (purchases
From Beijing Yan Hua set associatives company), main water quality is：Calcium ion 900mg/L, total hardness is 1350mg/L,
Total alkalinity 220mg/L, Cl-350mg/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 the compound slow corrosion of 6.4mg/L
Agent (is 3 containing weight ratio:3:2 ATMP, HPAA and zinc nitrate).Corrosion of carbon steel speed and adhesion
Speed is respectively 0.04mm/a and 9mg/ (cm2Month), the total heterotrophic bacteria count of recirculated water is less than after testing
1×105Individual/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 (8)
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
It is 0.2-1mg/L, preferably 0.4-0.8mg/L to obtain the chlorine residue in circulating cooling water containing sulfur, and described being combined is delayed
Erosion agent contains water-soluble zinc salt and organophosphorus-type corrosion inhibiter.
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, the circulating cooling water containing sulfur relative to every liter,
The consumption that the composite corrosion inhibitor is counted with butt as 2-20mg, preferably 4.5-8.5mg.
4. the method according to claim 1 or 3, wherein, the weight of the water-soluble zinc salt with
Ratio between the weight of the organophosphorus-type corrosion inhibiter is 1:1-15, preferably 1:1.8-8, it is described organic
The weight of phosphorous corrosion inhibiter is in terms of butt.
5. the method according to claim 1 or 4, wherein, the water-soluble zinc salt is selected from chlorination
At least one of zinc, zinc nitrate and zinc sulfate.
6. the method according to claim 1 or 4, wherein, the organophosphorus-type corrosion inhibiter is selected from
Hydroxyethylidene diphosphonic acid guanidine-acetic acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, ATMP, ethylene diamine tetra methylene phosphonic acid,
2- phosphonic acid butane -1,2,4- tricarboxylic acids, hydroxyethylidene diphosphonic acid guanidine-acetic acid sodium, 1-hydroxy ethylidene-1,1-diphosphonic acid sodium, amino
Three methene Alendronates, ethylene diamine tetra methylene phosphonic acid sodium, 2- phosphonic acid butane -1,2,4- sodium tricarboxylates, hydroxyl
Phosphono-acetic acid potassium, 1-hydroxy ethylidene-1,1-diphosphonic acid potassium, ATMP potassium, ethylene diamine tetra methylene phosphonic acid
At least one in potassium, 2- phosphonic acid butanes -1,2,4- tricarboxylic acids potassium and PAPE.
7. the method according to any one in claim 1-6, wherein, it is described cold containing sulfur cycle
But the content of sulphion is 0.1-1mg/L in water.
8. the method according to any one in claim 1-7, wherein, with CaCO3Meter, institute
The content of calcium ion in circulating cooling water containing sulfur is stated in more than 700mg/L.
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| CN109422354A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Circulating cooling water containing sulfur processing system and its application |
| CN109422356A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Circulating cooling water containing sulfur composition for treating and its application |
| CN109422351A (en) * | 2017-08-29 | 2019-03-05 | 中国石油化工股份有限公司 | Circulating cooling water containing sulfur processing system and its application |
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