CN101962233A - Dendritic polymer and sodium polyaspartate compound scale inhibitor for inhibiting silicon scale deposition in water - Google Patents
Dendritic polymer and sodium polyaspartate compound scale inhibitor for inhibiting silicon scale deposition in water Download PDFInfo
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Abstract
The invention belongs to the technical field of industrial water treatment, and particularly relates to a dendritic polymer and sodium polyaspartate compound scale inhibitor for inhibiting silicon scale deposition in water. The compound scale inhibitor is compounded by using dendritic polymer and sodium polyaspartate. The dendritic polymer used in the compound scale inhibitor is a 0 to 2 generation product in polyamide-amine type polymers, and has obvious performance of inhibiting silicon dioxide scale deposition in the water. The sodium polyaspartate used in the compound scale inhibitor can obviously improve the silicon dioxide scale inhibiting performance of polyamide-amine, and can effectively disperse white floccus generated when the polyamide-amine inhibits the silicon dioxide scale. The compound scale inhibitor can effectively prevent the deposition of the silicon dioxide scale, is easy to compound, does not contain phosphorus, is biodegradable, can reduce eutrophication pollution of the water body, and is favorable for environmental protection.
Description
Technical field
The invention belongs to the Treatment of Industrial Water technical field, be specifically related to a kind of branch-shape polymer and poly (sodium aspartate) composite scale inhibitor that suppresses silicon dirt deposition in the 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) waiting inorganic salt crust, silicon-dioxide can polymerization form insoluble colloid silica dirt, and these dirt depositions work the mischief in water treatment pipeline and equipment surface.And silicon dioxide dirt is different from inorganic salt crust, and in a single day silicon dioxide dirt forms, and just is difficult to remove.
At occurring in nature, element silicon usually exists with the form of silicon-dioxide and silicate.Silicon-dioxide is divided into crystal type SiO again
2With unformed SiO
2Powdered quartz solubleness＜6mgL
-1, the solubleness of amorphous silica is 120mgL when neutral pH and 25 ℃
-1Silicate is except that alkali-metal silicate solubilities such as sodium, potassium, and all the other are all insoluble.
Solvability silicon-dioxide derives from ore and atmospheric disintegration of rocks in the natural water, dioxide-containing silica usually＜40mgL
-1, but some area is up to 40～180mgL
-1The dissolving in water of silicon-dioxide and silicate mainly is because the hydrolysis of Si-O-Si key forms positive silicic acid Si (OH)
4And be discharged in the water.SiO
2It is the acid anhydrides of positive silicic acid.Positive silicic acid H
4SiO
4Be a kind of weak acid, its ionization constant pKa
1=9.5, illustrate that at pH be at 9.5 o'clock, 50% silicic acid generation ionization is arranged.PH7～9 o'clock, H
4SiO
4Ionization seldom, SiO
2Substantially be with non-dissociated H
4SiO
4Form exists, though H
4SiO
4Can polymerization reaction take place, but in the silicon-dioxide saturated solution, dimeric its content＜5%.At pH＞9, H
4SiO
4Be decomposed into water-soluble positive preferably silicic acid ion (H gradually
3SiO
4 -), this moment SiO
2Be with H
3SiO
4 -Form exist, the solubleness degree obviously improves.The solubleness of silicon-dioxide depends on temperature and pH strongly, and the solubleness of silicon-dioxide in water is meant amorphous silica usually, and in the time of 25 ℃, the solubleness under the different pH sees Table 1.
During table 125 ℃, SiO under the condition of different pH
2Solubleness
| pH | 5 | 6 | 7-8 | 8.5 | 9 | 10 |
| Solubleness/mgL -1 | 126 | 126 | 120 | 180 | 236 | 419 |
In Treatment of Industrial Water, pH is generally 7～9, and silicon-dioxide is with a large amount of unionized monomer H in the solution at this moment
4SiO
4With a spot of positive silicic acid ion (H
3SiO
4 -) the form existence.When under certain condition, when the silicon-dioxide in the water reaches supersaturation, will the monomeric polymerization of positive silicic acid take place.At first be polymerized to dimer, its process is slow, but generates tripolymer at once once forming, be polymerized to the tetramer, pentamer then again rallentando, when forming six aggressiveness, begin to present ring texture, become the polymer of crosslinking structure at last, volume also increases gradually, and its core is by SiO
2Form, the surface is made up of silanol (≡ Si-OH).When pH＞7, the silanol of polymer surfaces forms colloid silica because ionization and electronegative makes bigger polymer stable existence in solution.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, cause colloidal deposition and form the silicon dirt.This silicon dirt is unformed, in fact by polymeric SiO
2Particle and form at the polysilicate of particle surface.
In industrial water conditioning system, when water is concentrated, SiO
2Amount when surpassing its solubleness, will cause unformed SiO
2Deposition and form the silicon dirt.The accumulation of silicon dirt will influence the normal operation of water treating equipment such as boiler, heat exchanger, reverse osmosis unit, reduce heat exchanger effectiveness and reduce flow by heat exchanger and film.Because the silicon dirt is in case formation is difficult to remove, when using the water of high silicon dioxide content, the operation of cooling system and reverse osmosis system just must be carried out under lower efficient, to guarantee to be no more than SiO
2Solubleness, reverse osmosis must just limit its rate of recovery like this, cooling water system must just limit its cycles of concentration, has so increased water loss greatly, increases production cost.
Stoping two kinds of traditional methods of dirt deposition is scale inhibition and dispersion, promptly adds traditional organic phosphine Scale inhibitors and anionic polymer dirt dispersion agent.In order to solve the deposition of silicon dirt, people just usually use organic phosphonate Scale inhibitors, these traditional Scale inhibitorss of anionic polymer dirt dispersion agent, for example U.S. Pat 4,711,725 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 polymkeric substance resistance silicon dispersion agent of traditional organic phosphine Scale inhibitors and anionic, and these organic phosphine Scale inhibitorss and anionic polymer dirt dispersion agent all are ionic compounds, for ionic crystal CaCO
3, CaSO
4, BaSO
4Be formed with very strong restraining effect, the Scale inhibitors of very low dose just can hinder the inorganic scale of hundred times even thousands of times.But for unformed silicon dirt, their effect is often limited, facts have proved that organic phosphine Scale inhibitors that these are traditional and anionic polymer dirt dispersion agent are for unformed SiO
2The sedimentary inhibition effect of dirt and bad (Eleftheria Neofotistou, Konstantinos D.Demadis.Use of antiscalants for mitigation of silica (SiO
2) fouling and deposition:fundamentals and applications in desalination systems[J] .Desalination, 2004,167 (8): 257-272.).The tradition Scale inhibitors will seek out and hinder the silicon effect preferably, must be under maximal dose (Euvrard, M., Hadi, L.and Foissy, A.Influence of PPCA (phosphinopolycarboxylicacid) and DETPMP (diethylenetriamine pentamethylene phosphosphonic acid) on silica fouling.[J] .Desalination, 2007,205:114-123.).Increased processing cost so on the one hand, these traditional organic phosphine Scale inhibitorss and the phosphorous or bio-refractory of anionic polymer Scale inhibitors in addition because environment protection, these contain the high density Scale inhibitors dense water by strict limiting emission in environment.
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.
Branch-shape polymer PAMAM more and more attracts much attention in the usefulness aspect the resistance silicon dirt in recent years, the research of Demadis.K.D (Demadis K.D., A structure/function study of polyaminoamide dendrimers as silicascale growth inhibitors.Journal of chemical technology and biotechnology, 2005, Vol.80:630～640) show: at a series of quadrols is (PAMAM-0.5G among the daiamid PAMAM of core, PAMAM-1.0G, PAMAM-1.5G, PAMAM-2.0G, PAMAM-2.5G), whole have the ability of good inhibition silicon dirt for PAMAM, and the ability of PAMAM-1.0G inhibition silicon dirt deposition is better than PAMAM2.0.But (Mavredaki E. is also found in research, Neofotistou E., Demadis K.D., Inhibition and Dissolution as DualMitigation Approaches for Colloidal Silica Fouling and Deposition in Process Water Systems:Functional Synergies.Ind.Eng.Chem.Res.2005, Vol.44 (17): 7019～7026) PAMAM-1.0G and PAMAM-2.0G are suppressing SiO
2In the time of dirt deposition, but can in solution, produce insoluble white flocks.The cotton-shaped sedimentary generation of this white will influence the practical application of PAMAM, because in Treatment of Industrial Water, any insoluble material all can bring out the deposition of inorganic salt crust (as lime carbonate, calcium phosphate, calcium sulfate etc.).
Summary of the invention
One of purpose of the present invention is to provide a kind of branch-shape polymer and poly (sodium aspartate) composite scale inhibitor that suppresses water silicon dirt deposition, to overcome existing organic phosphine Scale inhibitors and the anionic polymer dirt dispersion agent problem to the resistance silicon poor effect of silicon dioxide dirt.
Two of purpose of the present invention is to provide a kind of without phosphorus, biodegradable environmentally friendly resistivity silicon scale inhibitor that is used for stoping Treatment of Industrial Water silicon dirt deposition.
Three of purpose of the present invention is to provide a kind of and can be used with PAMAM, suppresses the composite resistivity silicon scale inhibitor of silicon dioxide dirt deposition in the water, produces the shortcoming of white flocks to overcome when PAMAM uses separately, improves the resistance silicon dirt performance of PAMAM simultaneously.Existing organic phosphine Scale inhibitors and anionic polymer dirt dispersion agent are to the problem of the resistance silicon poor effect of silicon dioxide dirt.
For achieving the above object, the environment-friendly type composite resistivity silicon scale inhibitor that the present invention proposes, form by branch-shape polymer daiamid (any one among PAMAM-0G, PAMAM-1G, the PAMAM-2G), poly (sodium aspartate) and water, in recombiner weight is 100%, and the weight percent of its component is:
Weight percentages of components wt%
Daiamid 25～30
Poly (sodium aspartate) 10～15
All the other are water, and its gross weight satisfies 100%.
Among the present invention, described branch-shape polymer daiamid (PAMAM) be with the amido be the 0-2 of end group for any one of (PAMAM-0G, PAMAM-1G, PAMANM-2G) in the product, molecular structural formula is as follows:
G0 is the daiamid 0 generation polymkeric substance (following represent with PAMAM-0G) of amido end;
G1 is the daiamid 1 generation polymkeric substance (following represent with PAMAM-1G) of amido end;
G2 is the daiamid 2 generation polymkeric substance (following represent with PAMAM-2G) of amido end.
Among the present invention, described poly (sodium aspartate) is commercially available liquid preparation, and solid content is 40%, and its molecular structural formula is:
Wherein, polymerization degree m, n are integer, and scope is 10～50.
The inventor finds when the rejection of silicon dirt is tested at research polymeric amide amine branch-shape polymer PAMAM-0G, PAMAM-1G, PAMAM-2G, though PAMAM-0G, PAMAM-1G, PAMAM-2G have good prevention effect to the deposition to the silicon dirt in the water, the PAMAM-0G performance is better than PAMAM-1G, PAMAM-2G.And document was not reported the research of the resistance silicon dirt performance of PAMAM-0G, had only the resistance silicon performance of PAMAM-1G to be better than report (Demadis, the K.D. of PAMAM-2G; Mavredaki, E.Green additives to enhance silicadissolution during water treatment.Env.Chem.Lett.2005,3,127.).Research finds that also PAMAM-0G and PAMAM-1G, PAMAM-2G also produce white cotton-shaped deposition equally when suppressing the silicon dirt deposition in addition.
The inventor also finds when using poly (sodium aspartate) (PASP) separately through research, to the not significant effect that suppresses of the silicon dirt deposition in the water, but when among itself and polymeric amide amine branch-shape polymer PAMAM-0G, PAMAM-1G, the PAMAM-2G any is used, both have significant collaborative resistance silicon effect, and poly (sodium aspartate) not only can improve the resistance silicon effect of daiamid.The cotton-shaped deposition that produces in the time of can also eliminating simultaneously independent use daiamid.
Though finding the daiamid (algebraically G 〉=3) of high algebraically, the inventor also has the effect that suppresses the silicon dirt deposition, but effect is not as the daiamid (algebraically G＜3) of low algebraically, the daiamid of high algebraically (algebraically G 〉=3) will reach the same effect of daiamid (algebraically G＜3) of low algebraically, need higher dosage, not good enough economically.Therefore the present invention uses the daiamid of low algebraically, and that best is PAMAM-0G.
Composite scale inhibitor proposed by the invention, form by any and poly (sodium aspartate) sodium among polymeric amide amine branch-shape polymer PAMAM-0G, PAMAM-1G, the PAMAM-2G, when composite, only daiamid, poly (sodium aspartate), deionized water join in the container successively in given ratio at normal temperatures, and stirring gets final product.
Composite resistivity silicon scale inhibitor provided by the invention has following advantage:
(1) daiamid of composite resistivity silicon scale inhibitor use provided by the invention is a kind of branch-shape polymer, has the performance that stops silicon dioxide dirt deposition in the water efficiently.
(2) composite resistivity silicon scale inhibitor provided by the invention, the daiamid base polymer of use be polymer P AMAM-0G, the PAMAM-1G of low algebraically, among the PAMAM-2G any.
(3) composite resistivity silicon scale inhibitor provided by the invention between the poly (sodium aspartate) and daiamid of use, has tangible resistance silicon synergistic effect, thereby has reduced medicament and used total concn.
(4) the white cotton-shaped deposition that composite resistivity silicon scale inhibitor provided by the invention, the poly (sodium aspartate) of use produced in the time of eliminating daiamid and use separately makes daiamid be able to practice.
When (5) composite scale inhibitor provided by the invention used, the total consumption of medicament is few, and was effective.
(6) composite scale inhibitor provided by the invention is without phosphorus, biodegradable environmentally friendly Scale inhibitors.
Embodiment
Further describe positively effect of the present invention below by a series of embodiment.
The performance test methods of the static state resistance silicon dioxide dirt in embodiment and the Comparative Examples is as follows: static resistance silicon dioxide dirt experimental technique: the 500mgL of preparation certain volume in Plastic Bottle
-1(with SiO
2Meter) sodium silicate solution adds a certain amount of Scale inhibitors; 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.
Medicament daiamid PAMAM-0G, PAMAM-1G, PAMAM-2G that embodiment and Comparative Examples are used derive from Sigma-Aldrich Chemical Co., and China is 20% methanol solution; The medicament poly (sodium aspartate) (PASP) that embodiment and Comparative Examples are used derives from Zibo Li Bang Fine Chemical Co., Ltd; Traditional organic phosphine Scale inhibitors that Comparative Examples is used and traditional polymer dirt dispersion agent derive from sea, river chemical industry company limited.
Embodiment 1: present embodiment is the composite scale inhibitor preparation of PAMAM-0G and PASP
Preparation process: being 20% PAMAM-0G methanol solution with the 150g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 30g of thick PAMAM-0G.Add the 25g solid content then and be 40% poly (sodium aspartate) (PASP) and 45g deionized water, stirring and promptly obtaining required solid content is 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-0G is 30%, and the effective concentration of poly (sodium aspartate) is 10%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 2: present embodiment is the composite scale inhibitor preparation of PAMAM-0G and PASP
Preparation process: being 20% PAMAM-0G methanol solution with the 137.5g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 27.5g of thick PAMAM-0G.Add the 31.25g solid content then and be 40% poly (sodium aspartate) (PASP) and 41.25g deionized water, stirring and promptly obtaining required solid content is 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-0G is 27.5%, and the effective concentration of poly (sodium aspartate) is 12.5%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 3: present embodiment is the composite scale inhibitor preparation of PAMAM-0G and PASP
Preparation process: being 20% PAMAM-0G methanol solution with the 125g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 25g of thick PAMAM-0G.Add the 37.5g solid content then and be 40% poly (sodium aspartate) (PASP) and 37.5g deionized water, stirring and promptly obtaining required solid content is 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-0G is 25%, and the effective concentration of poly (sodium aspartate) is 15%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 4; Present embodiment is the composite scale inhibitor preparation of PAMAM-1G and PASP
Preparation process: being 20% PAMAM-1G methanol solution with the 150g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 30g of thick PAMAM-1G.Add the 25g solid content then and be 40% poly (sodium aspartate) (PASP) and 45g deionized water, stirring and promptly obtaining required solid content is 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-1G is 30%, and the effective concentration of poly (sodium aspartate) is 10%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 5: present embodiment is the composite scale inhibitor preparation of PAMAM-1G and PASP
Preparation process: being 20% PAMAM-1G methanol solution with the 137.5g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 27.5g of thick PAMAM-1G.Add the 31.25g solid content then and be 40% poly (sodium aspartate) (PASP) and 41.25g deionized water, stir, promptly obtain required solid content and be 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-1G is 27.5%, and the effective concentration of poly (sodium aspartate) is 12.5%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 6: present embodiment is the composite scale inhibitor preparation of PAMAM-1G and PASP
Preparation process: being 20% PAMAM-1G methanol solution with the 125g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 25g of thick PAMAM-1G.Add the 37.5g solid content then and be 40% poly (sodium aspartate) (PASP) and 37.5g deionized water, stir, promptly obtain required solid content and be 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-1G is 25%, and the effective concentration of poly (sodium aspartate) is 15%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 7: present embodiment is the composite scale inhibitor preparation of PAMAM-2G and PASP
Preparation process: being 20% PAMAM-2G methanol solution with the 150g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 30g of thick PAMAM-2G.Add the 25g solid content then and be 40% poly (sodium aspartate) (PASP) and 45g deionized water, stir, promptly obtain required solid content and be 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-2G is 30%, and the effective concentration of poly (sodium aspartate) is 10%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 8: present embodiment is the composite scale inhibitor preparation of PAMAM-2G and PASP
Preparation process: being 20% PAMAM-2G methanol solution with the 137.5g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 27.5g of thick PAMAM-2G.Add the 31.25g solid content then and be 40% poly (sodium aspartate) (PASP) and 41.25g deionized water, stir, promptly obtain required solid content and be 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-2G is 27.5%, and the effective concentration of poly (sodium aspartate) is 12.5%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Embodiment 9: present embodiment is the composite scale inhibitor preparation of PAMAM-2G and PASP
Preparation process: being 20% PAMAM-2G methanol solution with the 125g effective content removes methyl alcohol with the evaporation under less than 50 ℃ condition of rotary evaporation in vacuo instrument, obtains the about 25g of thick PAMAM-2G.Add the 37.5g solid content then and be 40% poly (sodium aspartate) (PASP) and 37.5g deionized water, stirring and promptly obtaining required solid content is 40% composite resistivity silicon scale inhibitor 100.00g.In the prepared composite resistivity silicon scale inhibitor, the effective concentration of PAMAM-2G is 25%, and the effective concentration of poly (sodium aspartate) is 15%.
The above-mentioned composite scale inhibitor for preparing is carried out the performance test experiment of static resistance silicon dioxide dirt, and the solution clear after the experiment does not have white cotton-shaped deposition, and its soluble silica content sees Table 2.
Comparative Examples 1～3: Comparative Examples 1 is to use the resistance silicon effect of branch-shape polymer PAMAM-0G separately; Comparative Examples 2 is to use the resistance silicon effect of branch-shape polymer PAMAM-0G separately; Comparative Examples 3 is to use the resistance silicon effect of branch-shape polymer PAMAM-0G separately, the cotton-shaped deposition of solution adularescent after the experiment, and its soluble silica content sees Table 2.
Comparative Examples 4～5: Comparative Examples 4～5 is the resistance silicon effect when using poly (sodium aspartate) (PASP) separately, and experimental result sees Table 2.
Comparative Examples 6～9: Comparative Examples 6～7 is the resistance silicon effect when using commercially available organic phosphine Scale inhibitors 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) separately; Comparative Examples 8～9 is to use commercially available organic phosphine corrosion inhibiting and descaling agent 2-phosphonic acids butane-1,2 separately, the resistance silicon effect during 4-tricarboxylic acid (PBTCA), and experimental result sees Table 2.
Comparative Examples 10～13: the resistance silicon effect when Comparative Examples 10～11 is used commercially available polymeric scale inhibitor dispersion agent polyacrylic acid (PAA) separately; Comparative Examples 12～13 be commercially available polymeric scale inhibitor dispersion agent vinylformic acid/2-methyl-2 '-resistance silicon effect during acrylamido propane sulfonic acid copolymer (AA/AMPS), experimental result sees Table 2.
Blank example: the experimental result of the blank solution of blank example when not adding any medicament, experimental result sees Table 2.
Table 2SiO
2Stability experiment
The experimental result of table 2 shows: the composite scale inhibitor of branch-shape polymer provided by the present invention and poly aspartic acid has the effect of good resistance silicon dioxide dirt deposition, can overcome independent use branch-shape polymer simultaneously and produce the cotton-shaped sedimentary phenomenon of white.Experimental result shows that also traditional organic phosphine and polymer antisludging agent then do not suppress the effect of silicon dirt deposition.
Claims (4)
1. a branch-shape polymer and poly (sodium aspartate) composite scale inhibitor that suppresses silicon dirt deposition in the water is characterized in that described composite scale inhibitor is made up of branch-shape polymer, poly (sodium aspartate) and water, and the weight percent of its component is:
Weight percentages of components wt%
Branch-shape polymer 25～30
Poly (sodium aspartate) 10～15
All the other are water, and its gross weight satisfies 100%.
2. composite scale inhibitor according to claim 1 is characterized in that described branch-shape polymer is the polyamide-amide branch-shape polymer based on quadrol nuclear core.
3. composite scale inhibitor according to claim 1 and 2 is characterized in that described branch-shape polymer is any one in the polymkeric substance in 0～2 generation in the polyamide-amide, has following structural formula:
Wherein:
G0 is the daiamid 0 generation polymkeric substance of amido end;
G1 is the daiamid 1 generation polymkeric substance of amido end;
G2 is the daiamid 2 generation polymkeric substance of amido end.
4. composite scale inhibitor according to claim 1 is characterized in that described poly (sodium aspartate) has following structural formula:
Wherein: polymerization degree m, n are integer, and scope is 10～50.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167451A (en) * | 2011-03-25 | 2011-08-31 | 上海美净环保材料有限公司 | Composite multiple dirt dispersion agent for oilfield flooding treatment and preparation method thereof |
| CN103214107A (en) * | 2013-04-10 | 2013-07-24 | 同济大学 | Silicate and polyamidoamine composite and environment-friendly corrosion inhibitor applied to deionized water circulating cooling system |
| CN109133389A (en) * | 2018-10-12 | 2019-01-04 | 山东理工大学 | Non-phosphorus composite scale inhibitor |
| CN109126474A (en) * | 2018-10-12 | 2019-01-04 | 山东理工大学 | Compound without phosphorus reverse osmosis antisludging agent |
| CN110183667A (en) * | 2019-06-24 | 2019-08-30 | 南京大学 | A kind of preparation method and applications of the without phosphorus broom shaped polymer of silica gel load |
| CN111377550A (en) * | 2020-04-23 | 2020-07-07 | 西安热工研究院有限公司 | Scale and corrosion inhibitor for ultra-high temperature heat supply network system |
| CN115044379A (en) * | 2022-06-07 | 2022-09-13 | 北京十玉农业科技有限公司 | Heavy metal contaminated soil remediation agent based on graphene oxide and application thereof |
| CN115044379B (en) * | 2022-06-07 | 2024-06-04 | 北京十玉农业科技有限公司 | Heavy metal contaminated soil restoration agent based on graphene oxide and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167451A (en) * | 2011-03-25 | 2011-08-31 | 上海美净环保材料有限公司 | Composite multiple dirt dispersion agent for oilfield flooding treatment and preparation method thereof |
| CN103214107A (en) * | 2013-04-10 | 2013-07-24 | 同济大学 | Silicate and polyamidoamine composite and environment-friendly corrosion inhibitor applied to deionized water circulating cooling system |
| CN109133389A (en) * | 2018-10-12 | 2019-01-04 | 山东理工大学 | Non-phosphorus composite scale inhibitor |
| CN109126474A (en) * | 2018-10-12 | 2019-01-04 | 山东理工大学 | Compound without phosphorus reverse osmosis antisludging agent |
| CN109126474B (en) * | 2018-10-12 | 2020-12-15 | 山东理工大学 | Composite non-phosphorus reverse osmosis scale inhibitor |
| CN110183667A (en) * | 2019-06-24 | 2019-08-30 | 南京大学 | A kind of preparation method and applications of the without phosphorus broom shaped polymer of silica gel load |
| CN110183667B (en) * | 2019-06-24 | 2021-07-16 | 南京大学 | Preparation method and application of silica gel loaded phosphorus-free broom-like polymer |
| CN111377550A (en) * | 2020-04-23 | 2020-07-07 | 西安热工研究院有限公司 | Scale and corrosion inhibitor for ultra-high temperature heat supply network system |
| CN115044379A (en) * | 2022-06-07 | 2022-09-13 | 北京十玉农业科技有限公司 | Heavy metal contaminated soil remediation agent based on graphene oxide and application thereof |
| CN115044379B (en) * | 2022-06-07 | 2024-06-04 | 北京十玉农业科技有限公司 | Heavy metal contaminated soil restoration agent based on graphene oxide and application thereof |
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