CN102730873B - Method for processing oil leakage circulation water - Google Patents
Method for processing oil leakage circulation water Download PDFInfo
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Abstract
The invention provides a method for processing oil leakage circulation water, which comprises the following steps: a) adding an oxidized bactericide and optional glutaraldehyde; b) adding a scale inhibition corrosion inhibitor, wherein the scale inhibition corrosion inhibitor comprises polyepoxysuccinic acid or polyaspartic acid, at least an organic carboxylic acid polymer, an optional copper material corrosion inhibitor and optional zinc salt; and c) adding a polysorbate non-ionic surfactant and/or a polyoxyethylene non-ionic surfactant. The method of the invention is capable of removing oil of a circulation water system and removing the microbial sludge, the method can be finished at once without discharge of large amount of sludge.
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 non-phosphorus scale and corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises poly-epoxy succinic acid or poly aspartic acid, 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 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.
When composite scale-inhibiting corrosion inhibitor is used for to recirculated cooling water, also can contain zinc salt as inhibiter, 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: poly-epoxy succinic acid or poly aspartic acid are 2-15mg/L, organic carboxyl acid base polymer concentration is 2-15mg/L, 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 counted 0-3.0mg/L, is preferably 0.5-3.0mg/L with Zn2+.
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.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).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 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 can, by poly-epoxy succinic acid or poly aspartic acid, organic carboxyl acid base polymer, zinc salt (if any) and copper material corrosion inhibitor (if any), 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 restoration methods after circulating water system oil leakage.
Embodiment
The following examples will contribute to illustrate the present invention, but not limit to its scope.
In embodiment, polysorbas20, polysorbate40, polysorbate60, tween 80 used is the production of Guangzhou Xi Lu Chemical Co., Ltd. below.Paregal O-8 used, paregal O-10, paregal O-15, paregal O-20, be Shanghai Kai Meisite water technology company limited and produce; Op-6 used, op-10, op-20, NP-10, NP-21, 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: the corrosion inhibition of the following examples is all tested according to the mensuration rotary hanging plate method > > of State Standard of the People's Republic of China GB/T 18175-2000 < < water conditioner 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 and supplement respectively Ca
2+numerical value when cycles of concentration is 5 times separately to it with basicity, 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 respectively Ca by testing former water in table 1
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)
Embodiment 1
The preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 39.9 grams of water, be uniformly dissolved, adding 8g effective content is 50% PESA (poly-epoxy succinic acid, Limiting Viscosity in the time of 30 ℃ is 0.038dl/g), adding 43.3g solid content is that (in multipolymer, vinylformic acid and Propylene glycol monoacrylate mass ratio are 7: 3 for vinylformic acid/Propylene glycol monoacrylate multipolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.068dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, PESA, vinylformic acid/Propylene glycol monoacrylate multipolymer, Zn in water
2+effective concentration be respectively 4mg/L, 13mg/L and 2mg/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: the PASP (poly aspartic acid that is 40% by 32.5g effective content, Limiting Viscosity in the time of 30 ℃ is 0.068dl/g) be dissolved in 40.8g water, adding 26.7g solid content is that (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 7: 3 for acrylate/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PASP, acrylate/Styrene Sulfonic Acid Copolymer is respectively 13mg/L and 8mg/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: the PESA that is 50% by 20g effective content (30 ℃ time Limiting Viscosity be 0.045dl/g) adds in 41.37g water, adding 16.7g solid content is 30% polyacrylic acid (30 ℃ time Limiting Viscosity be 0.069dl/g), adding 16.7g solid content is that (mass ratio of vinylformic acid and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 7: 3 for vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer of 30% again, Limiting Viscosity in the time of 30 ℃ is 0.071dl/g), add 5.23g zinc chloride, shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, PESA, polyacrylic acid, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and Zn in water
2+effective concentration be respectively 10mg/L, 5mg/L, 5mg/L and 2.5mg/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-30 30mg/L and polysorbate40 40mg/L, test-results is in Table 2.
Embodiment 4
The preparation of anti-incrustation corrosion inhibitor: the PASP that is 40% by 20g effective content (30 ℃ time Limiting Viscosity be 0.075dl/g) is dissolved in 60g water, adding 20g solid content is that (in multipolymer, the mass ratio of vinylformic acid and Propylene glycol monoacrylate, methyl acrylate is 3: 1: 1 for vinylformic acid/Propylene glycol monoacrylate/methyl acrylate terpolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.065dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PASP, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer is respectively 8mg/L and 6mg/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-15 20mg/L and polysorbate60 50mg/L, test-results is in Table 2.
Embodiment 5
The preparation of anti-incrustation corrosion inhibitor: the PESA that is 50% by 12g effective content (30 ℃ time Limiting Viscosity be 0.050dl/g) adds in 47.2g water, be uniformly dissolved, adding 26.7g solid content is vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (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), adding 13.3g solid content is 30% polymaleic anhydride (30 ℃ time Limiting Viscosity be 0.077dl/g), add again 0.8g benzotriazole, shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PESA, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, polymaleic anhydride and benzotriazole is respectively 6mg/L, 8mg/L, 4mg/L and 0.8mg/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-10 10mg/L and polysorbate60 60mg/L, test-results is in Table 2.
Embodiment 6
The preparation of anti-incrustation corrosion inhibitor: the PASP that is 40% by 27.5g effective content (30 ℃ time Limiting Viscosity be 0.066dl/g) adds in 58.2g water, adding 13.3g solid content is that (in multipolymer, the mass ratio of toxilic acid and styrene sulfonic acid is 8: 2 for toxilic acid/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.067dl/g), add mercaptobenzothiazole 1.0g, shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PASP, toxilic acid/Styrene Sulfonic Acid Copolymer and mercaptobenzothiazole is respectively 11mg/L, 4mg/L, 1.0mg/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-20 20mg/L and tween 80 20mg/L, test-results is in Table 2.
Embodiment 7
The preparation of anti-incrustation corrosion inhibitor: the PESA that is 50% by 6g effective content (30 ℃ time Limiting Viscosity be 0.041dl/g) adds in 51.3g water, adding 10g solid content is acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (vinylformic acid in multipolymer of 30%, the mass ratio of acrylate and 2-methyl-2 '-acrylamido propane sulfonic acid is 3: 1: 1, Limiting Viscosity in the time of 30 ℃ is 0.076dl/g), adding 26.7g concentration is that (mass ratio of vinylformic acid and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 7: 3 for vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer of 30% again, Limiting Viscosity in the time of 30 ℃ is 0.072dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PESA, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer is respectively 3mg/L, 3mg/L and 8mg/L.
During corrosion inhibition test, in beaker, add 200mg wax oil, add 50mg wax oil, then add respectively op-20 30mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 8
The preparation of anti-incrustation corrosion inhibitor: the PASP that is 40% by 32.5g effective content (30 ℃ time Limiting Viscosity be 0.075dl/g) adds in 37.5g water, adding 30.0g 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 of 30%, Limiting Viscosity in the time of 30 ℃ is 0.067dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PASP and toxilic acid/allyl sulphonic acid multipolymer is respectively 13mg/L and 9mg/L.
During corrosion inhibition test, in beaker, add 200mg pyrolysis gasoline, add 50mg pyrolysis gasoline, then add respectively NP-10 20mg/L during antisludging test in volumetric flask, test-results is in Table 2.
Embodiment 9
The preparation of anti-incrustation corrosion inhibitor: the PESA that is 50% by 10g effective content (30 ℃ time Limiting Viscosity be 0.048dl/g) adds in 50.0g water, adding 40.0g concentration is that (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3 for vinylformic acid/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.065dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PESA and vinylformic acid/Styrene Sulfonic Acid Copolymer is respectively 5mg/L and 12mg/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: the PASP that is 40% by 22.5g effective content (30 ℃ time Limiting Viscosity be 0.077dl/g) adds in 50.8g water, adding 26.7g solid content is that (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 8: 2 for acrylate/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.066dl/g), shake up.
With the scale inhibitor agent solution preparing by the scale inhibitor agent concentration of 100mg/L when adding in test water, in water, the effective concentration of PASP and acrylate/Styrene Sulfonic Acid Copolymer is respectively 9mg/L and 8mg/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.
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.
Table 2 embodiment corrosion-mitigation scale-inhibition result
Note: embodiment 5 and 6 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 recirculated water of oil-containing, 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 11～18 is dynamic simulation experiment.The control parameter of all dynamic simulation experiments is all according to following control indexes.
Control parameter is as follows:
Test water quality: the former water of table 1
Calcium hardness+total alkalinity value: A tower 1000 ± 50mg/L, B tower 1000 ± 50mg/L
Flow velocity: 1.0m/s
Temperature in: 32 ± 1 ℃
PH is uncomfortable
Embodiment 11
The preparation of anti-incrustation corrosion inhibitor: the preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 39.9 grams of water, be uniformly dissolved, add 8g effective content and be 50% PESA (30 ℃ time Limiting Viscosity be 0.045dl/g), adding 43.3g solid content is that (in multipolymer, vinylformic acid and Propylene glycol monoacrylate mass ratio are 7: 3 for vinylformic acid/Propylene glycol monoacrylate multipolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.068dl/g), shake up.
Anti-incrustation corrosion inhibitor dosage 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 100mg/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 not except adding op-20 polysorbas20, and test conditions and testing sequence are with A tower.Test-results in Table 3, table 4.
Embodiment 12
The preparation of anti-incrustation corrosion inhibitor: the PASP that is 40% by 20.0g effective content (30 ℃ time Limiting Viscosity be 0.067dl/g) adds in 53.3g water, adding 26.7g solid content is that (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 8: 2 for acrylate/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.066dl/g), shake up.
Anti-incrustation corrosion inhibitor dosage 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 100mg/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.
Embodiment 13
The preparation of anti-incrustation corrosion inhibitor: the PESA that is 50% by 10.0g effective content (30 ℃ time Limiting Viscosity be 0.041dl/g) adds in 55.9g water, be uniformly dissolved, adding 20.0g solid content is vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer (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), adding 13.3g solid content is 30% polymaleic anhydride (30 ℃ time Limiting Viscosity be 0.077dl/g), add again 0.8g methyl benzotriazazole, shake up.
Anti-incrustation corrosion inhibitor dosage 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 100mg/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.
Embodiment 14
The preparation of anti-incrustation corrosion inhibitor: the PESA that is 50% by 10g effective content (30 ℃ time Limiting Viscosity be 0.049dl/g) adds in 50.0g water, adding 40.0g concentration is that (mass ratio of vinylformic acid, acrylamide and 2-methyl-2 in multipolymer '-acrylamido propane sulfonic acid is 3: 1: 1 for acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.075dl/g), shake up.
Anti-incrustation corrosion inhibitor dosage 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 100mg/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, 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.
Embodiment 15
The preparation of anti-incrustation corrosion inhibitor: the PASP that is 40% by 25.0g effective content (30 ℃ time Limiting Viscosity be 0.078dl/g) adds in 55.0g water, adding 20.0g solid content is that (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 8: 2 for acrylate/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.066dl/g), shake up.
Anti-incrustation corrosion inhibitor dosage 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 100mg/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.
Embodiment 16
The preparation of anti-incrustation corrosion inhibitor: the preparation of anti-incrustation corrosion inhibitor: the Zinc Sulphate Heptahydrate of 8.8g is dissolved in 39.9 grams of water, be uniformly dissolved, adding 8g effective content is 50% PESA (30 ℃ time Limiting Viscosity be 0.045dl/g), adding 43.3g solid content is that (in multipolymer, vinylformic acid and Propylene glycol monoacrylate mass ratio are 7: 3 for vinylformic acid/Propylene glycol monoacrylate multipolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.068dl/g), shake up.
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 100mg/L, in test water, add, add again paregal O-1040mg/L, polysorbas20 40mg/L and the bromo-3-of 1-chloro-5,5-dimethyl is for glycolylurea 25mg/L, 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.
Embodiment 17
The preparation of anti-incrustation corrosion inhibitor: the PASP that is 40% by 20.0g effective content (30 ℃ time Limiting Viscosity be 0.067dl/g) adds in 53.3g water, adding 26.7g solid content is that (in multipolymer, the mass ratio of acrylate and styrene sulfonic acid is 8: 2 for acrylate/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.066dl/g), shake up.
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 100mg/L, in test water, add, add again op-640mg/L and TCCA (Trichloroisocyanuric acid) 25mg/L, then every three days, add TCCA (Trichloroisocyanuric acid) 20mg/L.Test-results in Table 3, table 4.
Embodiment 18
The preparation of anti-incrustation corrosion inhibitor: the PESA that is 50% by 10g effective content (30 ℃ time Limiting Viscosity be 0.048dl/g) adds in 50.0g water, adding 40.0g concentration is that (in multipolymer, the mass ratio of vinylformic acid and styrene sulfonic acid is 7: 3 for vinylformic acid/Styrene Sulfonic Acid Copolymer of 30%, Limiting Viscosity in the time of 30 ℃ is 0.065dl/g), shake up.
Added amount of chemical is as follows:
A tower: contain solar oil 100mg/L in the water in A tower, with the scale inhibitor agent solution preparing, by the scale inhibitor agent concentration of 100mg/L, in test water, add, add again NP-21 35mg/L and bromine chloride 25mg/L, then every three days, add bromine chloride 20mg/L.Test-results in Table 3, table 4.
Table 3 dynamic analog test test tube result
*
*the test of carrying out in B tower in embodiment is simultaneous test.
Table 4 heterotrophic bacterium monitoring result
*
*the test of carrying out in 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 at oil 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 0.025-0.035mm/a, reach China Petrochemical Industry " fine " level and " good level " standard, adhere to speed between 7.4-9.1mcm, reach " good level " standard, be better than the treatment effect of comparative example.
Claims (19)
1. a leakage of oil circulating water treatment method, it comprises the following steps: a) add oxidative bactericide and optional glutaraldehyde; B) add non-phosphorus scale and corrosion inhibitor, described anti-incrustation corrosion inhibitor comprises poly-epoxy succinic acid or poly aspartic acid, 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 described copper material corrosion inhibitor is mercaptobenzothiazole, methyl benzotriazazole or benzotriazole.
9. 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.
10. 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.
11. leakage of oil circulating water treatment methods according to claim 10, 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.
12. leakage of oil circulating water treatment methods according to claim 11, 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.
13. leakage of oil circulating water treatment methods according to claim 12, 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.
14. 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.
15. leakage of oil circulating water treatment methods according to claim 14, is characterized in that described polysorbate nonionogenic tenside is selected from polyoxyethylene (10-30) anhydrous sorbitol C
12～C
18fatty acid ester.
16. leakage of oil circulating water treatment methods according to claim 15, 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.
17. 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 the effective concentration of each component in pending aqueous solution total amount anti-incrustation corrosion inhibitor being: poly-epoxy succinic acid or poly aspartic acid are 2-15mg/L, organic carboxyl acid base polymer concentration is 2-15mg/L, 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.
18. 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 for 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 Determination of Polyoxyethylene Non-ionic Surfactants, 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.
19. 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.
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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28-30页 * |
| 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), |
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