CN102730865B - Treatment method of circulating water with leaked oil - Google Patents
Treatment method of circulating water with leaked oil Download PDFInfo
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- CN102730865B CN102730865B CN201110082713.3A CN201110082713A CN102730865B CN 102730865 B CN102730865 B CN 102730865B CN 201110082713 A CN201110082713 A CN 201110082713A CN 102730865 B CN102730865 B CN 102730865B
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Abstract
The invention provides a treatment method of circulating water with leaked oil. The method comprises the following steps: a) adding an oxidation-type bactericide and an optional glutaraldehyde; b) adding a corrosion and scale inhibitor containing one of water-soluble borate, water-soluble gluconate and water-soluble silicate or a mixture of the three, at least one organic carboxylic acid polymer, an optional copper corrosion inhibitor and an optional zinc salt; and c) adding a polysorbate nonionic surfactant and / or polyoxyethylene-type nonionic surfactant. The method of the invention can carry out oil removal and microbial slime stripping on equipment in a circulating water system by one time, without mass 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 borate, gluconate and silicate, at least one organic carboxyl acid base polymer, optional copper material corrosion inhibitor and optional zinc salt; C) add polysorbate nonionogenic tenside and/or Polyoxyethylene Ether Nonionic Surfactant.
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.
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 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.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).
Determination of Polyoxyethylene Non-ionic Surfactants of the present invention is selected from long-chain fat polyoxyethylenated alcohol and alkylphenol polyoxyethylene; The preferred self-drifting of described long-chain fat polyoxyethylenated alcohol is
compound, R wherein
3for C
12-C
18alkyl, the natural number that n is 8-40, be preferably 8-35; Object lesson has paregal O-8 (C
12-C
18aliphatic alcohol polyethenoxy (8) ether), paregal O-10 (C
12-C
18aliphatic alcohol polyethenoxy (10) ether), paregal O-15 (C
12-C
18aliphatic alcohol polyethenoxy (15) ether), paregal O-20 (C
12-C
18aliphatic alcohol polyethenoxy (20) ether), paregal O-30 (C
12-C
18aliphatic alcohol polyethenoxy (30) ether).The preferred self-drifting of described alkylphenol polyoxyethylene is
compound, R wherein
4for C
8-C
12alkyl, be preferably C
8, C
9, C
12alkyl, the natural number that n is 3-30, more preferably from octyl phenol polyoxy ethene (10-20) ether, Nonyl pheno (10-20) ether and dodecyl phenol polyethenoxy (10-20) ether, concrete example has op-3 (sim alkylphenol polyoxyethylene (3) ether), op-6 (sim alkylphenol polyoxyethylene (6) ether), op-10 (sim alkylphenol polyoxyethylene (10) ether), op-20 (sim alkylphenol polyoxyethylene (20) ether), op-30 (sim alkylphenol polyoxyethylene (30) ether), NP-4 (nonyl phenol polyethenoxy (4) ether), NP-6 (nonyl phenol polyethenoxy (6) ether), NP-10 (nonyl phenol polyethenoxy (10) ether), NP-21 (nonyl phenol polyethenoxy (21) ether), NP-30 (nonyl phenol polyethenoxy (30) ether).
With respect to pending aqueous solution total amount, the effective concentration of Determination of Polyoxyethylene Non-ionic Surfactants of the present invention is 0-50mg/L, the effective concentration of polysorbate nonionogenic tenside is 0-100mg/L, and the effective concentration of the effective concentration of Determination of Polyoxyethylene Non-ionic Surfactants and polysorbate nonionogenic tenside is zero when different; Preferably the effective concentration of Determination of Polyoxyethylene Non-ionic Surfactants is 20-50mg/L, and the effective concentration of polysorbate nonionogenic tenside is 30-100mg/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, the reinforced order of each component is unimportant, for example inorganic acid salt (borate, gluconate, silicate), organic carboxyl acid base polymer, zinc salt (if any) and copper material corrosion inhibitor (if any) and water can be mixed in predetermined ratio, can make required composite scale-inhibiting corrosion inhibitor.In the preparation process of composite scale-inhibiting corrosion inhibitor, also can add a small amount of acid (as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), to promote the dissolving of zinc salt, obtain as early as possible needing the uniform solution of the composite scale-inhibiting corrosion inhibitor of concentration.
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 and tween 80 used is the production of Guangzhou Xi Lu Chemical Co., Ltd., and paregal O-8 used, paregal O-10, paregal O-15, paregal O-20, paregal O-30 are Shanghai Kai Meisite water technology company limited and produce; Op-6 used, op-10, op-20, NP-6, NP-10, NP-30 are Zibo Hai Jie Chemical Co., Ltd. and produce.
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 supplement 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 supplement 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 the water distribution 1 of comparative example use-testing, 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 39.3g deionized water for stirring even, 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 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 1 and 2, in water, the effective concentration of sodium borate decahydrate, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer is respectively 60.0mg/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 respectively polysorbas20 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 85.4g deionized water for stirring even, 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 2, in water, anhydrous sodium metasilicate, 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, 5mg/L and 4mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add respectively paregal O-8 40mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 3
The preparation of anti-incrustation corrosion inhibitor: taking 95.0g Sunmorl N 60S, to join 56.2g deionized water for stirring even, add solid content be 30% acrylic acid/acrylamide/2-methyl-2 ' (mass ratio of vinylformic acid, acrylamide and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 3: 1: 1 to-acrylamido propane sulfonic acid multipolymer 40.0g, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g), add Zinc Sulphate Heptahydrate 8.8g, stir, be made into inhibiter 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 1 and 2, aqueous humor glucose acid sodium, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and Zn
2+effective concentration be respectively 95mg/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 NP-3030mg/L and polysorbate40 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 94.0g deionized water for stirring even, 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 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 1 and 2, in water, the effective concentration of five hydration potassium tetraborates, Potassium Gluconate, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and benzotriazole is respectively 20mg/L, 20mg/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 paregal O-1520mg/L and polysorbate60 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 203.5g deionized water for stirring even, 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 2, in water, the effective concentration of four hydration eight Sodium Tetraboratees, Sunmorl N 60S and vinylformic acid/vinyl sulfonic acid multipolymer is respectively 53.4mg/L, 21.6mg/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 op-1015mg/L and polysorbate60 60mg/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 52.0g deionized water for stirring even, 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 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 1 and 2, in water, the effective concentration of metasilicate pentahydrate sodium, Zinc Gluconate, vinylformic acid/allyl sulphonic acid multipolymer is respectively 27.5mg/L, 27.5mg/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 paregal O-2015mg/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 72.6g deionized water for stirring even, 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 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 1 and 2, the effective concentration of water mesosilicic acid potassium, Potassium Gluconate and toxilic acid/allyl sulphonic acid multipolymer is respectively 30mg/L, 35mg/L and 9mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add respectively op-2030mg/L during antisludging test in volumetric flask, 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 58.1g deionized water for stirring even, 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 2, in water, the effective concentration of five hydration sodium tetraborates, non-hydrate sodium metasilicate and acrylate/Styrene Sulfonic Acid Copolymer multipolymer is respectively 28.2mg/L, 56.8mg/L and 6mg/L.
During corrosion inhibition test, in beaker, add 200mg pyrolysis gasoline, add 50mg pyrolysis gasoline, then add respectively NP-1020mg/L during antisludging test in volumetric flask, 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 53.4g deionized water for stirring even, 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 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 1 and 2, in water, the effective concentration of five hydration sodium tetraborates, anhydrous sodium metasilicate and vinylformic acid/Styrene Sulfonic Acid Copolymer is respectively 11.0mg/L, 44.0mg/L and 11.0mg/L.
During corrosion inhibition test, in beaker, add 200mg solar oil, add 50mg solar oil, then add respectively polysorbate40 30mg/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), 8.0g Sunmorl N 60S, that 0.8g methyl benzotriazazole joins 103.6g deionized water for stirring is even, 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 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 1 and 2, in water, the effective concentration of five hydration sodium tetraborates, metasilicate pentahydrate sodium, Sunmorl N 60S, methyl benzotriazazole and toxilic acid/Styrene Sulfonic Acid Copolymer is respectively 14.7mg/L, 12.3mg/L, 8.0mg/L, 0.8mg/L and 5mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add respectively polysorbas20 70mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 11
The preparation of anti-incrustation corrosion inhibitor: take 97.2g metasilicate pentahydrate sodium (containing SiO
227.5g), 27.5g Zinc Gluconate, join 52.0g deionized water for stirring even, 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 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 1 and 2, in water, the effective concentration of metasilicate pentahydrate sodium, Zinc Gluconate, vinylformic acid/allyl sulphonic acid multipolymer is respectively 27.5mg/L, 27.5mg/L and 7mg/L.
During corrosion inhibition test, in beaker, add 200mg solar oil, add 50mg solar oil, then add respectively paregal O-1030mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 12
The preparation of anti-incrustation corrosion inhibitor: take 62.4g potassium silicate (containing SiO
230.0g), 35.0g Potassium Gluconate, join 72.6g deionized water for stirring even, 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 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 1 and 2, the effective concentration of water mesosilicic acid potassium, Potassium Gluconate and toxilic acid/allyl sulphonic acid multipolymer is respectively 30mg/L, 35mg/L and 9mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add respectively paregal O-3045mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 13
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 58.1g deionized water for stirring even, 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 2, in water, the effective concentration of five hydration sodium tetraborates, non-hydrate sodium metasilicate and acrylate/Styrene Sulfonic Acid Copolymer multipolymer is respectively 28.2mg/L, 56.8mg/L and 6mg/L.
During corrosion inhibition test, in beaker, add 200mg pyrolysis gasoline, add 50mg pyrolysis gasoline, then add respectively op-645mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 14
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 53.4g deionized water for stirring even, 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 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 1 and 2, in water, the effective concentration of five hydration sodium tetraborates, anhydrous sodium metasilicate and vinylformic acid/Styrene Sulfonic Acid Copolymer is respectively 11.0mg/L, 44.0mg/L and 11.0mg/L.
During corrosion inhibition test, in beaker, add 200mg solar oil, add 50mg solar oil, then add respectively NP-2115mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 15
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 104.4g deionized water for stirring even for 8.0g Sunmorl N 60S, 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 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 1 and 2, in water, the effective concentration of five hydration sodium tetraborates, metasilicate pentahydrate sodium, Sunmorl N 60S and toxilic acid/Styrene Sulfonic Acid Copolymer is respectively 14.7mg/L, 12.3mg/L, 8.0mg/L and 5mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add respectively NP-645mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Comparative example 1
Test is not except adding polysorbas20, 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 paregal O-8, 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 NP-30 and polysorbate40, 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 paregal O-15 and polysorbate60, 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 op-10 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 paregal O-20 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 op-20, 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 NP-10, 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 polysorbate40, 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 polysorbas20, and test conditions and testing sequence are with embodiment 10, and test-results is in Table 2.
Comparative example 11
Test is not except adding paregal O-10, and test conditions and testing sequence are with embodiment 11, and test-results is in Table 2.
Comparative example 12
Test is not except adding paregal O-30, and test conditions and testing sequence are with embodiment 12, and test-results is in Table 2.
Comparative example 13
Test is not except adding op-6, and test conditions and testing sequence are with embodiment 13, and test-results is in Table 2.
Comparative example 14
Test is not except adding NP-21, and test conditions and testing sequence are with embodiment 14, and test-results is in Table 2.
Comparative example 15
Test is not except adding NP-6, and test conditions and testing sequence are with embodiment 15, 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 0.001mm/a.
Data by above-described embodiment and comparative example can be found out: while adopting method of the present invention to process the high and low hardness water 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 is dynamic simulation experiment.
Embodiment 16
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 94.5g deionized water for stirring even, 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 36.7g, 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, in water, the effective concentration of five hydration sodium tetraborates, Zinc Gluconate and toxilic acid/Styrene Sulfonic Acid Copolymer is respectively 15.7mg/L, 39.3mg/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 op-2030mg/L, polysorbas20 80mg/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 except not op-20 and polysorbas20, 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 1 of table 1
Calcium hardness: A tower 800 ± 50mg/L, B tower 800 ± 50mg/L
PH value A tower 8.0 ± 0.2, B tower 8.0 ± 0.2
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
Embodiment 17
The preparation of anti-incrustation corrosion inhibitor:
Take 73.6g water glass (containing SiO
224.0g), to join 71.6g deionized water for stirring even for 16.0g Sunmorl N 60S and 8.8g Zinc Sulphate Heptahydrate, 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, zine ion and vinylformic acid/Propylene glycol monoacrylate multipolymer is respectively 24.0mg/L, 16.0mg/L, 2.0mg/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 polysorbate40 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 polysorbate40, 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 18
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 183.7g deionized water for stirring even, 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, polymaleic anhydride, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and zine ion is respectively 30.0mg/L, 30.0mg/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 paregal O-840mg/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 19
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 84.0g deionized water for stirring even for 13.5g Potassium Gluconate and 1.0g mercaptobenzothiazole, 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, the effective concentration of five hydration potassium tetraborates, potassium metasilicate, Potassium Gluconate, mercaptobenzothiazole and acrylic acid/esters/2-methyl-2 in water '-acrylamido propane sulfonic acid multipolymer is respectively 12.6mg/L, 18.9mg/L, 13.5mg/L, 1.0mg/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 NP-1030mg/L and 2,2-bis-bromo-3-time aminopropan acid amides 35mg/L, then every three days, throw 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 20
The preparation of anti-incrustation corrosion inhibitor:
Take 178.9g anhydrous sodium metasilicate (containing SiO
288.00g) join 204.4g deionized water for stirring even, 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 and vinylformic acid/allyl sulphonic acid multipolymer is respectively 88.0mg/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 polysorbate60 30mg/L and 1,3-bis-is chloro-5, and 5-dimethyl hydantion 40mg/L, then added 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 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 21
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 203.5g deionized water for stirring even, 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, in water, the effective concentration of four hydration eight Sodium Tetraboratees, Sunmorl N 60S and vinylformic acid/vinyl sulfonic acid multipolymer is respectively 53.4mg/L, 21.6mg/L and 10.0mg/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 400mg/L, in test water, add, add again paregal O-840mg/L, polysorbas20 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 15mg/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 22
The preparation of anti-incrustation corrosion inhibitor: take 97.2g metasilicate pentahydrate sodium (containing SiO
227.5g), 27.5g Zinc Gluconate, join 52.0g deionized water for stirring even, 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 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, in water, the effective concentration of metasilicate pentahydrate sodium, Zinc Gluconate, vinylformic acid/allyl sulphonic acid multipolymer is respectively 27.5mg/L, 27.5mg/L and 7mg/L.
Added amount of chemical is as follows:
A tower: containing pyrolysis gasoline 150mg/L, add in test water by the concentration of 200mg/L with the scale inhibitor agent solution preparing, then add polysorbate40 45mg/L and clorox 30mg/L in the water in A tower, then added clorox 20mg/L every three days.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 ℃
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 0.021-0.037mm/a, reach China Petrochemical Industry " fine " level and " good level " standard, adhere to speed between 6.2-9.2mcm, reach " good level " standard, be better than comparative example.
Claims (21)
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 carboxyl acid base polymer, optional copper material corrosion inhibitor and optional zinc salt; C) add polysorbate nonionogenic tenside and/or Determination of Polyoxyethylene Non-ionic Surfactants.
2. leakage of oil circulating water treatment method according to claim 1, is characterized in that described oxidized form series bactericidal agent 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 organic carboxyl acid base polymer is selected from homopolymer, copolymer and terpolymer.
7. leakage of oil circulating water treatment method according to claim 6, 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.
8. 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.
9. leakage of oil circulating water treatment method according to claim 8, is characterized in that borate is selected from Sodium Tetraborate; Silicate is selected from Starso.
10. 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 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.
11. 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.
12. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described zinc salt is zinc sulfate or zinc chloride.
13. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that described Determination of Polyoxyethylene Non-ionic Surfactants is selected from long-chain fat polyoxyethylenated alcohol and alkylphenol polyoxyethylene.
14. leakage of oil circulating water treatment methods according to claim 13, is characterized in that described long-chain fat polyoxyethylenated alcohol is selected from general formula and is
compound, R wherein
3for C
12～C
18alkyl, the natural number that n is 8-40; Described alkylphenol polyoxyethylene is selected from general formula
compound, R wherein
4for C
8～C
12alkyl, the natural number that n is 3～30.
15. leakage of oil circulating water treatment methods according to claim 14, is characterized in that the n in described long-chain fat polyoxyethylenated alcohol general formula is 8-35; R in described alkylphenol polyoxyethylene general formula
4for C
8, C
9, C
12alkyl.
16. leakage of oil circulating water treatment methods according to claim 15, is characterized in that described alkylphenol polyoxyethylene is selected from octyl phenol polyoxy ethene (10～20) ether, Nonyl pheno (10～20) ether and dodecyl phenol polyethenoxy (10～20) ether.
17. 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.
18. leakage of oil circulating water treatment methods according to claim 17, is characterized in that described polysorbate nonionogenic tenside is selected from polyoxyethylene (10-30) anhydrous sorbitol C
12～C
18fatty 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 laurate, polyoxyethylene (10-30) anhydrous sorbitol cetylate, polyoxyethylene (10-30) Span60 and polyoxyethylene (10-30) sorbitan monooleate.
20. 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 in borate, gluconate and silicate, a kind of salt is cooked inhibiter, its effective working concentration is 50-150mg/L, when multiple salt 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 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.
21. according to the leakage of oil circulating water treatment method described in claim 1-5 any one, it is characterized in that as c) step is when adding nonionogenic tenside and being polysorbate nonionogenic tenside or Determination of Polyoxyethylene Non-ionic Surfactants, effective concentration with respect to pending aqueous solution total amount Determination of Polyoxyethylene Non-ionic Surfactants is 0-50mg/L, effective concentration with respect to pending aqueous solution total amount polysorbate nonionogenic tenside is 0-100mg/L, and the effective concentration of the effective concentration of Determination of Polyoxyethylene Non-ionic Surfactants and polysorbate nonionogenic tenside is zero when different, as c) step is when adding nonionogenic tenside and being polysorbate nonionogenic tenside and oxygen ethylene type nonionogenic tenside, the effective concentration of Determination of Polyoxyethylene Non-ionic Surfactants is 20-50mg/L, and the effective concentration of polysorbate nonionogenic tenside is 30-100mg/L.
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|---|---|---|---|
| CN201110082713.3A CN102730865B (en) | 2011-04-02 | 2011-04-02 | Treatment method of circulating water with leaked oil |
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|---|---|---|---|
| CN201110082713.3A CN102730865B (en) | 2011-04-02 | 2011-04-02 | Treatment method of circulating water with leaked oil |
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| CN105623889B (en) * | 2014-11-03 | 2018-03-02 | 中国石油化工股份有限公司 | One kind peels off cleansing composition and its application method |
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| CN106219778A (en) * | 2016-08-29 | 2016-12-14 | 山东天庆科技发展有限公司 | A kind of non-phosphorus scale and corrosion inhibitor with sterilization algae removal function 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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