CN102730864B - Method for treating oil-leaking circulating water - Google Patents
Method for treating oil-leaking circulating water Download PDFInfo
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Abstract
The invention provides a method for treating oil-leaking circulating water, comprising the following steps of: a) adding an oxidation type bactericide and optional glutaraldehyde; b) adding a scale and corrosion inhibitor which comprises one component selected from the group consisting of water-soluble borate, water-soluble gluconate and water-soluble silicate or a mixture thereof, at least an organophosphonate acid, at least an organic carboxylic acid polymer, an optional copper corrosion inhibitor and optional zinc salt; and c) adding a quaternary phosphonium salt type cationic surfactant and an optional polysorbate nonionic surfactant. The method provided by the invention can be used to remove oil and peel off microbial slime from equipment of the circulating water system at a time without large-scale pollution discharge.
Description
Technical field
The present invention relates to a kind for the treatment of process of recirculated water, relate in particular to a kind of leakage of oil circulating water treatment method.
Background technology
In circulating water system, often oil leak can occur, the oil product that is leaked to circulating water system generally comprises lightweight oil and wax oil.Lightweight oil is generally made a general reference the hydrocarbon mixture of the about 50-350 of boiling spread ℃.In petroleum refining industry, it can refer to light ends oil, also can refer to clean or white.The former comprises cut and the topses such as gasoline (or petroleum naphtha), pyrolysis gasoline, kerosene (or rocket engine fuel), solar oil (or atmospheric gas oil), raffinates oil etc., and they are mainly from devices such as crude distillation, catalytic cracking, thermally splitting, petroleum coking, hydrocracking and catalytic reforming; The latter is the oil product that light ends oil obtains after treating process.Wax oil refers to the heavy component oil of the content of wax, is the intermediate product of oil refining process, is liquid under normal temperature, and not soluble in water, viscosity is larger.Oil leak is the common a kind of of distillation system's material from leakage.
Oil product can produce following harm while revealing: 1) make microorganism grow in a large number, and water quality severe exacerbation, its characteristic slowly discharging makes system water blame to recover; 2) oil product that enters water cooling tower is easily attached on filler, reduces radiating effect and also makes the heavy burden of filler support increase, and when serious, can cause collapsing of filler; 3) oil product is attached on pipeline, can make corrosion-mitigation scale-inhibition medicament not play a role, and causes serious underdeposit corrosion; 4) oil product and the biological clay grown in a large number can adhere in a large number in heat exchange manifold, have a strong impact on heat transfer effect, even can blocking pipe when of a serious nature.
The circulating water treatment of revealing for oil product, large chemical complex takes the treatment process of large excretion and large complement conventionally, first adds adhesive mud remover, peels off rear a large amount of draining, then adds corrosion inhibiting and descaling agent.The method has consumed a large amount of fresh waters and has produced the sewer of equivalent, has wasted water treatment agent, and after blowdown, needs again to improve cycles of concentration, and treatment effect is unsatisfactory.
Chinese patent application CN1193609A discloses the cleaning prefilming agent that waits dirt in a kind of circulating water system for cleaning system microorganism dirt, clean prefilming agent and consist of biological enzyme scavenging agent, biostats, inorganic salt complex agent and the conventional water quality stabilizer that is comprised of inhibiter and dispersion agent, wherein inorganic salt complex agent is comprised of silicate, manganate, carbonate, orthophosphoric acid salt.Purging method is under the normal operating condition of circulating water regiment commander thermal load, biological enzyme scavenging agent, biostats, inorganic salt complex agent and conventional water quality stabilizer are joined in recirculated water by the certain concentration of always possessing the water yield respectively, and maintain this concentration 15-60 days.Chinese patent application CN1125697A discloses the using method of a kind of biological cleanser in circulating water system, and biological enzyme scavenging agent is added in circulating water system, and biological enzyme scavenging agent is fat hydrolase.In circulating water system, can add conventional water quality stabilizer.Adopt the method the greasy dirt in recirculated water can be removed, make leaked substance degraded.Its shortcoming is has used expensive biological enzyme scavenging agent.
Summary of the invention
The object of the present invention is to provide a kind of leakage of oil circulating water treatment method.Use method of the present invention can carry out oil removing to the equipment of circulating water system, peel off microorganism viscosity mud, can once complete, keep water treatment effect stability, without a large amount of blowdowns.
To achieve the above object of the invention, the invention provides a kind of leakage of oil circulating water treatment method, it comprises the following steps: a) add oxidative bactericide and optional glutaraldehyde; B) add anti-incrustation corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises a kind of or its mixture in water-soluble borate, Water-Soluble Glucose hydrochlorate and water-soluble silicate, at least one organic phospho acid, at least one organic carboxyl acid base polymer, optional copper material corrosion inhibitor and optional zinc salt; C) add quaternary phosphine salt type cats product and optional polysorbate nonionogenic tenside.
Oxidative bactericide of the present invention is at least one is selected from the sterilant of chloride sterilant and brominated sterilant; Described chloride sterilant is preferably from chlorine, hypochlorous acid and salt thereof, dichloroisocyanuric acid sodium, TCCA (Trichloroisocyanuric acid), 1,3-bis-chloro-5,5-dimethyl hydantion, the bromo-3-of 1-are chloro-5,5-dimethyl hydantion, and wherein hypochlorite is more preferably from clorox, Losantin; Described brominated sterilant is preferably from hypobromous acid and salt, organo bromine microbicide and bromine chloride, wherein hypobromite more preferably from sodium hypobromite and hypobromous acid calcium, organo bromine microbicide more preferably from 2,2-bis-bromo-3-time aminopropan acid amides and the bromo-3-of 1-are chloro-5, and 5-dimethyl is for glycolylurea; Most preferably, with respect to pending aqueous solution total amount, the effective concentration of oxidative bactericide of the present invention is 10-50mg/L, and the effective concentration of glutaraldehyde is 0-120mg/L, be preferably 30-120mg/L.
Method of the present invention comprises according to a conventional method add conventional oxidative bactericide and optional glutaraldehyde in recirculated cooling water, with the microorganism in controlled circulation cooling water system.Conventional oxidative bactericide, effectively the microorganism of controlled circulation cooling water system, prevents a large amount of generations of microorganism excess growth and foundry loam; The use of glutaraldehyde, controls very effective for the foundry loam of leakage of oil recirculated water.
In anti-incrustation corrosion inhibitor of the present invention, organic carboxyl acid base polymer is selected from homopolymer, copolymer and terpolymer, preferably from polyacrylic acid, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said acrylate is preferably from vinylformic acid C
1-8ester, more preferably from methyl acrylate, ethyl propenoate and Propylene glycol monoacrylate.
In anti-incrustation corrosion inhibitor of the present invention, organic phospho acid is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methylenephosphonic acids, L-glutamic acid two methylenephosphonic acids, thionamic acid two methylenephosphonic acids and taurine two methylenephosphonic acids and polyether-based polyamino methylene phosphonic acid.
While using equipment made of copper in recirculating cooling water system, anti-incrustation corrosion inhibitor of the present invention also contains heterogeneous ring compound as copper material corrosion inhibitor, is preferably mercaptobenzothiazole, methyl benzotriazazole or benzotriazole.
For the stronger recirculated cooling water of corrodibility, its inhibition problem should be the major issue that will solve, and when composite scale-inhibiting corrosion inhibitor is used for to recirculated cooling water, also can contain zinc salt as inhibiter, and described zinc salt is preferably zinc sulfate or zinc chloride.
Anti-incrustation corrosion inhibitor of the present invention with respect to the effective concentration of pending each component of aqueous solution total amount is: when single medicament is done inhibiter, its effective working concentration is 50-150mg/L, when various medicaments is composite, total effectively working concentration of inhibiter is 30-100mg/L, and wherein boratory concentration is with B
4o
7 2-the concentration of meter, gluconate in the concentration of gluconate, silicate with SiO
2meter.Organic carboxyl acid base polymer concentration is 2-15mg/L, and organic phospho acid concentration is 2-15mg/L, and the effective concentration of copper material corrosion inhibitor is 0-1.5mg/L, is preferably 0.5-1.5mg/L, and the effective concentration of zinc salt is with Zn
2+count 0-3.0mg/L, be preferably 0.5-3.0mg/L.
The adding purpose of tensio-active agent is to peel off the microorganism viscosity mud on equipment tube wall and prevents from again adhering to.The preferred self-drifting of quaternary alkylphosphonium salt of the present invention is (R)
4pX quaternary alkylphosphonium salt, wherein R is identical or different, for being selected from alkyl, the carbonatoms that carbonatoms is 1-20, is 2-20 alkoxyalkyl or phenyl, and X is chlorine or bromine, more preferably from 4-butyl phosphonium chloride, four butyl phosphonium bromides, tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, trityl group phosphonium chloride, triphenyl ethyl phosphonium chloride, triphenyl Bing Ji phosphonium chloride, triphenyl butyl phosphonium chloride, trityl group phosphonium bromide, tri-phenyl-ethyl phosphonium bromide, triphenyl propyl group phosphonium bromide, triphenyl butyl phosphonium bromide, dodecyl tributyl phosphonium bromide, dodecyl tributyl phosphonium chloride, tetradecyl tributyl phosphonium bromide, tetradecyl tributyl phosphonium chloride, phosphonium hexadecanyl-3-butyl chloride, hexadecyl tributyl phosphonium bromide, dodecyloxy methyl tributyl phosphonium bromide, dodecyloxy methyl tributyl phosphonium chloride, dodecyloxy ethyl tributyl phosphonium chloride, dodecyloxy ethyl tributyl phosphonium bromide, tetradecyloxyaniline ethyl tributyl phosphonium chloride, tetradecyloxyaniline ethyl tributyl phosphonium bromide, methoxyl methyl triphenyl phosphonium chloride and methoxyl methyl three phenyl phosphonium bromides.
Polysorbate nonionogenic tenside of the present invention is selected from polyoxyethylene sorbitan fatty acid ester; Preferred selfpolyoxyethylene (10-30) anhydrous sorbitol C
12-C
18fatty acid ester; More preferably selfpolyoxyethylene (10-30) anhydrous sorbitol laurate, polyoxyethylene (10-30) anhydrous sorbitol cetylate, polyoxyethylene (10-30) Span60 and polyoxyethylene (10-30) sorbitan monooleate; Selfpolyoxyethylene (10-30) anhydrous sorbitol laurate most preferably; Concrete example has polysorbas20 (polyoxyethylene (20) sorbitan mono-laurate), polysorbate40 (polyoxyethylene (20) anhydrous sorbitol monopalmitate), polysorbate60 (polyoxyethylene (20) sorbitan monostearate), tween 80 (polyoxyethylene (20) sorbitan monooleate).
With respect to pending aqueous solution total amount, the effective concentration of quaternary phosphine salt type cats product of the present invention is 10-100mg/L, and the effective concentration of polysorbate nonionogenic tenside is 0-100mg/L, is preferably 10-100mg/L.
B of the present invention) described in step anti-incrustation corrosion inhibitor can add in the mode of single dose, also can first be mixed with composite scale-inhibiting corrosion inhibitor, then composite scale-inhibiting corrosion inhibitor is once added in recirculated water, preferably in the latter's mode, carry out.Available ordinary method is prepared composite scale-inhibiting corrosion inhibitor of the present invention, and the reinforced order of each component is unimportant.
The addition step of leakage of oil circulating water treatment method of the present invention can be successively by a), b) and c) step carry out, also can be by carry out a)-c of other arbitrary orders) step, can also carry out these three steps simultaneously.
Method of the present invention is by adding oxidative bactericide and optional glutaraldehyde, tensio-active agent, can be in the oil product and microorganism viscosity mud effectively peeled off in exchanger tube wall, control microorganism growth, and prevent that microorganism viscosity mud from adhering to again, be applied in recirculated cooling water together with composite scale-inhibiting corrosion inhibitor, water treatment effect in the time of can guaranteeing circulating water system oil leak, makes system with low blowdown flow rate, compared with high concentration multiple smooth running.Advantage of the present invention is simple to operate, without the large excretion and large complement of water.Can be used for realizing the online recovery after circulating water system oil leakage.
Embodiment
The following examples will contribute to illustrate the present invention, but not limit to its scope.
In following embodiment and comparative example, polysorbas20, polysorbate40, polysorbate60, tween 80 used is the production of Guangzhou Xi Lu Chemical Co., Ltd..
Following embodiment and comparative example test raw water quality used is in Table 1.
Table 1 test raw water quality
Note: 1) pHWu unit, specific conductivity is μ s/cm, its counit is mg/L, Ca
2+, total alkalinity, total hardness be all with CaCO
3meter, lower same; 2) Ca
2+represent calcium hardness, lower same.
The Reliable Evaluating Methods of Their Performance of the composite scale-inhibiting corrosion inhibitor that following embodiment is prepared is as follows:
Corrosion inhibition: by 20
#carbon steel test piece is fixed on lacing film instrument, puts into the test water that is added with the scale inhibitor agent concentration adding by embodiment and (table 1 is tested to former water 1 and supplement Ca
2+numerical value while being 3 times to its cycles of concentration, as test water, in process of the test, controlling pH value is 8.0 ± 0.2; To test former water 2 and 3 and supplement respectively Ca
2+numerical value while being 5 times with basicity to its cycles of concentration, as test water), 40 ± 1 ℃ of steady temperatures, keep rotating speed 75r/min rotation 72h, and before and after record test, the weight of test piece, calculates average corrosion rate.
Average corrosion rate calculation formula is:
F＝(C×ΔW)/(A×T×ρ)
C: computational constant, take mm/a during as unit, C=8.76 * 10
7
Δ W: the corrosion weight loss of test specimen (g)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
Resistance calcium carbonate scale performance: get test water and (supplement Ca by testing former water 1 in table 1
2+numerical value while being 3 times to its cycles of concentration, as test water; To test former water 2 and 3 and supplement respectively Ca
2+numerical value while being 5 times with basicity to its cycles of concentration, as test water) add volumetric flask, then add required certain density anti-incrustation corrosion inhibitor, standing 10h in 80 ± 1 ℃ of waters bath with thermostatic control, remains Ca in sampling analysis water after cooling
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: the rear Ca of test solution test that adds water conditioner
2+concentration (mg/L)
C
0: with the Ca after the blank test solution test of water conditioner
2+concentration (mg/L)
C
1: Ca in the test solution configuring before test
2+concentration (mg/L)
The mensuration of heterotrophic bacterium: get test water sample, adopt 10 times of dilution technologies of former water in sterilisable chamber, test water sample is diluted to suitable multiple, and the water sample of corresponding extension rate is inoculated in culture dish.Then aseptic culture medium is poured in culture dish, mix with water sample, etc. being inverted after culture medium solidifying in the incubator be placed on 29 ± 1 ℃, cultivate 72 ± 4h.After cultivation, take out culture dish, select those culture dish with 30-300 bacterium colony to count, colony number is multiplied by the heterotrophic bacterium number that corresponding dilution training number is this water sample.
Adhere to the mensuration of speed: test tube is positioned in the bypass of interchanger, takes out test tube after off-test, clean after test tube outer wall, constant temperature drying, takes the heavy (W of band bur test tube
1).Then clean inboard wall of test tube bur, be dried, take the heavy (W of test tube
2), calculate and adhere to speed F '.
F’＝7.2×10
5×(W
1-W
2)/(A×t)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
When measuring scale-inhibiting properties, following embodiment and comparative example are used all adjust pHs not of any test water quality; When measuring corrosion inhibition, when following embodiment and comparative example use-testing water 1, need adjust pH.
Embodiment 1
The preparation of anti-incrustation corrosion inhibitor: take 147.4g sodium borate decahydrate (containing B
4o
7 2-60.0g) join 215.3g deionized water for stirring even, adding 24.0g effective constituent is 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, add solid content be 30% acrylic acid/esters/2-methyl-2 ' (mass ratio of vinylformic acid, acrylate and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 3: 1: 1 to-acrylamido propane sulfonic acid copolymer 1 3.3g, Limiting Viscosity in the time of 30 ℃ is 0.065dl/g), be made into inhibiter 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 2, the effective concentration of sodium borate decahydrate, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid and acrylic acid/esters/2-methyl-2 in water '-acrylamido propane sulfonic acid multipolymer is respectively 60.0mg/L, 12.0mg/L and 4mg/L.
During corrosion inhibition test, in beaker, add 200mg pyrolysis gasoline, during antisludging test, in volumetric flask, add 50mg pyrolysis gasoline, then add four butyl phosphonium bromide 95mg/L.Test-results is in Table 2.
Embodiment 2
The preparation of anti-incrustation corrosion inhibitor: take 284.6g anhydrous sodium metasilicate (containing SiO
2140.0g) join 77.4g deionized water for stirring even, adding 8.0g effective constituent is 50% Amino Trimethylene Phosphonic Acid, add solid content to be vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer 1 6.7g (vinylformic acid in multipolymer of 30%, the mass ratio of toxilic acid and 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity in the time of 30 ℃ is 0.075dl/g), and vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer 13.3g (vinylformic acid in multipolymer, the mass ratio of Propylene glycol monoacrylate and methyl acrylate is 3: 1: 1, Limiting Viscosity in the time of 30 ℃ is 0.068dl/g), be made into inhibiter 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 3, in water, anhydrous sodium metasilicate, Amino Trimethylene Phosphonic Acid, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer effective concentration are respectively 140mg/L, 4mg/L, 5mg/L and 4mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil during antisludging test in volumetric flask, then add dodecyl tributyl phosphonium bromide 50mg/L, test-results is in Table 2.
Embodiment 3
The preparation of anti-incrustation corrosion inhibitor: taking 95.0g Sunmorl N 60S, to join 240.2g deionized water for stirring even, adding 16.0g effective constituent is 50% 2-phosphonate group-1, 2, 4-butane tricarboxylate, add solid content to be acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer 40.0g (vinylformic acid in multipolymer of 30%, the mass ratio of acrylamide and 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g), add Zinc Sulphate Heptahydrate 8.8g, stir, be made into inhibiter 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 2 and 3, aqueous humor glucose acid sodium, 2-phosphonate group-1,2,4-butane tricarboxylate, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and Zn
2+effective concentration be respectively 95mg/L, 8mg/L, 12mg/L and 2mg/L.
During corrosion inhibition test, in beaker, add 200mg solar oil, add 50mg solar oil during antisludging test in volumetric flask, then add respectively dodecyl tributyl phosphonium chloride 40mg/L and polysorbas20 40mg/L, test-results is in Table 2.
Embodiment 4
The preparation of anti-incrustation corrosion inhibitor: take 41.7g five hydration potassium tetraborates (containing B
4o
7 2-20.0g), 20.0g Potassium Gluconate, join 269.0g deionized water for stirring even, adding 25.0g effective constituent is 40% hydroxyethylidene diphosphonic acid guanidine-acetic acid, add solid content be 30% vinylformic acid/2-methyl-2 ' (mass ratio of vinylformic acid and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 7: 3 to-acrylamido propane sulfonic acid multipolymer 43.3g, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), add benzotriazole 1.0g, be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 2, in water, the effective concentration of five hydration potassium tetraborates, Potassium Gluconate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and benzotriazole is respectively 20mg/L, 20mg/L, 10mg/L, 13mg/L and 1mg/L.
During corrosion inhibition test, in beaker, add 100mg wax oil, add 25mg wax oil during antisludging test in volumetric flask, then add respectively tetradecyl tributyl phosphonium bromide 60mg/L and polysorbate40 50mg/L, test-results is in Table 2.
Embodiment 5
The preparation of anti-incrustation corrosion inhibitor: take 141.6g tetra-hydration eight Sodium Tetraboratees (containing B
4o
7 2-53.4g), 21.6g Sunmorl N 60S, join 188.5g deionized water for stirring even, adding 15.0g effective constituent is 40% ethylene diamine tetra methylene phosphonic acid, adding solid content is that (in multipolymer, the mass ratio of vinylformic acid and vinyl sulfonic acid is 8: 2 for vinylformic acid/vinyl sulfonic acid multipolymer 33.3g of 30%, Limiting Viscosity in the time of 30 ℃ is 0.067dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 3, in water, the effective concentration of four hydration eight Sodium Tetraboratees, Sunmorl N 60S, ethylene diamine tetra methylene phosphonic acid and vinylformic acid/vinyl sulfonic acid multipolymer is respectively 53.4mg/L, 21.6mg/L, 6mg/L and 10.0mg/L.
During corrosion inhibition test, in beaker, add 40mg wax oil, add 10mg wax oil during antisludging test in volumetric flask, then add respectively tetradecyl tributyl phosphonium chloride 30mg/L and polysorbate60 90mg/L, test-results is in Table 2.
Embodiment 6
The preparation of anti-incrustation corrosion inhibitor: take 97.2g metasilicate pentahydrate sodium (containing SiO
227.5g), 27.5g Zinc Gluconate, join 239.5g deionized water for stirring even, adding 12.5g effective constituent is 40% diethylene triamine pentamethylene phosphonic, adding solid content is that (in multipolymer, the mass ratio of vinylformic acid and allyl sulphonic acid is 7: 3 for vinylformic acid/allyl sulphonic acid multipolymer 23.3g of 30%, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 2 and 3, in water, the effective concentration of metasilicate pentahydrate sodium, Zinc Gluconate, diethylene triamine pentamethylene phosphonic, vinylformic acid/allyl sulphonic acid multipolymer is respectively 27.5mg/L, 27.5mg/L, 5mg/L and 7mg/L.
During corrosion inhibition test, in beaker, add 200mg solar oil, add 50mg solar oil during antisludging test in volumetric flask, then add respectively dodecyloxy methyl tributyl phosphonium bromide 90mg/L and tween 80 20mg/L, test-results is in Table 2.
Embodiment 7
The preparation of anti-incrustation corrosion inhibitor: take 62.4g potassium silicate (containing SiO
230.0g), 35.0g Potassium Gluconate, join 252.6g deionized water for stirring even, add effective constituent be 40% to two phosphono and sulfonic 10.0g and polyether-based polyamino methylene phosphonic acid 10.0g, adding solid content is that (in multipolymer, the mass ratio of toxilic acid and allyl sulphonic acid is 7: 3 for toxilic acid/allyl sulphonic acid multipolymer 30.0g of 30%, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 2, water mesosilicic acid potassium, Potassium Gluconate, the effective concentration of two phosphono and sulfonics, polyether-based polyamino methylene phosphonic acid and toxilic acid/allyl sulphonic acid multipolymer is respectively to 30mg/L, 35mg/L, 10mg/L, 10mg/L and 9mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil during antisludging test in volumetric flask, then add dodecyloxy methyl tributyl phosphonium chloride 60mg/L, test-results is in Table 2.
Embodiment 8
The preparation of anti-incrustation corrosion inhibitor: take 53.0g five hydration sodium tetraborates (containing B
4o
7 2-28.2g), 268.9g non-hydrate sodium metasilicate is (containing SiO
256.8g), join 43.1g deionized water for stirring even, add effective constituent to be 40% glycine two methylenephosphonic acid 7.5g and taurine two methylenephosphonic acid 7.5g, adding solid content is that (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 7: 3 to 30% acrylate/Styrene Sulfonic Acid Copolymer 20.0g, Limiting Viscosity in the time of 30 ℃ is 0.074dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 3, in water, the effective concentration of five hydration sodium tetraborates, non-hydrate sodium metasilicate, glycine two methylenephosphonic acids, taurine two methylenephosphonic acids and acrylate/Styrene Sulfonic Acid Copolymer multipolymer is respectively 28.2mg/L, 56.8mg/L, 3mg/L, 3mg/L and 6mg/L.
During corrosion inhibition test, in beaker, add 200mg pyrolysis gasoline, add 50mg pyrolysis gasoline during antisludging test in volumetric flask, then add dodecyloxy ethyl tributyl phosphonium chloride 20mg/L, test-results is in Table 2.
Embodiment 9
The preparation of anti-incrustation corrosion inhibitor: take 20.6g five hydration sodium tetraborates (containing B
4o
7 2-11.0g), 89.3g anhydrous sodium metasilicate is (containing SiO
244.0g), join 230.9g deionized water for stirring even, adding 22.5g effective constituent is 40% L-glutamic acid two methylenephosphonic acids, adding solid content is that (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3 to 30% vinylformic acid/Styrene Sulfonic Acid Copolymer 36.7g, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 2 and 3, in water, the effective concentration of five hydration sodium tetraborates, anhydrous sodium metasilicate, L-glutamic acid two methylenephosphonic acids and vinylformic acid/Styrene Sulfonic Acid Copolymer is respectively 11.0mg/L, 44.0mg/L, 9.0mg/L and 11.0mg/L.
During corrosion inhibition test, in beaker, add 200mg solar oil, add 50mg solar oil, then add tri-phenyl-ethyl phosphonium bromide 60mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 10
The preparation of anti-incrustation corrosion inhibitor: take 27.6g five hydration sodium tetraborates (containing B
4o
7 2-14.7g), 43.3g metasilicate pentahydrate sodium is (containing SiO
212.3g), to join 276.1g deionized water for stirring even for 8.0g Sunmorl N 60S and 0.8g mercaptobenzothiazole, adding 27.5g effective constituent is 40% thionamic acid two methylenephosphonic acids, adding solid content is that (in multipolymer, the mass ratio of toxilic acid and styrene sulfonic acid is 7: 3 to 30% toxilic acid/Styrene Sulfonic Acid Copolymer 16.7g, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water 1 and 2, in water, the effective concentration of five hydration sodium tetraborates, metasilicate pentahydrate sodium and toxilic acid/Styrene Sulfonic Acid Copolymer, mercaptobenzothiazole is respectively 10.5mg/L, 8.75mg/L, 5.75mg/L, 5mg/L and 0.8mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add hexadecyl tributyl phosphonium bromide 70mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Comparative example 1
Test is not except adding four butyl phosphonium bromides, and test conditions and testing sequence are with embodiment 1, and test-results is in Table 2.
Comparative example 2
Test is not except adding dodecyl tributyl phosphonium bromide, and test conditions and testing sequence are with embodiment 2, and test-results is in Table 2.
Comparative example 3
Test is not except adding dodecyl tributyl phosphonium chloride and polysorbas20, and test conditions and testing sequence are with embodiment 3, and test-results is in Table 2.
Comparative example 4
Test is not except adding tetradecyl tributyl phosphonium bromide and polysorbate40, and test conditions and testing sequence are with embodiment 4, and test-results is in Table 2.
Comparative example 5
Test is not except adding tetradecyl tributyl phosphonium chloride and polysorbate60, and test conditions and testing sequence are with embodiment 5, and test-results is in Table 2.
Comparative example 6
Test is not except adding dodecyloxy methyl tributyl phosphonium bromide and tween 80, and test conditions and testing sequence are with embodiment 6, and test-results is in Table 2.
Comparative example 7
Test is not except adding dodecyloxy methyl tributyl phosphonium chloride, and test conditions and testing sequence are with embodiment 7, and test-results is in Table 2.
Comparative example 8
Test is not except adding dodecyloxy ethyl tributyl phosphonium chloride, and test conditions and testing sequence are with embodiment 8, and test-results is in Table 2.
Comparative example 9
Test is not except adding tri-phenyl-ethyl phosphonium bromide, and test conditions and testing sequence are with embodiment 9, and test-results is in Table 2.
Comparative example 10
Test is not except adding hexadecyl tributyl phosphonium bromide, and test conditions and testing sequence are with embodiment 10, and test-results is in Table 2.
Table 2 embodiment corrosion-mitigation scale-inhibition result
Note: embodiment 4 and 10 corrosion inhibition test all hang with copper sheet, and its erosion rate is respectively 0.002mm/a and 0.003mm/a.
Data by above-described embodiment and comparative example can be found out: while adopting method of the present invention to process the various water quality of oil product leakage, adding of tensio-active agent do not affect the inhibition of anti-incrustation corrosion inhibitor and resistance calcium carbonate scale performance.
For simulated field, by the test method described in the chemical industry standard HG/T2160-91 of the People's Republic of China (PRC), carried out dynamic analog test, following embodiment 11～17 is dynamic simulation experiment.
Embodiment 11
The preparation of anti-incrustation corrosion inhibitor:
Take 29.5g five hydration sodium tetraborates (containing B
4o
7 2-15.7g), 39.3g Zinc Gluconate, join 78.5g deionized water for stirring even, adding 16.0g effective constituent is 50% 2-phosphonate group-1,2,4-butane tricarboxylate, adding solid content is 30% toxilic acid/Styrene Sulfonic Acid Copolymer 36.7g (in multipolymer, the mass ratio of toxilic acid and styrene sulfonic acid is 7: 3, and the Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), is made into composite corrosion inhibitor 200.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 200mg/L when adding in test water, five hydration sodium tetraborates, Zinc Gluconate, 2-phosphonate group-1 in water, the effective concentration of 2,4-butane tricarboxylate and toxilic acid/Styrene Sulfonic Acid Copolymer is respectively 15.7mg/L, 39.3mg/L, 8.0mg/L and 11.0mg/L.
Added amount of chemical is as follows:
A tower: waxy oil 100mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 200mg/L, in test water, add, add again dodecyloxy methyl tributyl phosphonium chloride 50mg/L, polysorbas20 40mg/L and 1,3-bis-is chloro-5, and 5-dimethyl hydantion 25mg/L, added 1 every three days, 3-bis-chloro-5,5-dimethyl hydantion 20mg/L, by the 8th day, adds glutaraldehyde 50mg/L.
B tower: test is not except adding dodecyloxy methyl tributyl phosphonium chloride and tween, and test conditions and testing sequence are with A tower.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 3 of table 1
Calcium hardness adds basicity: A tower 1000 ± 50mg/L, B tower 1000 ± 50mg/L
PH value is not all controlled
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 12
The preparation of anti-incrustation corrosion inhibitor:
Take 73.6g water glass (containing SiO
224.0g), 16.0g Sunmorl N 60S, join 52.9g deionized water for stirring even, adding 27.5g effective constituent is 40% thionamic acid two methylenephosphonic acids, adding solid content is that (in multipolymer, the mass ratio of vinylformic acid and Propylene glycol monoacrylate is 7: 3 to 30% vinylformic acid/Propylene glycol monoacrylate multipolymer 30.0g, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be made into composite corrosion inhibitor 200.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 200mg/L when adding in test water, the effective concentration of water mesosilicic acid sodium, Sunmorl N 60S, thionamic acid two methylenephosphonic acids and vinylformic acid/Propylene glycol monoacrylate multipolymer is respectively 24.0mg/L, 16.0mg/L, 11.0mg/L and 9.0mg/L.
Added amount of chemical is as follows:
A tower: contain pyrolysis gasoline 100mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 200mg/L, in test water, add, add again dodecyl tributyl phosphonium bromide 70mg/L and TCCA (Trichloroisocyanuric acid) 25mg/L, then every three days, add TCCA (Trichloroisocyanuric acid) 20mg/L, by the 8th day, add glutaraldehyde 70mg/L.
B tower: test is not except adding dodecyl tributyl phosphonium bromide, and test conditions and testing sequence are with A tower.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness: A tower 130 ± 20mg/L, B tower 130 ± 20mg/L
PH value is not all controlled
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 13
The preparation of anti-incrustation corrosion inhibitor:
Take 73.7g sodium borate decahydrate (containing B
4o
7 2-30.0g), 106.1g metasilicate pentahydrate sodium is (containing SiO
230.0g), join 175.7g deionized water for stirring even, adding 8.0g effective constituent is 50% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, adding solid content is that 30% vinylformic acid/2-methyl-2 ' (mass ratio of vinylformic acid and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 7: 3 to-acrylamido propane sulfonic acid copolymer 1 6.7g, Limiting Viscosity in the time of 30 ℃ is 0.069dl/g), adding solid content is 30% polymaleic anhydride 16.7g (30 ℃ time Limiting Viscosity be 0.071dl/g), add 3.1g zinc chloride, be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water, in water, the effective concentration of sodium borate decahydrate, metasilicate pentahydrate sodium, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, polymaleic anhydride, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and zine ion is respectively 30.0mg/L, 30.0mg/L, 4.0mg/L, 5.0mg/L, 5.0mg/L and 1.5mg/L.
Added amount of chemical is as follows:
A tower: contain solar oil 200mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 400mg/L, in test water, add, add again tetradecyl tributyl phosphonium chloride 40mg/L and dichloroisocyanuric acid sodium 30mg/L, then every three days, add dichloroisocyanuric acid sodium 20mg/L, by the 8th day, add glutaraldehyde 100mg/L.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness: A tower 130 ± 20mg/L
PH value is not controlled
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 14
The preparation of anti-incrustation corrosion inhibitor:
Take 26.3g five hydration potassium tetraborates (containing B
4o
7 2-12.6g), 48.5g potassium metasilicate is (containing SiO
218.9g), to join 59.0g deionized water for stirring even for 13.5g Potassium Gluconate, add 26.0g effective constituent be 50% to two phosphono and sulfonics, adding solid content is that 30% acrylic acid/esters/2-methyl-2 ' (mass ratio of vinylformic acid, acrylate and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 3: 1: 1 to-acrylamido propane sulfonic acid multipolymer 26.7g, Limiting Viscosity in the time of 30 ℃ is 0.074dl/g), be made into composite corrosion inhibitor 200.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 200mg/L when adding in test water, five hydration potassium tetraborates, potassium metasilicate, Potassium Gluconate in water, the effective concentration of two phosphono and sulfonics and acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer is respectively to 12.6mg/L, 18.9mg/L, 13.5mg/L, 13.0mg/L and 8.0mg/L.
Added amount of chemical is as follows:
A tower: contain pyrolysis gasoline 150mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 200mg/L, in test water, add, add again dodecyl tributyl phosphonium chloride 90mg/L, tween 80 30mg/L and 2,2-bis-bromo-3-time aminopropan acid amides 35mg/L, then every three days, add 2,2-bis-bromo-3-time aminopropan acid amides 15mg/L, by the 8th day, add glutaraldehyde 80mg/L.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 1 of table 1
Calcium hardness: A tower 800 ± 50mg/L
PH value A tower 8.0 ± 0.2
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 15
The preparation of anti-incrustation corrosion inhibitor:
Take 178.9g anhydrous sodium metasilicate (containing SiO
288.00g) and 1.0g mercaptobenzothiazole to join 183.4g deionized water for stirring even, adding 20.0g effective constituent is 50% diethylene triamine pentamethylene phosphonic, adding solid content is that (in multipolymer, the mass ratio of vinylformic acid and allyl sulphonic acid is 7: 3 for vinylformic acid/allyl sulphonic acid copolymer 1 6.7g of 30%, Limiting Viscosity in the time of 30 ℃ is 0.074dl/g), be made into inhibiter 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water, in water, the effective concentration of anhydrous sodium metasilicate, diethylene triamine pentamethylene phosphonic, mercaptobenzothiazole and vinylformic acid/allyl sulphonic acid multipolymer is respectively 88.0mg/L, 10.0mg/L, 1.0mg/L and 5.0mg/L.
Added amount of chemical is as follows:
A tower: waxy oil 100mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the concentration of 400mg/L, in test water, add, add again tetradecyl tributyl phosphonium bromide 40mg/L and 1,3-bis-is chloro-5, and then 5-dimethyl hydantion 40mg/L threw 1 every three days, 3-bis-chloro-5,5-dimethyl hydantion 20mg/L, by the 8th day, adds glutaraldehyde 60mg/L.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 3 of table 1
Calcium hardness adds basicity: A tower 1000 ± 50mg/L
PH value is not controlled
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 16
The preparation of anti-incrustation corrosion inhibitor: take 20.6g five hydration sodium tetraborates (containing B
4o
7 2-11.0g), 89.3g anhydrous sodium metasilicate is (containing SiO
244.0g), join 230.9g deionized water for stirring even, adding 22.5g effective constituent is 40% L-glutamic acid two methylenephosphonic acids, adding solid content is that (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3 to 30% vinylformic acid/Styrene Sulfonic Acid Copolymer 36.7g, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water, in water, the effective concentration of five hydration sodium tetraborates, anhydrous sodium metasilicate, L-glutamic acid two methylenephosphonic acids and vinylformic acid/Styrene Sulfonic Acid Copolymer is respectively 11.0mg/L, 44.0mg/L, 9.0mg/L and 11.0mg/L.
Added amount of chemical is as follows:
A tower: contain solar oil 200mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 400mg/L, in test water, add, add again methoxyl methyl three phenyl phosphonium bromide 40mg/L and the bromo-3-of 1-chloro-5,5-dimethyl is for glycolylurea 30mg/L, then every three days, add the bromo-3-of 1-chloro-5,5-dimethyl is for glycolylurea 20mg/L.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 2 of table 1
Calcium hardness: A tower 130 ± 20mg/L
PH value is not controlled
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 17
The preparation of anti-incrustation corrosion inhibitor: take 27.6g five hydration sodium tetraborates (containing B
4o
7 2-14.7g), 43.3g metasilicate pentahydrate sodium is (containing SiO
212.3g), to join 276.9g deionized water for stirring even for 8.0g Sunmorl N 60S, adding 27.5g effective constituent is 40% thionamic acid two methylenephosphonic acids, adding solid content is that (in multipolymer, the mass ratio of toxilic acid and styrene sulfonic acid is 7: 3 to 30% toxilic acid/Styrene Sulfonic Acid Copolymer 16.7g, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), be made into composite corrosion inhibitor 400.0g of the present invention.With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 400mg/L when adding in test water, in water, the effective concentration of five hydration sodium tetraborates, metasilicate pentahydrate sodium, Sunmorl N 60S, thionamic acid two methylenephosphonic acids and toxilic acid/Styrene Sulfonic Acid Copolymer is respectively 14.7mg/L, 12.3mg/L, 8.0mg/L, 11.0mg/ and 5mg/L.
Added amount of chemical is as follows:
A tower: contain pyrolysis gasoline 150mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 400mg/L, in test water, add, add again trityl group phosphonium bromide 80mg/L, polysorbate40 30mg/L and Losantin 35mg/L, then every three days, add Losantin 20mg/L.Test-results in Table 3, table 4.
Control parameter is as follows:
Test water quality: the former water 1 of table 1
Calcium hardness: A tower 800 ± 50mg/L
PH value A tower 8.0 ± 0.2
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Table 3 dynamic analog test test tube result *
* the test of carrying out in the B tower in embodiment is simultaneous test.
Table 4 heterotrophic bacterium monitoring result *
* the test of carrying out in the B tower in embodiment is simultaneous test.
In standard GB/T 50050-95 < < Code for design of industrial recirculating cooling water treatment > > 3.1.6, stipulate, the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a; In the < < water coolant analysis of production department of China PetroChemical Corporation and development division establishment and test method > >, the corrosion speed of the small-sized experimental analogic method > > of < < testing laboratory regulation carbon steel is " fine " level at 0-0.028mm/a, between 0.028-0.056mm/a, being " good " level, is " can allow " level at 0.056-0.070mm/a; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, at 15-20mcm, is " can allow " level.Heterotrophic bacterium is controlled at 10
5individual/mL is qualified below.
As seen from the above table, apply under the various condition of water quality that leakage of oil circulating water treatment method of the present invention is 100mg/L-200mg/L in oil product concentration, the effect that prevents microorganism adhering and local corrosion is all fine, and can effectively control containing the microorganism in the recirculated cooling water of leakage oil product by controlling the dosage of sterilant, the erosion rate of test tube is between 0.023-0.034mm/a, reach China Petrochemical Industry " fine " level and " good level " standard, adhere to speed between 7.2-8.7mcm, reach " good level " standard, be better than comparative example.
Claims (41)
1. a leakage of oil circulating water treatment method, it comprises the following steps: a) add oxidative bactericide and optional glutaraldehyde; B) add anti-incrustation corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises a kind of or its mixture in water-soluble borate, Water-Soluble Glucose hydrochlorate and water-soluble silicate, at least one organic phospho acid, at least one organic carboxyl acid base polymer, optional copper material corrosion inhibitor and optional zinc salt; C) add quaternary phosphine salt type cats product and optional polysorbate nonionogenic tenside.
2. leakage of oil circulating water treatment method according to claim 1, is characterized in that described oxidative bactericide is at least one is selected from the sterilant of chloride sterilant and brominated sterilant.
3. leakage of oil circulating water treatment method according to claim 2, it is characterized in that described chloride sterilant is selected from chlorine, hypochlorous acid and salt thereof, dichloroisocyanuric acid sodium, TCCA (Trichloroisocyanuric acid), 1,3-bis-is chloro-5, and 5-dimethyl hydantion, the bromo-3-of 1-are chloro-5,5-dimethyl hydantion; Described brominated sterilant is selected from hypobromous acid and salt, organo bromine microbicide and bromine chloride.
4. leakage of oil circulating water treatment method according to claim 3, is characterized in that described hypochlorite is selected from clorox, Losantin; Described hypobromite is selected from sodium hypobromite and hypobromous acid calcium; Described organo bromine microbicide be selected from 2,2-, bis-bromo-3-time aminopropan acid amides and the bromo-3-of 1-chloro-5,5-dimethyl is for glycolylurea.
5. leakage of oil circulating water treatment method according to claim 1, is characterized in that the effective concentration with respect to pending aqueous solution total amount oxidative bactericide is 10-50mg/L.
6. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described quaternary alkylphosphonium salt is selected from general formula for (R)
4pX quaternary alkylphosphonium salt, wherein R is identical or different, and for being selected from the alkyl that carbonatoms is 1-20, alkoxyalkyl or the phenyl that carbonatoms is 2-20, X is chlorine or bromine.
7. leakage of oil circulating water treatment method according to claim 6, is characterized in that described quaternary alkylphosphonium salt is selected from 4-butyl phosphonium chloride, four butyl phosphonium bromides, tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, trityl group phosphonium chloride, triphenyl ethyl phosphonium chloride, triphenyl Bing Ji phosphonium chloride, triphenyl butyl phosphonium chloride, trityl group phosphonium bromide, tri-phenyl-ethyl phosphonium bromide, triphenyl propyl group phosphonium bromide, triphenyl butyl phosphonium bromide, dodecyl tributyl phosphonium bromide, dodecyl tributyl phosphonium chloride, tetradecyl tributyl phosphonium bromide, tetradecyl tributyl phosphonium chloride, phosphonium hexadecanyl-3-butyl chloride, hexadecyl tributyl phosphonium bromide, dodecyloxy methyl tributyl phosphonium bromide, dodecyloxy methyl tributyl phosphonium chloride, dodecyloxy ethyl tributyl phosphonium chloride, dodecyloxy ethyl tributyl phosphonium bromide, tetradecyloxyaniline ethyl tributyl phosphonium chloride, tetradecyloxyaniline ethyl tributyl phosphonium bromide, methoxyl methyl triphenyl phosphonium chloride and methoxyl methyl three phenyl phosphonium bromides.
8. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that the effective concentration with respect to pending aqueous solution total amount quaternary alkylphosphonium salt is 10-100mg/L.
9. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described organic carboxyl acid base polymer is selected from homopolymer, copolymer and terpolymer.
10. leakage of oil circulating water treatment method according to claim 9, it is characterized in that described organic carboxyl acid base polymer is selected from polyacrylic acid, polymaleic anhydride, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/Styrene Sulfonic Acid Copolymer, vinylformic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2'-acrylamido propane sulfonic acid multipolymer and vinylformic acid/toxilic acid/2-methyl-2'-acrylamido propane sulfonic acid multipolymer.
11. leakage of oil circulating water treatment methods according to claim 10, is characterized in that described acrylate is selected from vinylformic acid C
1-8ester.
12. leakage of oil circulating water treatment methods according to claim 11, is characterized in that described acrylate is selected from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
13. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that borate is selected from Sodium Tetraborate and potassium borate; Gluconate is selected from Sunmorl N 60S, Potassium Gluconate and Zinc Gluconate; Silicate is selected from sodium metasilicate, Starso, positive potassium silicate and potassium metasilicate.
14. leakage of oil circulating water treatment methods according to claim 13, is characterized in that borate is selected from Sodium Tetraborate; Silicate is selected from Starso.
15. leakage of oil circulating water treatment methods according to claim 14, is characterized in that described borate is selected from sodium borate decahydrate, five hydration sodium tetraborates and four hydration eight Sodium Tetraboratees; Silicate is selected from metasilicate pentahydrate sodium, non-hydrate sodium metasilicate, anhydrous sodium metasilicate.
16. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described organic phospho acid is selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, 2-phosphonate group-1,2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methylenephosphonic acids, L-glutamic acid two methylenephosphonic acids, thionamic acid two methylenephosphonic acids and taurine two methylenephosphonic acids and polyether-based polyamino methylene phosphonic acid.
17. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described copper material corrosion inhibitor is mercaptobenzothiazole, methyl benzotriazazole or benzotriazole; Described zinc salt is zinc sulfate or zinc chloride.
18. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described polysorbate nonionogenic tenside is selected from polyoxyethylene sorbitan fatty acid ester.
19. leakage of oil circulating water treatment methods according to claim 18, is characterized in that described polysorbate nonionogenic tenside is selected from polyoxyethylene (10-30) anhydrous sorbitol C
12～C
18fatty acid ester.
20. leakage of oil circulating water treatment methods according to claim 19, is characterized in that described polysorbate nonionogenic tenside is selected from polyoxyethylene (10-30) anhydrous sorbitol laurate, polyoxyethylene (10-30) anhydrous sorbitol cetylate, polyoxyethylene (10-30) Span60 and polyoxyethylene (10-30) sorbitan monooleate.
21. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that the effective concentration with respect to pending aqueous solution total amount polysorbate nonionogenic tenside is 10-100mg/L.
22. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that with respect to pending aqueous solution total amount, in anti-incrustation corrosion inhibitor, the effective concentration of each component is: when single medicament is done inhibiter, its effective working concentration is 50-150mg/L, when various medicaments is composite, total effectively working concentration of inhibiter is 30-100mg/L, and wherein boratory concentration is with B
4o
7 2-the concentration of meter, gluconate in the concentration of gluconate, silicate with SiO
2meter; Organic carboxyl acid base polymer concentration is 2-15mg/L, and organic phospho acid concentration is 2-15mg/L, and the effective concentration of copper material corrosion inhibitor is 0.5-1.5mg/L, and the effective concentration of zinc salt is with Zn
2+count 0.5-3.0mg/L.
23. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
24. leakage of oil circulating water treatment methods according to claim 6, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
25. leakage of oil circulating water treatment methods according to claim 7, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
26. leakage of oil circulating water treatment methods according to claim 8, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
27. leakage of oil circulating water treatment methods according to claim 9, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
28. leakage of oil circulating water treatment methods according to claim 10, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
29. leakage of oil circulating water treatment methods according to claim 11, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
30. leakage of oil circulating water treatment methods according to claim 12, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
31. leakage of oil circulating water treatment methods according to claim 13, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
32. leakage of oil circulating water treatment methods according to claim 13, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
33. leakage of oil circulating water treatment methods according to claim 14, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
34. leakage of oil circulating water treatment methods according to claim 15, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
35. leakage of oil circulating water treatment methods according to claim 16, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
36. leakage of oil circulating water treatment methods according to claim 17, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
37. leakage of oil circulating water treatment methods according to claim 18, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
38. leakage of oil circulating water treatment methods according to claim 19, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
39. leakage of oil circulating water treatment methods according to claim 20, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
40. leakage of oil circulating water treatment methods according to claim 21, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
41. leakage of oil circulating water treatment methods according to claim 22, is characterized in that the effective concentration with respect to pending aqueous solution total amount glutaraldehyde is 30-120mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110082712.9A CN102730864B (en) | 2011-04-02 | 2011-04-02 | Method for treating oil-leaking circulating water |
Applications Claiming Priority (1)
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| CN103109850A (en) * | 2013-01-30 | 2013-05-22 | 武汉华科特新技术有限公司 | Composite bactericide for efficiently inhibiting iron bacteria |
| CN105198180A (en) * | 2015-02-20 | 2015-12-30 | 新疆科力新技术发展有限公司 | Improved water washing treating-agent and method for realizing standard oily sludge treatment in oil field by employing same |
| CN106242086A (en) * | 2016-08-29 | 2016-12-21 | 山东胜伟园林科技有限公司 | A kind of carbonate bases ground antisludging agent and preparation method thereof |
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| CN1417139A (en) * | 2001-11-08 | 2003-05-14 | 北京燕山石油化工公司研究院 | Method for reusing ammonia nitrogen containing effluent as circular cooling water |
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| 缓释型多功能水处理剂的综合介绍;黄文氢等;《化工进展》;20001231(第6期);第29页第1.3节 * |
| 黄文氢等.缓释型多功能水处理剂的综合介绍.《化工进展》.2000,(第6期),第29页第1.3节. |
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