CN1603253A - Composite anti-dirty corrosion inhibiting agent and application thereof - Google Patents

Composite anti-dirty corrosion inhibiting agent and application thereof Download PDF

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Publication number
CN1603253A
CN1603253A CNA031264964A CN03126496A CN1603253A CN 1603253 A CN1603253 A CN 1603253A CN A031264964 A CNA031264964 A CN A031264964A CN 03126496 A CN03126496 A CN 03126496A CN 1603253 A CN1603253 A CN 1603253A
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acid
corrosion inhibitor
multipolymer
water
poly aspartic
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CN1261377C (en
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郦和生
王亭
王吉龙
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INST OF BEIJING YANSHAN BRANCH CHINA PETROCHEMICAL CORP
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INST OF BEIJING YANSHAN BRANCH CHINA PETROCHEMICAL CORP
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention relates to a compound encrustation-blocking corrosion inhibitor. It includes phosphonic acid containing poly aspartic acid and at least one corrosion inhibitor. It has good complex encrustation-blocking corrosion inhibitor combination property. It has good function to blocking CaCO3 and Ca3(PO4)2, stabilizes Zn2+ in water and corrosion inhibits. The invention can be used to circulating cooling water process to increase the condense multiple. For example, it can be used under the situation of the sum of calcium hardness and total alkalinity reached to 1200mg/L after condense of the circulation cooling water.

Description

A kind of composite scale-inhibiting corrosion inhibitor and application thereof
Technical field
The present invention relates to a kind of composite scale-inhibiting corrosion inhibitor and the application in recirculated cooling water is handled thereof, specifically, the present invention relates to a kind of composite scale-inhibiting corrosion inhibitor and application in recirculated cooling water is handled thereof that contains the phosphonate group poly aspartic acid.
Background technology
The channel of industry water saving has three approach from the industrial production aspect: the cycles of concentration, reform technology, the reusing sewage that improve recirculated water.The cycles of concentration that wherein improves recirculated water is the most effective the most direct approach, compares with reusing sewage, has the following advantages: the one, need not increase initial cost; The 2nd, operating safety factor will be higher than reusing sewage, can not determine factor because sewage has a lot, and the water quality instability; The 3rd, the expense the when working cost of recirculated water will be lower than reusing sewage.Therefore, external professional water treatment company, the cycles of concentration that improves recirculated water as water-saving primary approach.
Circulating water treatment technology mainly is divided into two kinds: a kind of is nature pH operation process, and control calcium hardness and total alkalinity sum were less than 900mgL after recirculated water concentrated -1, to calcium hardness and total alkalinity sum less than 300mgL -1About middle soft water quality comparatively suitable.Another kind is an accent pH technology, and basic ideas are with adding H 2SO 4The method pH value of coming Control Circulation water, reduce the basicity in the recirculated water, and then anti-locking system fouling; The inhibiter during increase is filled a prescription simultaneously and the consumption of dispersion agent, the etching problem of emphasis resolution system generally adopts organic phosphine, sulfonic group multipolymer and zinc salt compound prescription, and this technology is 300mgL to calcium hardness and total alkalinity sum -1Above high rigidity, high basicity water quality are comparatively suitable.
To calcium hardness and total alkalinity sum is 100-300mgL -1About medium hardness, basicity water quality, usually adopting not, adjust pH moves prescription naturally, system pH can reach 9.0, at cycles of concentration greater than 3 o'clock, the general compound prescription that adopts 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) and T225 (vinylformic acid and Propylene glycol monoacrylate multipolymer) of its prescription, or HEDP, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), sulfonic group multipolymer (be generally contain 2-methyl-2 '-the sulfonic group multipolymer of acrylamido propane sulfonic acid (AMPS)) compound prescription, prescription stresses scale inhibition.These two prescriptions have the low advantage of erosion rate as long as move under the cycles of concentration that requires.But,, save the fresh water consumption if improve cycles of concentration, these two prescriptions just are difficult to realize, because the compositional analysis from filling a prescription, calcium hardness and total alkalinity sum after recirculated water concentrates can not surpass 900mg/L, be preferably in about 800mg/L and move, otherwise will cause fouling.Calcium hardness and total alkalinity sum are 100-300mgL -1About medium hardness, basicity water quality, if moisturizing is 200mg/L, the cycles of concentration of recirculated water is preferably in 4 times so, the highest can not be above 4.5 times.
Existing multipolymer, as T225 and contain AMPS sulfonic group multipolymer, its performance shows as satisfactory stability zinc salt and calcium phosphate performance, and the performance of stablizing lime carbonate is then not very good.
Recompounded multielement antisludging corrosion inhibitor when Chinese patent application CN1258649A discloses a kind of suitable reusing sewage, main component is organic phospho acid, contain sulfonic group multipolymer and zinc salt, prescription stresses inhibition, the inhibition problem when solving reusing sewage, but the scale inhibition effect of this prescription is not ideal.
Summary of the invention
The object of the present invention is to provide a kind of composite scale-inhibiting corrosion inhibitor, it has good resistance CaCO 3With resistance Ca 3(PO 4) 2The dirt function also has Zn in the satisfactory stability water 2+Ability and corrosion inhibition.
Another object of the present invention is that composite scale-inhibiting corrosion inhibitor of the present invention is applied to recirculated cooling water to be handled, and it can improve the cycles of concentration of recirculated water, thereby saves the consumption of fresh water.
For achieving the above object, the invention provides a kind of composite scale-inhibiting corrosion inhibitor, comprising containing phosphonate group poly aspartic acid and at least a anti-incrustation corrosion inhibitor, the described general formula that contains the phosphonate group poly aspartic acid is:
R wherein 1, R 2, R 3And R 4Be H or CH independently 2-PO 3H 2, the molecular weight of poly aspartic acid is 2000-20000, be preferably 3000-5000,4000-5000 more preferably, and the content of the described organic phosphine that contains the phosphonate group poly aspartic acid is (with PO 4Meter) is at least 2 weight %.
H in the poly aspartic acid on the nitrogen is by CH 2-PO 3H 2What replace is many more, and the content of organic phosphine is high more, and its scale-inhibiting properties is good more, but the content of organic phosphine can unrestrictedly not increase, its maximum be in the poly aspartic acid H on the nitrogen all by CH 2-PO 3H 2Replace, organic phosphine content of the present invention is with PO 4Meter is preferably 2 weight %-11 weight %, 5 weight %-11 weight % more preferably.
When the present invention contained the phosphonate group poly aspartic acid in preparation, can adopt with poly aspartic acid, phosphorus trichloride, formaldehyde and water was feedstock production, and also can adopt poly aspartic acid, phosphorous acid, formaldehyde and water is feedstock production.
The phosphonate group poly aspartic acid that contains of the present invention can be by following method preparation, this method is included in and adds formaldehyde and water under 10-30 ℃ in the poly aspartic acid aqueous solution, controlled temperature is not higher than 50 ℃, drip phosphorus trichloride, treat to be warming up to again after phosphorus trichloride adds 60-110 ℃, preferred 80-100 ℃, and under 60-110 ℃, preferred 80-100 ℃, reacted 1-4 hour, obtain containing the phosphonate group poly aspartic acid; Perhaps control the poly aspartic acid aqueous temperature and be not higher than 50 ℃, drip phosphorus trichloride, treat to be warming up to again after phosphorus trichloride adds 60-110 ℃, preferred 80-100 ℃, drip formaldehyde, treat formaldehyde dropwise the back 60-110 ℃, preferred 80-100 ℃ following insulation reaction 1-4 hour, obtain containing the phosphonate group poly aspartic acid.Wherein the weight ratio of poly aspartic acid and phosphorus trichloride is: poly aspartic acid/phosphorus trichloride=15/ (3-18); The mol ratio of phosphorus trichloride and formaldehyde is: phosphorus trichloride/formaldehyde=1/ (1-1.1).
The phosphonate group poly aspartic acid that contains of the present invention also can be by another kind of method preparation, this method is included in and adds formaldehyde, phosphorous acid and water under 10-30 ℃ in the poly aspartic acid aqueous solution, controlled temperature is not higher than 50 ℃, drip concentrated hydrochloric acid, treat to be warming up to 60-110 ℃ again after concentrated hydrochloric acid adds, to be preferably 80-100 ℃, and 60-110 ℃, be preferably 80-100 ℃ of down reaction 1-4 hour, obtain containing the phosphonate group poly aspartic acid.Wherein the weight ratio of poly aspartic acid and phosphorous acid is: poly aspartic acid/phosphorous acid=15/ (2-11); The mol ratio of phosphorous acid and formaldehyde is: phosphorous acid/formaldehyde=1/ (1-1.1).The purpose that concentrated hydrochloric acid adds is to carry out in order to make to be reflected under the acidic conditions, and its consumption is had no particular limits, and the mol ratio of preferred hydrogenchloride and poly aspartic acid is 0.5-2 for well.
Anti-incrustation corrosion inhibitor of the present invention is organic phospho acid and/or contains the carboxylic acid-based copolymer.
Organic phospho acid of the present invention is at least a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) that is selected from, Amino Trimethylene Phosphonic Acid (ATMP), 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), ethylene diamine tetra methylene phosphonic acid (EDTMPS), diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic compounds, be preferably at least a 2-of being selected from phosphonate group-1,2, the 4-butane tricarboxylate, diethylene triamine pentamethylene phosphonic, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic compounds.Wherein amino acid two methene phosphonic acids add phosphorus trichloride (PCl afterwards again by amino acid (as glycine, L-glutamic acid) and formaldehyde (HCHO) solution is simultaneously soluble in water 3) reaction obtain; Perhaps, add the concentrated hydrochloric acid reaction again and obtain by amino acid (as glycine, L-glutamic acid), phosphorous acid and formaldehyde solution is simultaneously soluble in water.
Of the present inventionly contain the carboxylic acid-based copolymer for copolymer or terpolymer, be preferably at least a vinylformic acid (the AA)/Propylene glycol monoacrylate multipolymer that is selected from, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, 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/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-multipolymer of acrylamido propane sulfonic acid multipolymer.Wherein said acrylate is preferably from vinylformic acid C1-8 ester, more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate (HPA).
When using copper material equipment in the circulation cooling water system, composite scale-inhibiting corrosion inhibitor of the present invention also can contain heterogeneous ring compound as copper material corrosion inhibitor.Described copper material corrosion inhibitor is preferably from mercaptobenzothiazole and benzotriazole.
The phosphonate group poly aspartic acid that contains of the present invention is 2-12mg/L with respect to the effective concentration of pending aqueous solution total amount.
Organic phospho acid of the present invention (if any) is 2-10mg/L with respect to the effective concentration of pending aqueous solution total amount.
The carboxylic acid-based copolymer of containing of the present invention (if any) is 2-10mg/L with respect to the effective concentration of pending aqueous solution total amount.
Copper material corrosion inhibitor of the present invention (if any) is 0.5-1.5mg/L with respect to the effective concentration of pending aqueous solution total amount.
Available ordinary method prepares composite scale-inhibiting corrosion inhibitor of the present invention, the reinforced order of each component is unimportant, for example can be with anti-incrustation corrosion inhibitor, contain phosphonate group poly aspartic acid and copper material corrosion inhibitor (if any) and water by predetermined mixed, can make required composite scale-inhibiting corrosion inhibitor.
Owing to contain the phosphonate group poly aspartic acid and have good scale inhibition ability, and and organic phospho acid and/or contain the carboxylic acid-based copolymer good synergy is arranged, therefore, composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO 3With resistance Ca 3(PO 4) 2The dirt function also has Zn in the satisfactory stability water 2+Ability and corrosion inhibition.When being used for the recirculated cooling water processing, can improve the cycles of concentration of recirculated water, thereby save the consumption of fresh water.
Composite scale-inhibiting corrosion inhibitor of the present invention can be applicable to recirculated cooling water and handles, and being particularly suitable for being applied to calcium hardness and total alkalinity sum is 100-300mgL -1The processing of not adjust pH recirculated cooling water of medium hardness, moderate alkalinity water quality.Composite corrosion inhibitor scale-inhibiting properties of the present invention is good, can improve cycles of concentration.As be applied to that recirculated water concentrates the back calcium hardness and the total alkalinity sum reaches 1200mg/L (with CaCO 3Meter) has good scale-inhibiting properties the time.
For calcium hardness and total alkalinity sum is 300mgL -1Above high rigidity, high basicity water quality, when it is used for recirculated cooling water, for preventing fouling, often adopt sour adjust pH, reduce the basicity in the water, at this moment, the inhibition problem should be the major issue that will solve, when composite scale-inhibiting corrosion inhibitor of the present invention is used for the processing of recirculated cooling water, also should increase the good component of corrosion inhibition, as zinc salt etc.
For calcium hardness and total alkalinity sum is 100mgL -1Following soft, low basicity water quality, when it was used for recirculated cooling water, the major issue that solve also was the inhibition problem, equally, when composite scale-inhibiting corrosion inhibitor of the present invention is used for the processing of recirculated cooling water, also should increase the good component of corrosion inhibition, as zinc salt etc.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
The test raw water quality sees Table 1.
Table 1 test raw water quality
Water quality ????Ca 2+ Total alkalinity Total hardness ??Cl - ???SO 4 2- ????pH Specific conductivity Total molten solid
Former water 1 ????97 ????155 ????176 ??14 ???35 ????7.8 ????210 ????315
Former water 2 ????265 ????380 ????370 ??78 ???120 ????7.8 ????1020 ????756
Former water 3 ????25 ????31 ????37 ??9 ???11 ????7.4 ????120 ????69
Annotate: 1) pH does not have unit, and specific conductivity is μ s/cm, and its counit is mg/l, Ca 2+, total alkalinity, total hardness be all with CaCO 3Meter, down together;
2), Ca 2+Represent calcium hardness, down together.
" water coolant analysis and the test method " that the measuring method of water quality is write with reference to production department of China PetroChemical Corporation and development division (1993, general petrochemical works, Anqing information center publishes).
The assessment of performance method that contains phosphonate group poly aspartic acid and composite scale-inhibiting corrosion inhibitor of following embodiment gained is as follows:
Resistance calcium carbonate scale performance: get the former water of test, add 8mgL -1(in effective concentration) contains phosphonate group poly aspartic acid (embodiment 1-9, test former water 1) or by drug concentration (embodiment 10-20, Comparative Examples 1-4) that embodiment added, evaporation concentration in 80 ± 1 ℃ of waters bath with thermostatic control, to cycles of concentration (test former water 1 and 3 to 5 times of cycles of concentration, the test former water 2 to 2 times of cycles of concentration), remain Ca in the sampling analysis water 2+Concentration, make blank sample simultaneously, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C0)/(nC1-C0) * 100%
C: actual measurement Ca 2+Concentration
C0: the Ca of blank sample 2+Concentration
C1: the Ca in the former water 2+Concentration
N: be cycles of concentration
Resistance calcium phosphate scale performance: get distilled water and add a certain amount of calcium ion, preparation Ca 2+Concentration is 250mgL -1, PO 4 3-Concentration is 5mgL -1Test water, add 8mgL -1Contain phosphonate group poly aspartic acid (embodiment 1-9) or, in 80 ± 1 ℃ of waters bath with thermostatic control, left standstill 10 hours, make blank sample simultaneously, and remain PO in the sampling analysis water by the medicament of the drug concentration (embodiment 10-20, Comparative Examples 1-4) that embodiment added 4 3-Concentration, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C0)/(C1-C0) * 100%
C: actual measurement PO 4 3-Concentration
C0: PO in the blank sample 4 3-Concentration
C1: PO in the former water 4 3-Concentration
Stablize the zinc salt performance: get distilled water preparation Ca 2+Concentration is 250mgL -1, basicity is 250mgL -1And Zn 2+Be 5mgL -1Test water, add 8mgL -1Contain phosphonate group poly aspartic acid (embodiment 1-9) or, in 80 ± 1 ℃ of waters bath with thermostatic control, left standstill 10 hours, remain Zn in the sampling analysis water by the medicament of the drug concentration (embodiment 10-20, Comparative Examples 1-4) that embodiment added 2+Concentration, make blank sample simultaneously, and calculate resistance zinc rate.
Resistance zinc rate calculation formula is: resistance zinc rate=(C-C0)/(C1-C0) * 100%
C: actual measurement Zn 2+Concentration
C0: the Zn of blank sample 2+Concentration
C1: the Zn in the former water 2+Concentration
Resistance zinc rate is high more, and the stability of zinc salt in water is good more, and it is good more to illustrate that medicament is stablized the performance of zinc salt.
Corrosion inhibition: the test piece of 20# qualitative carbon steel is fixed on the lacing film instrument, puts into and be added with 8mgL -1Contain phosphonate group poly aspartic acid (embodiment 1-9, the former water 1 of concentration test is to 5 times of multiples) or (the former water 1 of concentration test and 3 is to 5 times of multiples, not adjust pH by the test water of the drug concentration (embodiment 10-20, Comparative Examples 1-4) that embodiment added; The former water 2 of concentration test is to 2 times of multiples, and adjust pH) in, 40 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72 hours, and the weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is: F=C * Δ W/A * T * ρ
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 * 10 7
Δ W: the corrosion weight loss of test specimen (gram)
A: the area of test specimen (centimetre 2)
T: the corrosion test time (hour)
ρ: the density (kilogram/rice of material for test 3)
The measuring method total phosphorus of phosphorus, positive phosphorus, phosphorous measuring method are with reference to total phosphorus, positive phosphorus, phosphorous measuring method among " People's Republic of China's specialized standard " ZB G 71002～71004-89.
Organic phosphine Determination on content formula is: X2=X1 * 3.067-X3 * 1.203-X4
X1: total phosphorous (in P);
X2: organic phosphine content is (with PO 4Meter);
3.067: the coefficient that becomes the phosphate radical quality by the phosphorus mass conversion;
X3: inferior phosphorus content is (with PO 3Meter);
1.203: the coefficient that is converted into phosphate radical by orthophosphite;
X4: positive phosphorus content is (with PO 4Meter).
Embodiment 1
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 70 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 8.2%.
Embodiment 2
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 105 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 7.3%.
Embodiment 3
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 4 hours, cool off product.The organic phosphine content of product is 9.5%.
Embodiment 4
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 9.4%.
Embodiment 5
(the too bright chemical engineering industry in Shanxi company limited produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 8000-18000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) down in room temperature (20 ℃).Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 9.4%.
Embodiment 6
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Below 50 ℃, drip phosphorus trichloride 45.2g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃, drip formalin 26.6g (effective constituent is by 36%), treat that formalin dropwises back insulation reaction 2 hours under 90 ± 2 ℃ of temperature, cool off product.The organic phosphine content of product is 10.1%.
Embodiment 7
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 167ml water, start stirring, poly aspartic acid is fully dissolved.Add formalin 26.6g (effective constituent is by 36%) and phosphorous acid 26.9g (effective constituent is by 97%) down in room temperature (20 ℃).Below 50 ℃, drip concentrated hydrochloric acid 11.7g with the cooling bath control reaction temperature.Treat that concentrated hydrochloric acid dropwises, be warming up to 90 ± 2 ℃ and insulation reaction 2 hours, cool off product.The organic phosphine content of product is 9.3%.
Embodiment 8
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Below 50 ℃, drip phosphorus trichloride 27.1g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃, drip formalin 16.5g (effective constituent is by 36%), treat that formalin dropwises back insulation reaction 2 hours under 90 ± 2 ℃ of temperature, cool off product.The organic phosphine content of product is 6.4%.
Embodiment 9
(Chang Mao Biochemical Engineering Co produces to add poly aspartic acid in four neck flasks of agitator, reflux exchanger, constant pressure funnel and thermometer are housed, content: 40%, molecular weight: 4000-5000) 91.6g and 157ml water, start stirring, poly aspartic acid is fully dissolved.Below 50 ℃, drip phosphorus trichloride 13.5g (effective constituent is by 97%) with the cooling bath control reaction temperature.Treat that phosphorus trichloride dropwises, be warming up to 90 ± 2 ℃, drip formalin 8.2g (effective constituent is by 36%), treat that formalin dropwises back insulation reaction 2 hours under 90 ± 2 ℃ of temperature, cool off product.The organic phosphine content of product is 3.5%.
Embodiment 10
Process for preparation: preparation contains phosphonate group poly aspartic acid composite scale-inhibiting corrosion inhibitor 100g
Taking by weighing the 30g solid content and be 20% contain phosphonate group poly aspartic acid, active ingredient by embodiment 1 preparation is 50% PBTCA 16g, adds 54g water, shakes up, and promptly obtains the 100g medicament of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the medicament for preparing, the effective concentration that contains phosphonate group poly aspartic acid, PBTCA in the water is respectively 6mg/L, 8mg/L.
Embodiment 11
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 40g solid content and be 20% contain phosphonate group poly aspartic acid and 10g active ingredient by embodiment 3 preparations is 50% diethylene triamine pentamethylene phosphonic, joins in the 50g water, shakes up, and promptly obtains the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration that contains phosphonate group poly aspartic acid, diethylene triamine pentamethylene phosphonic in the water is respectively 8mg/L, 5mg/L.
Embodiment 12
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 40g solid content and be 20% contain phosphonate group poly aspartic acid and 26.7g active ingredient by embodiment 4 preparations is that (limit viscosity number is 0.078dl/g 30 ℃ the time for 30% T225, weight ratio is AA/HPA=80/20), join in the 33.3g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration that contains phosphonate group poly aspartic acid, T225 in the water is respectively 8mg/L, 8mg/L.
Embodiment 13
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 30g solid content and be 20% contain phosphonate group poly aspartic acid, active ingredient by embodiment 5 preparations is that 50% PBTCA 8g and active ingredient are 50% ATMP 4g, joins in the 58g water, shakes up, and promptly obtains the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration that contains phosphonate group poly aspartic acid, PBTCA, ATMP in the water is respectively 6mg/L, 4mg/L, 2mg/L.
Embodiment 14
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 30g solid content and be 20% contain phosphonate group poly aspartic acid, active ingredient by embodiment 6 preparations is 30% T225 (limit viscosity number is 0.072dl/g 30 ℃ the time, weight ratio is AA/HPA=80/20) 13.3g and AA/AMPS contain carboxylic acid group and sulfonic group copolymer simultaneously (limit viscosity number be 0.074dl/g 30 ℃ the time, weight ratio is AA/AMPS=70/30) 16.7g, join in the water of 40g, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L, contain the effective concentration that phosphonate group poly aspartic acid, T225, AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously in the water and be respectively 6mg/L, 4mg/L, 5mg/L with the liquid medicine for preparing.
Embodiment 15
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 30g solid content and be 20% contain phosphonate group poly aspartic acid, active ingredient by embodiment 7 preparations is that (limit viscosity number is 0.075dl/g 30 ℃ the time for 30% T225, weight ratio is AA/HPA=80/20) 10g and active ingredient be 50% glycine two methene phosphonic acids 10g, join in the 50g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L, contain phosphonate group poly aspartic acid, T225, glycine two methene phosphonic effective concentration in the water and be respectively 6mg/L, 3mg/L, 5mg/L with the liquid medicine for preparing.
Embodiment 16
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 20g solid content and be 20% contain phosphonate group poly aspartic acid, active ingredient by embodiment 8 preparations is that 50% PBTCA 8g, active ingredient are that 50% L-glutamic acid two methene phosphonic acids 4g and active ingredient are that 30% AA/AMPS/HPA contains carboxylic acid group and sulfonic group terpolymer simultaneously (limit viscosity number is 0.073dl/g 30 ℃ the time, weight ratio is AA/AMPS/HPA=60/20/20) 20g, join in the 48g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L, contain the effective concentration that phosphonate group poly aspartic acid, PBTCA, L-glutamic acid two methene phosphonic acids and AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously in the water and be respectively 4mg/L, 4mg/L, 2mg/L, 6mg/L with the liquid medicine for preparing.
Embodiment 17
Process for preparation: preparation 100g liquid medicine
Taking by weighing the 30g solid content and be 20% contain phosphonate group poly aspartic acid, active ingredient by embodiment 6 preparations is that 50% thionamic acid two methene phosphonic acids 8g, active ingredient are 30% T225 (limit viscosity number is 0.075dl/g 30 ℃ the time, weight ratio is AA/HPA=80/20) 6.7g and AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously (limit viscosity number be 0.078dl/g 30 ℃ the time, weight ratio is AA/AMPS/HPA=70/15/15) 6.7g, join in the 48.6g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L, contain the effective concentration that phosphonate group poly aspartic acid, thionamic acid two methene phosphonic acids, T225, AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously and be respectively 6mg/L, 4mg/L, 2mg/L, 2mg/L with the liquid medicine for preparing.
Embodiment 18
Process for preparation: preparation 100g liquid medicine
Take by weighing the 20g solid content and be 20% and contain the phosphonate group poly aspartic acid by embodiment 6 preparations, active ingredient is 30% T225, and (limit viscosity number is 0.072dl/g 30 ℃ the time, weight ratio is AA/HPA=80/20) 6.7g and AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously (limit viscosity number be 0.073dl/g 30 ℃ the time, weight ratio is AA/AMPS/HPA=60/25/15) 13.4g, active ingredient is that 50% PBTCA 4g and active ingredient are that 50% taurine two methene phosphonic acids 6g join in the 49.9g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L, contain the effective concentration that phosphonate group poly aspartic acid, taurine two methene phosphonic acids, PBTCA, T225 and AA/AMPS/HPA contain carboxylic acid group and sulfonic group terpolymer simultaneously and be respectively 4mg/L, 3mg/L, 2mg/L, 2mg/L, 4mg/L with the liquid medicine for preparing.
Embodiment 19
Process for preparation: preparation 100g contains the zinc salt liquid medicine
The add-on of removing Zinc vitriol is 8.75g, and the add-on of water is outside the 41.15g, and other component and add-on are with embodiment 18, and the 100g that makes required preparation contains the zinc salt liquid medicine.
When adding in test former water 2 (with sulfuric acid adjust pH 7.8-8.2) and former water 3 by the drug concentration of 100mg/L, contain phosphonate group poly aspartic acid, taurine two methene phosphonic acids, PBTCA, T225, Zn with the liquid medicine for preparing 2+The effective concentration that contains carboxylic acid group and sulfonic group terpolymer with AA/AMPS/HPA simultaneously is respectively 4mg/L, 3mg/L, 2mg/L, 2mg/L, 2mg/L, 4mg/L.
Embodiment 20
Process for preparation: preparation 100g contains the zinc salt liquid medicine
The add-on of removing Zinc vitriol is 10.94g, and the add-on of water is outside the 37.66g, and other component and add-on are with embodiment 17, and the 100g that makes required preparation contains the zinc salt liquid medicine.
When adding in test former water 2 (with sulfuric acid adjust pH 7.8-8.2) and former water 3 by the drug concentration of 100mg/L, contain phosphonate group poly aspartic acid, thionamic acid two methene phosphonic acids, Zn with the liquid medicine for preparing 2+, T225, the AA/AMPS/HPA effective concentration that contains carboxylic acid group and sulfonic group terpolymer simultaneously is respectively 6mg/L, 4mg/L, 2.5mg/L, 2mg/L, 2mg/L.
Comparative Examples 1
Process for preparation: preparation 100g liquid medicine
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 20g solid content and be the terpolymer of 30% AA/AMPS/HPA, weight ratio is AA/AMPS/HPA=60/20/20), active ingredient is 50% PBTCA 9g, HEDP 9g, add in the 62g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of the terpolymer of AA/AMPS/HPA, PBTCA, HEDP is respectively 6mg/L, 4.5mg/L, 4.5mg/L.
Comparative Examples 2
Process for preparation: contain zinc salt liquid medicine 100g
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 20g solid content and be the terpolymer of 30% AA/AMPS/HPA, weight ratio is AA/AMPS/HPA=60/20/20), active ingredient is 50% PBTCA 9g, HEDP 9g and 6.25g Zinc Chloride Anhydrous, add in the 55.75g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the terpolymer of AA/AMPS/HPA, PBTCA, HEDP, Zn 2+Effective concentration be respectively 6mg/L, 4.5mg/L, 4.5mg/L, 3mg/L.
Comparative Examples 3
Process for preparation: preparation 100g liquid medicine
(Chang Mao Biochemical Engineering Co produces to take by weighing the 15g solid content and be 40% poly aspartic acid, molecular weight: 4000-5000), active ingredient is 50% PBTCA 9g and HEDP 9g and joins in the 67g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in the former water 1 of test by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of poly aspartic acid, PBTCA, HEDP is respectively 6mg/L, 4.5mg/L, 4.5mg/L in the water.
Comparative Examples 4
Process for preparation: preparation 100g liquid medicine
(Chang Mao Biochemical Engineering Co produces to take by weighing the 15g solid content and be 40% poly aspartic acid, molecular weight: 4000-5000), active ingredient is 50% PBTCA 9g and HEDP 9g, 13.13g Zinc vitriol and joins in the 53.87g water, shake up, promptly obtain the 100g liquid medicine of required preparation.
When adding in test former water 2 (with sulfuric acid adjust pH 7.8-8.2) and former water 3 by the drug concentration of 100mg/L with the liquid medicine for preparing, poly aspartic acid, PBTCA, HEDP, Zn in the water 2+Effective concentration be respectively 6mg/L, 4.5mg/L, 4.5mg/L, 3mg/L.
Carry out static test by the above-mentioned concentration that adds, inhibition and scale inhibition effect see Table 2.
The inhibition of table 2 medicament and scale inhibition effect
Embodiment Lime carbonate scale inhibition performance/% Calcium phosphate scale inhibition performance/% Resistance zinc rate/% Corrosion speed/mm.a -1
???????1 ?????65.8 ????????78.8 ????19.4 ????0.305
???????2 ?????61.4 ????????65.4 ????12.8 ????0.317
???????3 ?????72.4 ????????87.9 ????30.5 ????0.278
???????4 ?????71.8 ????????86.8 ????29.2 ????0.342
???????5 ?????68.3 ????????80.9 ????21.6 ????0.295
???????6 ?????75.2 ????????90.5 ????32.8 ????0.259
???????7 ?????71.5 ????????86.1 ????27.0 ????0.345
???????8 ?????65.1 ????????76.2 ????19.6 ????0.378
???????9 ?????52.5 ????????44.3 ????12.3 ????0.452
???????10 ?????83.5 ????????82.3 ????25.4 ????0.035
???????11 ?????80.9 ????????72.7 ????21.5 ????0.029
???????12 ?????80.5 ????????98.9 ????45.7 ????0.040
???????13 ?????83.4 ????????93.4 ????40.5 ????0.024
???????14 ?????80.4 ????????99.2 ????56.8 ????0.034
???????15 ?????83.8 ????????94.8 ????48.2 ????0.026
???????16 ?????84.1 ????????99.4 ????58.9 ????0.023
???????17 ?????82.7 ????????99.1 ????55.6 ????0.025
???????18 ?????84.5 ????????99.5 ????60.4 ????0.022
???????19 Former water 2 ?????84.8 ????????99.1 ????61.1 ????0.024
Former water 3 ?????96.4 ????0.025
???????20 Former water 2 ?????85.5 ????????98.9 ????54.9 ????0.028
Former water 3 ?????98.7 ????0.030
Comparative Examples 1 ?????75.3 ????????85.4 ????42.7 ????0.042
Comparative Examples 2 Former water 2 ?????80.4 ????????84.5 ????42.3 ????0.038
Former water 3 ?????94.7 ????0.044
Comparative Examples 3 ?????71.7 ????????0 ????0 ????0.178
Comparative Examples 4 Former water 2 ?????75.3 ????????0 ????0 ????0.125
Former water 3 ?????82.7 ????0.347
Table 2 data declaration, composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO 3With resistance Ca 3(PO 4) 2The dirt function also has Zn in the satisfactory stability water 2+Ability and corrosion inhibition.Can improve the cycles of concentration of system, the conserve water resource.
Embodiment 21
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-91 of the People's Republic of China (PRC), and controlled variable is as follows.
Cycles of concentration control is controlled with calcium hardness+total alkalinity value:
Concentrate the A tower: 850 ± 50mg/L B tower, 1150 ± 50mg/L
Flow velocity: 1.0m/s
Medicament: A tower: the compound of Comparative Examples 1
The compound of B tower: embodiment 18
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality sees Table 1 former water 1.
Dynamic analog test test piece and test tube the results are shown in Table 3.
Test piece of table 3 dynamic analog test and test tube result
Test conditions The test tube result
Medicament Working time Erosion rate (mm/a) Adhere to speed (mcm)
The A tower 15 days ????0.029 ???7.3
The B tower 15 days ????0.024 ???6.9
Stipulate that the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a among standard GB 50050-95 " Code for design of industrial recirculating cooling water treatment " 3.1.6; " the small-sized experimental analogic method of testing laboratory " regulation corrosion of Carbon Steel speed is " good " level between 0.028-0.056mm/a in " the water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, is " can allow " level at 0.056-0.070mm/a; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.
This shows, using the phosphonate group poly aspartic acid composite scale-inhibiting corrosion inhibitor that contains of the present invention is under the situation of 1150 ± 50mg/L in calcium hardness and total alkalinity sum, the erosion rate of test tube is 0.024mm/a, reach China Petrochemical Industry's " fine level " standard, adhere to speed 6.9mcm, reach " good level " standard, be better than inhibition and the scale-inhibiting properties of comparative formula when calcium hardness+total alkalinity is 850 ± 50mg/L.The result also shows, uses the rate of water make-up that contains phosphonate group poly aspartic acid composite scale-inhibiting corrosion inhibitor can economized cycle water of the present invention.

Claims (11)

1. composite scale-inhibiting corrosion inhibitor, comprising containing phosphonate group poly aspartic acid and at least a anti-incrustation corrosion inhibitor, the described general formula that contains the phosphonate group poly aspartic acid is:
R wherein 1, R 2, R 3And R 4Be H or CH independently 2-PO 3H 2, the molecular weight of poly aspartic acid is 2000-20000, with PO 4The content of meter organic phosphine is at least 2 weight %.
2. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that the molecular weight of described poly aspartic acid is 3000-5000, is preferably 4000-5000.
3. anti-incrustation corrosion inhibitor according to claim 1 and 2 is characterized in that the described content that contains the organic phosphine of phosphonate group poly aspartic acid is 2 weight %-11 weight %, is preferably 5 weight %-11 weight %.
4. according to each described anti-incrustation corrosion inhibitor of claim 1-3, it is characterized in that described anti-incrustation corrosion inhibitor is organic phospho acid and/or contains the carboxylic acid-based copolymer.
5. anti-incrustation corrosion inhibitor according to claim 4, it is characterized in that organic phospho acid is at least a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid that is selected from, Amino Trimethylene Phosphonic Acid, 2-phosphonate group-1,2, the 4-butane tricarboxylate, the hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic compounds, be preferably at least a 2-of being selected from phosphonate group-1,2, the 4-butane tricarboxylate, diethylene triamine pentamethylene phosphonic, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic compounds.
6. anti-incrustation corrosion inhibitor according to claim 4 is characterized in that containing the carboxylic acid-based copolymer and is at least a vinylformic acid/Propylene glycol monoacrylate multipolymer that is selected from, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, 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/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-multipolymer of acrylamido propane sulfonic acid multipolymer.
7. according to each described anti-incrustation corrosion inhibitor of claim 1-6, it is characterized in that also containing heterogeneous ring compound as copper material corrosion inhibitor.
8. anti-incrustation corrosion inhibitor according to claim 7 is characterized in that described copper material corrosion inhibitor selected from mercapto benzothiazole and benzotriazole.
9. anti-incrustation corrosion inhibitor according to claim 1, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: the organic phospho acid total concn is 2-10mg/L, containing phosphonate group poly aspartic acid concentration is 2-12mg/L, and containing carboxylic acid-based copolymer's concentration is 2-10mg/L.
10. according to claim 7 or 8 described anti-incrustation corrosion inhibitors, it is characterized in that the effective concentration with respect to pending aqueous solution total amount copper material corrosion inhibitor is 0.5-1.5mg/L.
11. the application of each described anti-incrustation corrosion inhibitor of claim 1-9 is characterized in that the described anti-incrustation corrosion inhibitor of claim 1-9 is applicable to the recirculated cooling water processing.
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