CN101245140A - Non-ionic polymeric compound for inhibiting deposition of silicon dioxide/silicate dirt in water and method of producing same - Google Patents
Non-ionic polymeric compound for inhibiting deposition of silicon dioxide/silicate dirt in water and method of producing same Download PDFInfo
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- CN101245140A CN101245140A CNA2008100345533A CN200810034553A CN101245140A CN 101245140 A CN101245140 A CN 101245140A CN A2008100345533 A CNA2008100345533 A CN A2008100345533A CN 200810034553 A CN200810034553 A CN 200810034553A CN 101245140 A CN101245140 A CN 101245140A
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Abstract
The invention pertains to the technical field of industrial water treatment, which more particularly relates to a non-ionic polymer which restricts the depositions of silica/silicates in water and a preparation method thereof. The polymer is a non-ionic copolymer which contains ether linkage, secondary amine linkage and peptide linkage, substantially the non-ionic copolymer is a hexanedioic acid/ amino terminated polyether / divinyl three amine copolymer. According to the regular condensation polymerization principle, a certain amount of amino terminated polyether D230 and a certain amount of divinyl three amine are mixed uniformly by water, and then a certain amount of hexanedioic acid is added in and stirred for dissolving. The condensation polymerization is carried out again under certain temperature and the released moisture in the process is removed. After 3-5 hours of condensation polymerization, the temperature is reduced to 120-125 DEG C and a certain amount of deionized water is added which is stirred for 2-3 hours under the same temperature. Subsequently the temperature is cooled to the room temperature and the required polymer is obtained. The polymer has good restriction and dispersal effects on the deposits of silicon dioxide/silicate in the water system and is a novel non-ionic polymer which is phosphate-free and biodegradable.
Description
Technical field
The invention belongs to the Treatment of Industrial Water technical field, be specifically related to sedimentary non-ionic polyalcohol of silica/silicon hydrochlorate and preparation method thereof in a kind of inhibition water.
Background technology
In the Treatment of Industrial Water field, former water contains a large amount of alkaline earth metal cations such as Ca usually
2+, Mg
2+, Ba
2+Deng and anionic group such as CO
3 3-, SO
4 2-And PO
4 3-Deng, and the silicon-dioxide of solubility.Under certain condition (as evaporation, concentrating etc.), these positively charged ions and negatively charged ion are very easily in conjunction with forming CaCO
3, CaSO
4, BaSO
4, Ca
3(PO
4) wait inorganic salt crust, be deposited on water treatment pipeline and equipment surface and work the mischief.The silicon-dioxide of solubility also can form insoluble silicon-dioxide and silicate deposit in water treatment pipeline and equipment surface at certain condition in the water, can work the mischief to water treatment system equally, and these silicon dirt formation in a single day, just be difficult to remove.
At occurring in nature, element silicon usually with silicon-dioxide (as quartzy SiO
2) and silicate (as asbestos CaMg
3(SiO
3)
4, kaolin Al
2Si
2O
5(OH)
4, garnet Ca
3Al
2(SiO
4)
3Deng) form exist.Silicon-dioxide is divided into crystal type SiO again
2(as quartzy, crystal) and unformed SiO
2(as diatomite).The solubleness of powdered quartz is very low, has only 5-6mg/l, and the solubleness of amorphous silica is 100～120mg/l when neutral pH and 20～25 ℃.
Solvability silicon-dioxide mainly is made up of silicic acid and silicate in natural water, derives from ore and atmospheric disintegration of rocks, and its dioxide-containing silica is usually at 1～40mg/l, but some area is up to 30mg/l～180mg/l.The dissolving in water of silicon-dioxide and silicate mainly is that its ratio depends on pH because the hydrolysis of Si-O-Si key causes that silicon-dioxide and silicate are discharged in the water.SiO
2It is the acid anhydrides of silicic acid.Silicic acid is diversified, with general formula xSiO
2YH
2O represents (claiming aqueous silicon dioxide again), and its condition of forming with formation changes, and metasilicic acid H is arranged
2SiO
3(x=1, y=1), positive silicic acid H
4SiO
4(x=1, y=2), disilicic acid H
6Si
2O
7(x=2, y=3).But when the aqueous solution formed, beginning mainly was positive silicic acid H
4SiO
4, when placement condition (when adding acid or alkali or other ionogen) changes, can gradually become metasilicic acid or disilicic acid form.Usually said silicon-dioxide (silica) is a general name, is meant the summation of powdered quartz, amorphous silica, aqueous silicon dioxide and hydroxylated silicon-dioxide.Silicate is by SiO
2Derive with silicic acid, be divided into solubility and insoluble two big classes.Having only alkali-metal silicate such as sodium, potassium is solubility, and the solubleness of ferric metasilicate and pure aluminium silicate has only 10mg/L.
Positive silicic acid H
4SiO
4Be a kind of weak acid, its ionization constant pKa
1=9.5, pKa
2=11.7, illustrate that at pH be at 9.5 o'clock, nearly 50% ionization takes place, and other 50% then with non-dissociated positive silicic acid H
4SiO
4Form exists.PH＞10 o'clock as can be seen from Table 1, the solubleness of silicon-dioxide just obviously improves, and is owing to generated water-soluble positive preferably silicic acid ion (H this moment
3SiO
4 -).PH＜9 o'clock, the dissolving form of silicon-dioxide is monomeric silicic acid Si (OH)
4, in most of pH is 7～8 natural water, positive silicic acid H
4SiO
4Ionization, SiO do not take place basically
2Be with non-dissociated positive silicic acid H
4SiO
4Form exists.
Positive silicic acid (silicic acid) is commonly referred to single silicic acid (monosilicic acid), active silica (reactive silica), monomer (monomer), solvability silicon-dioxide (soluble silica), hydrated SiO 2 (hydrated SiO
2).Though positive silicic acid can polymerization reaction take place, in the silicon-dioxide saturated solution, dimeric its content＜5%.The actual solubility of silicon-dioxide depends on temperature and pH strongly, and the degree of saturation of silicon-dioxide in water is by amorphous silica solubleness thermodynamic control under these conditions.Temperature one timing, SiO
2Solubleness in water depends on the pH of solution, and under 25 ℃, the solubleness under the different pH sees Table 1.
During 25 ℃ in table 1, SiO under the condition of different pH
2Solubleness
In Treatment of Industrial Water, pH is generally 7～9, and silicon-dioxide is with unionized monomer H in the solution at this moment
4SiO
4Form exist, when solution reached supersaturation, positive silicic acid can polymerization reaction take place.When under certain condition, when silicon-dioxide reached supersaturated solution, polymerization can take place in monomer.Insoluble SiO
2Derive from the polymerization of the positive silicic acid of solubility.Though being condensed into dimeric process by positive silicic acid is slowly,, almost generate tripolymer at once once formation.Form the linear tetramer, pentamer then again rallentando, begin to occur the side group polyreaction when forming six aggressiveness, present circle or cyclic form, become crosslinking structure at last, volume also increases gradually.Just the insoluble particle that forms is less than 0.1 μ m, and its core is by SiO
2Form, the surface is made up of silanol (≡ Si-OH).When pH＞7, the silanol on surface is with ionization, and it has determined the negative charge of silica polymerization body.Rate of polymerization relied on pH, 8.0～8.5 o'clock maximums.Bigger polymer then occurs as gluey, and stable existence in solution forms colloid silica.Since the divalent-metal ion in the water such as Ca, Mg, Fe almost always with SiO
2Exist simultaneously, these polyvalent metals destroy silicon dioxide colloid easily, and cause colloidal deposition and form the silicon dirt.This dirt is unformed, in fact by polymeric SiO
2Particle and form at the polysilicate of particle surface.
The accumulation of silicon dirt will influence the normal operation that reduces water treating equipment such as boiler, heat exchanger, reverse osmosis unit, reduce heat exchanger effectiveness and reduce flow by heat exchanger and film.When water is concentrated, SiO
2Amount when surpassing its solubleness, will cause unformed SiO
2Deposition, reduce the service efficiency of equipment.The silicon dirt is in case form very difficult the removal.When therefore using the water of high silicon dioxide content, the operation of cooling system and reverse osmosis system must be carried out under lower efficient, to guarantee to be no more than SiO
2Solubleness.Therefore reverse osmosis must limit its rate of recovery, and cooling water system must limit its cycles of concentration.So just increased water loss greatly.
Stoping two kinds of traditional methods of dirt deposition is scale inhibition and dispersion, in order to solve SiO
2With the deposition of silicate, the whole bag of tricks is disclosed, for example U.S. Pat 4,711, and 725 disclose the deposition of using silica/silicon hydrochlorate in independent use vinylformic acid/co-polymer of sulfonate prevention water.U.S. Pat 5,078,879 disclose independent use 2-phosphinylidyne butane-1,2,4-tricarboxylic acid or preferred 2-phosphinylidyne butane-1,2,4-tricarboxylic acid and carboxyl/sulfonic group multipolymer is used, to suppress the formation of silica/silicon hydrochlorate in the water.U.S. Pat 5,100,558 compound prescriptions that disclose employing HEDP, polyoxyethylene, vinylformic acid/propylene hydroxypropyl sulfonic acid ether copolymer (AA/AHPSE) are controlled the silica deposit in the water.U.S. Pat 5,300,231 disclose polyamino polyether methylene phosphonic acid (PAPEMP) and Amino Trimethylene Phosphonic Acid (ATMP) or 2-hydroxyl phosphino-acetate (HPA) is used, and can suppress pH and be 9.0, Ca
2+Be 180mgL
-1, Mg
2+Be 75mgL
-1, SiO
2Be 50mgL
-1The deposition of water mesosilicic acid salt.U.S. Pat 5,378,368 disclose that independent use polyamino polyether methylene phosphonic acid (PAPEMP) can suppress pH and is 9.0, Ca
2+Be 70mgL
-1, Mg
2+Be 25mgL
-1, SiO
2Be 100mgL
-1The deposition of water mesosilicic acid salt.Japanese Patent JP04236208 discloses and has used the inhibitor of the ampholyte copolymer of methacrylic acid and methacryloyl ethyl-trimethyl salmiac as the silicon dirt.Japanese Patent JP200427060 discloses and has used polyoxyalkylene and contain the formation that sulfonic monomer copolymer suppresses silicon-dioxide in the water.European patent EP 242900 discloses uses glycol, the composite inhibitor as silicon-dioxide of borax.Chinese patent publication number CN1307649A discloses use diethylenetriamine pentamethylenophosphonic acid(DTPP) (DETPMP) and SYNPERONIC PE/F68 or polyepoxysuccinic acid or 2-phosphinylidyne butane-1; 2,4-tricarboxylic acid or vinylformic acid/allyl group hydroxypropyl sulfonic acid copolymer is used the SiO that stops in the water
2Deposition.
What adopt as can be seen from above disclosed patent all is the traditional organic phosphine Scale inhibitors and the polymeric dispersant of ionic, and these organic phosphine Scale inhibitorss and anionic polymeric dispersing agent are to the inorganic salt crust such as the CaCO of ionic
3, CaSO
4, BaSO
4Good effect is arranged.Organic phosphine Scale inhibitors that these are traditional and anionic polymeric dispersing agent all are ionic compounds, and its effect is often limited, facts have proved for unformed SiO
2(EleftheriaNeofotistou, Konstantinos D.Demadis.Use of antiscalants for mitigation of silica (SiO are often kept the very short time in the sedimentary inhibition of dirt
2) foulingand deposition:fundamentals and applications in desalination systems[J] .Desalination, 2004,167 (8): 257-272.).
U.S. Pat 6,051, the 142 polymkeric substance SYNPERONIC PE/F68 (EOPO) that disclose independent use non-ionic type can suppress the SiO in the water system
2Deposition.U.S. Pat 7,316,787B2 discloses a kind of polymkeric substance of independent use non-ionic type, and promptly alkyl-blocked polyether compound suppresses the silica deposit in the water system.Illustrate that non-ionic polymers is to have good resistance silicon performance.
Summary of the invention
The object of the present invention is to provide sedimentary non-ionic polyalcohol of silica/silicon hydrochlorate and preparation method thereof in a kind of inhibition water, the molecular chain of this polymkeric substance has the structure of ehter bond, secondary amine key, peptide bond.
The sedimentary non-ionic polyalcohol of silica/silicon hydrochlorate in the inhibition water that the present invention proposes, this non-ionic polyalcohol molecular chain has the structure of ehter bond, secondary amine key, peptide bond, be specially hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer (Adipicacid/Amine-Terminated Polyethers D230/Diethylenetriamine, be abbreviated as AA/ATPEs/EDETA), its structural formula is as follows:
N, x, y, z represent mean polymerisation degree respectively in the formula, and n is 2～3, and x+z is 1～50, and y is 1～50, wherein
N, x, y, z are integer.
The preparation method of the sedimentary non-ionic polyalcohol of silica/silicon hydrochlorate at first mixes Amino Terminated polyether(ATPE) D230 and diethylenetriamine in the inhibition water that the present invention proposes, and under agitation adds deionized water dissolving again; Add hexanodioic acid then in batches, stir and to make its dissolving, the adding speed of control hexanodioic acid makes its temperature＜70 ℃; After adding hexanodioic acid, under nitrogen atmosphere, be warming up to 175～185 ℃ and carry out polycondensation, when the temperature of reaction solution rises to 120～125 ℃, begin to occur water of condensation, remove moisture, continue to be warming up to 175～185 ℃ by steam condenser and steam trap, and under this temperature, reacted 3～5 hours, obtain the thick thing of xanchromatic; Reaction solution is cooled to 120～125 temperature, adds deionized water, stirred 2～3 hours down, be cooled to room temperature then, promptly obtain required polymkeric substance at 120～125 ℃.
Among the present invention, the mole number M of Amino Terminated polyether(ATPE) D230
ATPEs, diethylenetriamine mole number M
EDETA, hexanodioic acid mole number M
AABetween the pass be: (M
ATPEs+ M
EDETA): M
(AA)=1: 0.98～1: 1.02.
Among the present invention, the mole number M of diethylenetriamine
EDETAMole number M with Amino Terminated polyether(ATPE) D230
ATPEsBetween the pass be: M
EDETA: M
ATPEs=1: 0.1～1: 0.3.
Among the present invention, this reaction solution is cooled to 120～130 ℃, adds deionized water, and the add-on of deionized water is: the mole number of deionized water: the mole number of hexanodioic acid=18: 1～21: 1.
The used Amino Terminated polyether(ATPE) D230 (Amine-Terminated Polyethers D230 is abbreviated as ATPEs) of the present invention is commercially available product, and its molecular structural formula is as follows:
Polymerization degree n is an integer in the formula, and scope is 2～3, and is average 2.6, and molecular weight is about 230.
The used diethylenetriamine (Diethylenetriamine is abbreviated as EDETA) of the present invention is commercially available product, and its molecular structure is as follows:
H
2N-CH
2-CH
2-NH-CH
2-CH
2-NH
2
The used hexanodioic acid (Adipic acid is abbreviated as AA) of the present invention is commercially available product, and its molecular structure is as follows:
Hexanodioic acid/Amino Terminated polyether(ATPE) provided by the invention/diethylenetriamine multipolymer is the non-ionic polyalcohol of the structure of a kind of ether-containing key, secondary amine key, peptide bond, can stop the deposition of silicon-dioxide and silicate in the water effectively.Can be widely used in aspects such as recirculating cooling water system, feedwater, oil-field water, sea water desalinization.
Embodiment
Further describe positively effect of the present invention below by a series of embodiment.
Embodiment 1 hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 34.5g Amino Terminated polyether(ATPE) D230 and 87.6g diethylenetriamine, under agitation slowly add the 70g deionized water after stirring again, stir after 10 minutes, add the 146g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 348g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 2 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 27.0g Amino Terminated polyether(ATPE) D230 and 109.0g diethylenetriamine, under agitation slowly add the 88g deionized water after stirring again, stir after 10 minutes, add the 175.2g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 120 ℃, slowly drips the 400g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 3 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 46.0g Amino Terminated polyether(ATPE) D230 and 82.4g diethylenetriamine, under agitation slowly add the 80g deionized water after stirring again, stir after 10 minutes, add the 160.7g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 370g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 4 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 30.4g Amino Terminated polyether(ATPE) D230 and 77.2g diethylenetriamine, under agitation slowly add the 65g deionized water after stirring again, stir after 10 minutes, add the 131.4g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 300g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 5 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 9.2g Amino Terminated polyether(ATPE) D230 and 77.5g diethylenetriamine, under agitation slowly add the 58g deionized water after stirring again, stir after 10 minutes, add the 116.8g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 5 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 260g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 6 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 34.5g Amino Terminated polyether(ATPE) D230 and 87.6g diethylenetriamine, under agitation slowly add the 75g deionized water after stirring again, stir after 10 minutes, add 148.9 hexanodioic acids while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slow Dropwise 35 0g deionized water, and under this temperature, continue to reflux to stir 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 7 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 38.6g Amino Terminated polyether(ATPE) D230 and 69.3g diethylenetriamine, under agitation slowly add the 60g deionized water after stirring again, stir after 10 minutes, add the 124.1g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 300g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 8 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 52.4g Amino Terminated polyether(ATPE) D230 and 78.5g diethylenetriamine, under agitation slowly add the 75g deionized water after stirring again, stir after 10 minutes, add the 146.0g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 360g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 9 hexanodioic acids/Amino Terminated polyether(ATPE)/diethylenetriamine copolymer
In the four neck flasks of being furnished with stirring, thermometer, ventpipe, steam condenser pipe and steam trap, add 36.8g Amino Terminated polyether(ATPE) D230 and 80.4g diethylenetriamine, under agitation slowly add the 68g deionized water after stirring again, stir after 10 minutes, add the 138.7g hexanodioic acid while stirring, controlled temperature＜70 ℃ in batches.After adding hexanodioic acid, feed nitrogen, and place oil bath to begin to be heated to 180 ℃, when temperature rises to 120 ℃～125 ℃, begin to have water of condensation to occur, collect condensed water by steam condenser pipe and steam trap, the temperature that continues to heat up until reaction solution reaches 180 ℃, reacted 4 hours down at 180 ℃, obtain the thick thing of xanchromatic.Then this reaction solution is cooled to 125 ℃, slowly drips the 330g deionized water, and under this temperature, continue to reflux stirred 2 hours, and then reduce to room temperature and obtain solid content and be no less than hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer of 40%.
Embodiment 10 performance tests experiment
Present embodiment is the performance test experiment of static resistance silicon dioxide dirt.
Static resistance silicon dioxide dirt experimental technique: 300～500mgL of preparation certain volume in Plastic Bottle
-1(with SiO
2Meter) sodium silicate solution adds a certain amount of resistance silicon medicament; With hydrochloric acid and sodium hydroxide the pH value of solution is adjusted to 7.0 ± 0.1 then, Plastic Bottle is placed water-bath, keeping solution temperature is 40 ℃, regularly gets a certain amount of water sample, with the membrane filtration of 0.45 μ m, measures SiO after the dilution certain multiple
2Content.SiO
2Measuring method adopts " circulating cooling water quality and water conditioner standard application guide ", and (water conditioner branch of national chemical standard Technical Committee compiles, the measuring method of dioxide-containing silica in the industrial circulating cooling water of the regulation, Chemical Industry Press in 2003).Carry out blank assay simultaneously.
Embodiment 1～9 in the performance test is prepared medicament hexanodioic acid/Amino Terminated polyether(ATPE) of the present invention/diethylenetriamine multipolymer (hereinafter to be referred as AA/ATPEs/EDETA); Comparative Examples 1～3 is commercially available organic phosphine corrosion inhibiting and descaling agent hexanediamine tetramethylene phosphonic acid (hereinafter to be referred as EDTPMP); Comparative Examples 4～6 is commercially available organic phosphine corrosion inhibiting and descaling agent polyamino polyether methylene phosphonic acids (hereinafter to be referred as PAPEMP); Comparative Examples 7～9 is commercially available dirt dispersion agent phosphino-polyacrylic acid (hereinafter to be referred as PPCA); Comparative Examples 10～12 be commercially available dirt dispersion agent vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer (hereinafter to be referred as AA/AMPS).Experimental result is shown in Table 2.The performance test experimental result of table 2 shows, the non-ionic polyalcohol of gained of the present invention---hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer has the effect of good inhibition silica deposit.
Table 2 SiO
2Stability experiment
| Comparative Examples 10 | AA/AMPS | 50 | 500 | 145 | 145 | 145 |
| Comparative Examples 11 | AA/AMPS | 100 | 500 | 220 | 200 | 150 |
| Comparative Examples 12 | AA/AMPS | 500 | 500 | 300 | 280 | 240 |
| Blank example | Do not have | 0 | 500 | 145 | 142 | 142 |
Claims (5)
1, the sedimentary non-ionic polyalcohol of silica/silicon silicate dirt in a kind of inhibition water, it is characterized in that described non-ionic polyalcohol molecular chain has the structure of ehter bond, secondary amine key, peptide bond, be specially hexanodioic acid/Amino Terminated polyether(ATPE)/diethylenetriamine multipolymer, its structural formula is as follows:
N, x, y, z represent mean polymerisation degree respectively in the formula, and n is 2～3, and x+z is 1～50, and y is 1～50, wherein
N, x, y, z are integer.
2, the preparation method of the sedimentary non-ionic polyalcohol of silica/silicon silicate dirt in the inhibition water according to claim 1 is characterized in that at first Amino Terminated polyether(ATPE) D230 and diethylenetriamine being mixed, and under agitation adds deionized water dissolving again; Add hexanodioic acid then in batches, stir and to make its dissolving, the adding speed of control hexanodioic acid makes its temperature＜70 ℃; After adding hexanodioic acid, under nitrogen atmosphere, be warming up to 175～185 ℃ and carry out polycondensation, when the temperature of reaction solution rises to 120～125 ℃, begin to occur water of condensation, remove moisture, continue to be warming up to 175～185 ℃ by steam condenser and steam trap, and under this temperature, reacted 3～5 hours, obtain the thick thing of xanchromatic; Reaction solution is cooled to 120～125 temperature, adds deionized water, stirred 2～3 hours down, be cooled to room temperature then, promptly obtain required polymkeric substance at 120～125 ℃.
3, preparation method according to claim 2 is characterized in that the mole number M of Amino Terminated polyether(ATPE) D230
ATPEs, diethylenetriamine mole number M
EDETA, hexanodioic acid mole number M
AABetween the pass be: (M
ATPEs+ M
EDETA): M
(AA)=1: 0.98～1: 1.02.
4, preparation method according to claim 3 is characterized in that the mole number M of diethylenetriamine
EDETAMole number M with Amino Terminated polyether(ATPE) D230
ATPEsBetween the pass be: M
EDETA: M
ATPEs=1: 0.1～1: 0.3.
5, preparation method according to claim 2 is characterized in that this reaction solution is cooled to 120～130 ℃, adds deionized water, and the add-on of deionized water is: the mole number of deionized water: the mole number of hexanodioic acid=18: 1～21: 1.
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| CNA2008100345533A CN101245140A (en) | 2008-03-13 | 2008-03-13 | Non-ionic polymeric compound for inhibiting deposition of silicon dioxide/silicate dirt in water and method of producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103394289A (en) * | 2013-08-16 | 2013-11-20 | 深圳市爱康泉水处理服务有限公司 | Reverse osmosis membrane scale inhibitor and applications thereof |
| CN108203509A (en) * | 2016-12-19 | 2018-06-26 | 财团法人纺织产业综合研究所 | Modify polyamide and preparation method thereof and nylon composite fibre |
| CN110921857A (en) * | 2019-12-25 | 2020-03-27 | 山东天庆科技发展有限公司 | Special scale inhibitor for MVR system and preparation method thereof |
| US10702557B2 (en) | 2016-05-25 | 2020-07-07 | Shaanxi Jianhua Biopharmaceutical Co., Ltd. | Combined external medicine for treating prostate diseases |
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2008
- 2008-03-13 CN CNA2008100345533A patent/CN101245140A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394289A (en) * | 2013-08-16 | 2013-11-20 | 深圳市爱康泉水处理服务有限公司 | Reverse osmosis membrane scale inhibitor and applications thereof |
| CN103394289B (en) * | 2013-08-16 | 2016-01-06 | 深圳市爱康泉水处理服务有限公司 | A kind of reverse osmosis membrane antisludging agent and application thereof |
| US10702557B2 (en) | 2016-05-25 | 2020-07-07 | Shaanxi Jianhua Biopharmaceutical Co., Ltd. | Combined external medicine for treating prostate diseases |
| CN108203509A (en) * | 2016-12-19 | 2018-06-26 | 财团法人纺织产业综合研究所 | Modify polyamide and preparation method thereof and nylon composite fibre |
| CN110921857A (en) * | 2019-12-25 | 2020-03-27 | 山东天庆科技发展有限公司 | Special scale inhibitor for MVR system and preparation method thereof |
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