CN104030461A - Scale inhibitor used for inhibiting formation of calcium sulfate scale and preparation method thereof - Google Patents
Scale inhibitor used for inhibiting formation of calcium sulfate scale and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a scale inhibitor used for inhibiting formation of calcium sulfate scale and a preparation method thereof. The scale inhibitor used for inhibiting formation of calcium sulfate scale is poly(citric acid), poly(citric acid-glycol) ester, poly(citric acid-propylene glycol) ester, poly(citric acid-glycerol) ester or poly(citric acid-triethanolamine) ester prepared by subjecting a raw material selected from the group consisting of citric acid, a mixture of citric acid and glycol, a mixture of citric acid and propylene glycol, a mixture of citric acid and glycerol and a mixture of citric acid and triethanolamine to condensation polymerization. The scale inhibitor is used as a scale inhibitor for calcium sulfate scale in a water system containing calcium ions and sulfate ions, and when the application amount of the scale inhibitor is 15 g/mL, the scale inhibition rate of the scale inhibitor reaches 94.5 to 97.5%; and the scale inhibitor has the characteristics of environment-friendliness, no pollution, etc.
Description
Technical field
The invention belongs to Treatment of Industrial Water technical field, be specifically related to a kind of for restraining Scale inhibitors of calcium sulfate scale formation and preparation method thereof.
Background technology
In Treatment of Industrial Water, scale problems has been subject to extensive concern.Directly increase production energy consumption because incrustation scale thermal conductivity is low, reduced economic benefit; In addition, incrustation scale also can cause the problems such as equipment corrosion, and this will greatly endanger the safe operation of equipment.Current, in various industrial raw water, often contain Ca2+, SO42-plasma, still can constantly accumulate and form the CaSO4 that is slightly soluble in water though treated, be deposited on equipment or pipe surface becomes hard scale, this,, by significantly reducing the working efficiency of equipment, even endangers production safety.
Adopt Scale inhibitors can effectively reduce scale formation.Scale inhibitors can effectively suppress separating out of incrustation ion in water, the incrustation scale of formation is scattered in water simultaneously, prevents the formation of equipment surface hard scale.Common Scale inhibitors is mainly divided into small molecules organo phosphorous compounds and macromole organic polymer.Small molecules organo phosphorous compounds low price, scale inhibition effect is good, but environment is had to stronger destruction.Common small molecules Scale inhibitors has Amino Trimethylene Phosphonic Acid (ATMP), diethylenetriamine pentamethylene phosphonic acids (DETPMP), hexanediamine tetramethylene phosphonic acid (HDTMP), hydroxy ethylene diphosphonic acid (HEDP), 2-phosphate-1,2,4-butane tricarboxylate (PBTCA) etc.Common Polymers Scale inhibitors has polyacrylic acid (PAA), poly aspartic acid (PASP), poly-epoxy succinic acid (PESA), polymaleic acid (HPMA) etc.The scale inhibition effect of these polymkeric substance is better, has certain environment friendly, but price is relatively high.Thereby the excellent eco-friendly Novel scale inhibitor of exploitation scale-inhibiting properties is necessary.The patented mandates of Novel scale inhibitor such as the at present existing dendritic polyethers dirt dispersion agent of environment-friendly type (CN102674567 B), maleic anhydride series Scale inhibitors (CN100503476C), but the cost of this class Scale inhibitors is higher.
Degradable polymer Scale inhibitors is as more in poly aspartic acid is applied to Scale inhibitors.In this polymer molecular structure, there is the groups such as a large amount of carboxyls and amido, calcium ion is had to stronger sequestering action.In addition, the people such as Wu Hua studies have shown that poly-(citric acid-1,3-PD) ester has good degradation characteristic.Accordingly, the present invention has developed the poly-citric acid and the derivative thereof that contain the groups such as a large amount of carboxyls, and by gathering citric acid and derivative thereof the Scale inhibitors as calcium sulfate scale, experimental results show that this polymkeric substance has excellent scale-inhibiting properties to calcium sulfate scale.There is no report for poly-citric acid and derivative thereof as the Scale inhibitors that suppresses calcium sulfate scale generation at present.
Summary of the invention
One of object of the present invention is to provide a kind of Scale inhibitors forming for restraining calcium sulfate scale of environmental friendliness Cheap highly effective.
It is above-mentioned a kind of for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms that two of object of the present invention is to provide.
Technical scheme of the present invention
A kind of Scale inhibitors forming for restraining calcium sulfate scale, taking the mixture of the mixture of the mixture of citric acid, citric acid and ethylene glycol composition, citric acid and propylene glycol composition, citric acid and glycerol composition or citric acid with the mixture of trolamine composition as raw material reacts by condensation polymerization, poly-citric acid, poly-(citric acid-ethylene glycol) ester of obtaining, gather (citric acid-propylene glycol) ester, gather (citric acid-glycerol) ester or gather (citric acid-trolamine) ester;
In the mixture of wherein said citric acid and ethylene glycol composition, citric acid and ethylene glycol calculate in molar ratio, i.e. ethylene glycol: citric acid is 1-1.1:1, is preferably 1.1:1;
In the mixture of citric acid and propylene glycol composition, citric acid and propylene glycol calculate in molar ratio, i.e. propylene glycol: citric acid is 1-1.1:1, is preferably 1.1:1;
In the mixture of citric acid and glycerol composition, citric acid and glycerol are calculated in molar ratio, i.e. glycerol: citric acid is 1-1.1:1, is preferably 1.1:1;
In the mixture of citric acid and trolamine composition, citric acid and trolamine calculate in molar ratio, i.e. trolamine: citric acid is 1-1.1:1, is preferably 1.1:1.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, first add solvent, then add the mixture of citric acid or the first monomer citric acid and the second monomer composition, stir and obtain solution;
Described solvent is tetrahydrofuran (THF), and its consumption is that 20-200g/L calculates by the concentration of final formed citric acid;
The second described monomer is ethylene glycol, propylene glycol, glycerol or trolamine, and its consumption calculates in molar ratio, i.e. the second monomer: the first monomer citric acid is 1-1.1:1;
(2), to control drop rate be that 0.05-0.5mL/min joins catalyzer in the solution of step (1) gained, be uniformly mixed post-heating to reflux state and carry out condensation polymerization reaction 4-24h;
Described catalyzer is the vitriol oil or the mixture that is made up of sulfur oxychloride and pyridine, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 1-4:1;
The described mixture being made up of sulfur oxychloride and pyridine, calculates by volume, preferably sulfur oxychloride: pyridine is 1:1;
(3), in above-mentioned steps (2):
When taking the vitriol oil as catalyzer, after step (2) back flow reaction finishes, it is neutral that gained reaction solution is regulated to pH with the aqueous sodium hydroxide solution of 5mol/L, control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, upper strata is tetrahydrofuran (THF) phase, the lower floor of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the Scale inhibitors forming for restraining calcium sulfate scale.
When taking sulfur oxychloride or pyridine as catalyzer, after step (2) back flow reaction finishes, be 20-30 DEG C by gained reaction solution control temperature, add sodium sulfate solid to form saturated aqueous sodium sulfate, be then transferred to separating funnel and carry out separatory, upper strata is tetrahydrofuran (THF) phase, the lower floor of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the Scale inhibitors forming for restraining calcium sulfate scale;
The aqueous systems that can be used for calcium ions and sulfate ion for restraining the Scale inhibitors of calcium sulfate scale formation of above-mentioned gained is used as the Scale inhibitors of calcium sulfate scale, and in the time that its consumption is 15g/mL, its scale inhibition performance can reach 94.5-97.5%.
Beneficial effect of the present invention
Of the present invention a kind of for restrain calcium sulfate scale form Scale inhibitors belong to Green Water treatment agent.Because the mixture that adopts citric acid, citric acid and ethylene glycol, propylene glycol, glycerol or trolamine composition is raw material, this raw material is cheap and easy to get, degradable, nontoxic, therefore the Scale inhibitors environmental protection forming for restraining calcium sulfate scale of final gained, when the aqueous systems of calcium ions and sulfate ion is used as the Scale inhibitors of calcium sulfate scale, there is environmental protection, the characteristic such as pollution-free.
Further, of the present invention a kind of for restrain calcium sulfate scale form Scale inhibitors the formation of calcium sulfate scale is had to obvious restraining effect.In the time that its consumption is 15g/mL, its scale inhibition performance can reach 94.5-97.5%.
Brief description of the drawings
Fig. 1, the scale inhibition performance situation of different poly-citric acid concentration to calcium sulfate scale.
Embodiment
Also by reference to the accompanying drawings the present invention is further set forth below by specific embodiment, but do not limit the present invention.
Gained of the present invention as follows for restraining the scale-inhibiting properties testing method of Scale inhibitors that calcium sulfate scale forms:
Preparation contains Ca2+ and SO42-concentration is the test water sample of 2040 mg/ L.
Taking above-mentioned test water sample as solvent, preparation is respectively the solution of 0 mg/ L, 0.1 mg/ L, 0.5 mg/ L, 1 mg/ L, 2 mg/ L, 3 mg/ L, 5 mg/ L, 10 mg/ L, 15 mg/ L, 20 mg/ L, 25 mg/ L containing the concentration that is useful on the Scale inhibitors of restraining calcium sulfate scale formation;
Above solution is placed in respectively after 10h is heated in 80 DEG C of waters bath with thermostatic control and is taken out, be cooled to after room temperature, filter, get the Erlenmeyer flask that filtrate 25.00mL is placed in 250mL, after thin up, add calconcarboxylic acid, with the titration of disodium ethylene diamine tetraacetate (EDTA) standardized solution.Scale inhibition performance is calculated as follows:
Scale inhibition performance=(V2-V0)/(V1-V0) × 100%
In formula:
V2---in water sample, add after Scale inhibitors heating the volume of the EDTA solution that volumetric soiutions consumes, mL;
V0---in water sample, do not add after Scale inhibitors heating the volume of the EDTA solution that volumetric soiutions consumes, mL;
The volume of the EDTA solution that V1---the former water sample of titration (not adding Scale inhibitors does not heat) consumes, mL.
Embodiment 1
The Scale inhibitors forming for restraining calcium sulfate scale, reacts the poly-citric acid obtaining by condensation polymerization taking citric acid as raw material.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, add 20 mL solvents, 4.0g citric acid, obtains solution after being uniformly mixed;
Described solvent is tetrahydrofuran (THF), and its consumption is that 200g/L calculates by the concentration of final formed citric acid;
(2), to control drop rate be that 0.05mL/min joins 2.2mL catalyzer in the solution of step (1) gained, be uniformly mixed post-heating to reflux state and carry out condensation polymerization reaction 4h;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 1:1;
(3) it is neutral, the reaction solution of gained in step (2) being regulated to pH with the aqueous sodium hydroxide solution of 5mol/L, control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, upper strata is tetrahydrofuran (THF) phase, the lower floor of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the poly-citric acid of Vandyke brown dope product, be the Scale inhibitors forming for restraining calcium sulfate scale.
Measure the i.e. scale inhibition performance of poly-citric acid to calcium sulfate scale of Scale inhibitors for preventing that calcium sulfate scale from forming of above-mentioned gained, test result as shown in Figure 1, as can be seen from Figure 1 scale inhibition performance increases with the concentration that uses poly-citric acid, and in the time that the concentration of poly-citric acid is 2mg/L, scale inhibition performance reaches 90% left and right, when poly-citric acid concentration is 15mg/L, scale inhibition performance is 97.5%.Visible, poly-citric acid is a kind of Scale inhibitors of extraordinary calcium sulfate scale.
Embodiment 2
The Scale inhibitors forming for restraining calcium sulfate scale, reacts the poly-citric acid obtaining by condensation polymerization taking citric acid as raw material.
The above-mentioned Scale inhibitors forming for restraining calcium sulfate scale, the preparation method of poly-citric acid, specifically comprises the steps:
(1), in reactor, add 90mL solvent, 1.8g citric acid, obtains solution after being uniformly mixed;
Described solvent is tetrahydrofuran (THF), and its consumption is that 20g/L calculates by the concentration of final formed citric acid;
(2), to control drop rate be that 0.5mL/min joins 3.9mL catalyzer in the solution of step (1) gained, be uniformly mixed post-heating to reflux state and carry out condensation polymerization reaction 24h and obtain reaction solution;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 4:1;
(3) it is neutral, the reaction solution of gained in step (2) being regulated to pH with the aqueous sodium hydroxide solution of 5mol/L, control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, upper strata is tetrahydrofuran (THF) phase, the lower floor of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the poly-citric acid of Vandyke brown dope product, be the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. scale inhibition performance of poly-citric acid to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 95.6%.
Embodiment 3
The Scale inhibitors forming for restraining calcium sulfate scale, reacts the poly-citric acid obtaining by condensation polymerization taking citric acid as raw material.
The above-mentioned Scale inhibitors forming for restraining calcium sulfate scale, the preparation method of poly-citric acid, specifically comprises the steps:
(1), in reactor, add 40 mL solvents, 4.0g citric acid, obtains solution after being uniformly mixed;
Described solvent is tetrahydrofuran (THF), and its consumption is that 100g/L calculates by the concentration of final formed citric acid;
(2), to control drop rate be that 0.25mL/min joins 4.5mL catalyzer in the solution of step (1) gained, is uniformly mixed post-heating to reflux state and carries out condensation polymerization reaction 12h, obtains reaction solution;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 2:1;
(3), regulate pH to neutrality with the aqueous sodium hydroxide solution of 5mol/L the reaction solution of gained in step (2), control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, the upper solution of gained is tetrahydrofuran (THF) phase, lower floor's solution of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the poly-citric acid of Vandyke brown dope product, be the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. scale inhibition performance of poly-citric acid to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 96.7%.
Embodiment 4
The Scale inhibitors forming for restraining calcium sulfate scale, reacts the poly-citric acid obtaining by condensation polymerization taking citric acid as raw material.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, add 12mL solvent, 2.4g citric acid, obtains solution after being uniformly mixed;
Described solvent is tetrahydrofuran (THF), and its consumption is that 200g/L calculates by the concentration of final formed citric acid;
(2), to control drop rate be that 0.05mL/min joins 8mL catalyzer in the solution of step (1) gained, is uniformly mixed post-heating to reflux state and carries out condensation polymerization reaction 24h, obtains reaction solution;
Described catalyzer is the mixture being made up of for 1:1 by volume sulfur oxychloride and pyridine, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 4:1;
(3) be, 20-30 DEG C by the reaction solution control temperature of step (2) gained, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, the upper solution of gained is tetrahydrofuran (THF) phase, lower floor's solution of gained is aqueous sodium persulfate solution, discards lower floor's aqueous sodium persulfate solution, takes out upper strata tetrahydrofuran (THF) and revolves mutually steaming to remove tetrahydrofuran (THF), obtain the poly-citric acid of Vandyke brown dope product, the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. scale inhibition performance of poly-citric acid to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 95%.
Embodiment 5
The Scale inhibitors forming for restraining calcium sulfate scale, taking the mixture of citric acid and glycerol composition as raw material reacts by condensation polymerization, what obtain gathers (citric acid-glycerol) ester.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, first add 20mL solvent, then add the mixture of 3.0g the first monomer citric acid and 1.2 mL the second monomer compositions, stir and obtain solution;
Described solvent is tetrahydrofuran (THF), and its consumption is that 150g/L calculates by the concentration of final formed citric acid;
The second described monomer is glycerol, and its consumption calculates in molar ratio, i.e. the second monomer glycerol: the first monomer citric acid is 1.1:1;
(2), to control drop rate be that 0.05mL/min joins 4.0mL catalyzer in the solution of step (1) gained, is uniformly mixed post-heating to reflux state and carries out condensation polymerization reaction 24h, obtains reaction solution;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 2.5:1;
(3), regulate pH to neutrality with the aqueous sodium hydroxide solution of 5mol/L the reaction solution of gained in step (2), control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, the upper solution of gained is tetrahydrofuran (THF) phase, lower floor's solution of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain poly-(citric acid-glycerol) ester of Vandyke brown dope product, the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. poly-scale inhibition performance of (citric acid-glycerol) ester to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 96.5%.
Embodiment 6
The Scale inhibitors forming for restraining calcium sulfate scale, taking the mixture of citric acid and trolamine composition as raw material reacts by condensation polymerization, what obtain gathers (citric acid-trolamine) ester.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, add 20mL solvent, the mixture of 4g the first monomer citric acid and 3mL the second monomer composition, stirs and obtains solution;
Described solvent is tetrahydrofuran (THF), and its consumption is that 200g/L calculates by the concentration of final formed citric acid;
The second described monomer is trolamine, and its consumption calculates in molar ratio, i.e. the second monomer trolamine: the first monomer citric acid is 1.1:1;
(2), to control drop rate be that 0.05mL/min joins 6.0mL catalyzer in the solution of step (1) gained, be uniformly mixed post-heating to reflux state and carry out condensation polymerization reaction 24h;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 2.75:1;
(3), regulate pH to neutrality with the aqueous sodium hydroxide solution of 5mol/L the reaction solution of gained in step (2), control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, the upper solution of gained is tetrahydrofuran (THF) phase, lower floor's solution of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain poly-(citric acid-trolamine) ester of Vandyke brown dope product, the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. poly-scale inhibition performance of (citric acid-trolamine) ester to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 94.5%.
Embodiment 7
The Scale inhibitors forming for restraining calcium sulfate scale, taking the mixture of citric acid and propylene glycol composition as raw material reacts by condensation polymerization, what obtain gathers (citric acid-propylene glycol) ester.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, add 20mL solvent, the first monomer citric acid of 3.0g and the mixture of 1.3mL the second monomer composition, stir and obtain solution;
Described solvent is tetrahydrofuran (THF), and its consumption is that 150g/L calculates by the concentration of final formed citric acid;
The second described monomer is propylene glycol, and its consumption calculates in molar ratio, i.e. the second monomer propylene glycol: the first monomer citric acid is 1.1:1;
(2), to control drop rate be that 0.05mL/min joins 4.0mL catalyzer in the solution of step (1) gained, is uniformly mixed post-heating to reflux state and carries out condensation polymerization reaction 24h, obtains reaction solution;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 2.5:1;
(3), regulate pH to neutrality with the aqueous sodium hydroxide solution of 5mol/L the reaction solution of gained in step (2), control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, the upper solution of gained is tetrahydrofuran (THF) phase, lower floor's solution of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain poly-(citric acid-propylene glycol) ester of Vandyke brown dope product, the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. poly-scale inhibition performance of (citric acid-propylene glycol) ester to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 95.5%.
Embodiment 8
The Scale inhibitors forming for restraining calcium sulfate scale, taking the mixture of citric acid and ethylene glycol composition as raw material reacts by condensation polymerization, what obtain gathers (citric acid-ethylene glycol) ester.
Above-mentioned for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, specifically comprise the steps:
(1), in reactor, add 20mL solvent, the mixture of 3.0g the first monomer citric acid and 0.95mL the second monomer composition, stirs and obtains solution;
Described solvent is tetrahydrofuran (THF), and its consumption is that 150g/L calculates by the concentration of final formed citric acid;
The second described monomer is ethylene glycol, and its consumption calculates in molar ratio, i.e. the second monomer ethylene glycol: the first monomer citric acid is 1.1:1;
(2), to control drop rate be that 0.05mL/min joins 4.0mL catalyzer in the solution of step (1) gained, is uniformly mixed post-heating to reflux state and carries out condensation polymerization reaction 24h, obtains reaction solution;
Described catalyzer is the vitriol oil, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 2.5:1;
(3), regulate pH to neutrality with the aqueous sodium hydroxide solution of 5mol/L the reaction solution of gained in step (2), control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, the upper solution of gained is tetrahydrofuran (THF) phase, lower floor's solution of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain poly-(citric acid-ethylene glycol) ester of Vandyke brown dope product, the Scale inhibitors forming for restraining calcium sulfate scale.
The i.e. poly-scale inhibition performance of (citric acid-ethylene glycol) ester to calcium sulfate scale of Scale inhibitors forming for restraining calcium sulfate scale of measuring above-mentioned gained, in the time that its consumption is 15mg/L, its scale inhibition performance to calcium sulfate scale reaches 97.0%.
In sum, a kind of Scale inhibitors forming for suppressing calcium sulfate scale of the present invention, i.e. poly-citric acid, poly-(citric acid-ethylene glycol) ester, poly-(citric acid-propylene glycol) ester, poly-(citric acid-glycerol) ester, poly-(citric acid-trolamine) ester.More than poly-citric acid, poly-(citric acid-ethylene glycol) ester, poly-(citric acid-propylene glycol) ester, poly-(citric acid-glycerol) ester, poly-(citric acid-trolamine) ester form and have obvious restraining effect calcium sulfate scale in water, are the Scale inhibitorss that a kind of effective inhibition calcium sulfate scale forms.
Foregoing is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (8)
1. the Scale inhibitors forming for restraining calcium sulfate scale, it is characterized in that the described Scale inhibitors forming for restraining calcium sulfate scale, taking the mixture of the mixture of the mixture of citric acid, citric acid and ethylene glycol composition, citric acid and propylene glycol composition, citric acid and glycerol composition or citric acid with the mixture of trolamine composition as raw material reacts by condensation polymerization, poly-citric acid, poly-(citric acid-ethylene glycol) ester of obtaining, gather (citric acid-propylene glycol) ester, gather (citric acid-glycerol) ester or gather (citric acid-trolamine) ester;
In the mixture of wherein said citric acid and ethylene glycol composition, citric acid and ethylene glycol calculate in molar ratio, i.e. ethylene glycol: citric acid is 1-1.1:1;
In the mixture of citric acid and propylene glycol composition, citric acid and propylene glycol calculate in molar ratio, i.e. propylene glycol: citric acid is 1-1.1:1;
In the mixture of citric acid and glycerol composition, citric acid and glycerol are calculated in molar ratio, i.e. glycerol: citric acid is 1-1.1:1;
In the mixture of citric acid and trolamine composition, citric acid and trolamine calculate in molar ratio, i.e. trolamine: citric acid is 1-1.1:1.
2. the Scale inhibitors forming for restraining calcium sulfate scale as claimed in claim 1, is characterized in that in the mixture of described citric acid and ethylene glycol composition, citric acid and ethylene glycol calculate in molar ratio, i.e. ethylene glycol: citric acid is 1.1:1.
3. the Scale inhibitors forming for restraining calcium sulfate scale as claimed in claim 1, is characterized in that in the mixture of described citric acid and propylene glycol composition, citric acid and propylene glycol calculate in molar ratio, i.e. propylene glycol: citric acid is 1.1:1.
4. the Scale inhibitors forming for restraining calcium sulfate scale as claimed in claim 1, is characterized in that in the mixture of described citric acid and glycerol composition, citric acid and glycerol are calculated in molar ratio, i.e. glycerol: citric acid is 1.1:1.
5. the Scale inhibitors forming for restraining calcium sulfate scale as claimed in claim 1, is characterized in that in the mixture of described citric acid and trolamine composition, citric acid and trolamine calculate in molar ratio, i.e. trolamine: citric acid is 1.1:1.
6. as described in as arbitrary in claim 1-5 for restraining the preparation method of the Scale inhibitors that calcium sulfate scale forms, it is characterized in that specifically comprising the steps:
(1), in reactor, first add solvent, then add citric acid or the mixture by the first monomer citric acid and the second monomer composition, stir and obtain solution;
Described solvent is tetrahydrofuran (THF), and its consumption is that 20-200g/L calculates by the concentration of final formed citric acid;
The second described monomer is ethylene glycol, propylene glycol, glycerol or trolamine, and its consumption calculates in molar ratio, i.e. the second monomer ethylene glycol, propylene glycol, glycerol or trolamine: the first monomer citric acid is 1-1.1:1;
(2), to control drop rate be that 0.05-0.5mL/min joins catalyzer in the solution of step (1) gained, be uniformly mixed post-heating to reflux state and carry out condensation polymerization reaction 4-24h;
Described catalyzer is the vitriol oil or the mixture that is made up of sulfur oxychloride and pyridine, and its consumption calculates in mass ratio, i.e. catalyzer: citric acid is 1-4:1;
(3), in above-mentioned steps (2):
When taking the vitriol oil as catalyzer, after step (2) back flow reaction finishes, it is neutral that gained reaction solution is regulated to pH with the aqueous sodium hydroxide solution of 5mol/L, control temperature is 20-30 DEG C, add sodium sulfate solid to form saturated aqueous sodium sulfate, then be transferred to separating funnel and carry out separatory, upper strata is tetrahydrofuran (THF) phase, the lower floor of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the Scale inhibitors forming for restraining calcium sulfate scale;
When the mixture taking sulfur oxychloride and pyridine composition is as catalyzer, after step (2) back flow reaction finishes, be 20-30 DEG C by gained reaction solution control temperature, add sodium sulfate solid to form saturated aqueous sodium sulfate, be then transferred to separating funnel and carry out separatory, upper strata is tetrahydrofuran (THF) phase, the lower floor of gained is aqueous sodium persulfate solution, discard lower floor's aqueous sodium persulfate solution, take out upper strata tetrahydrofuran (THF) and revolve mutually steaming to remove tetrahydrofuran (THF), obtain the Scale inhibitors forming for restraining calcium sulfate scale.
7. the preparation method of Scale inhibitors who forms for restraining calcium sulfate scale as claimed in claim 6, is characterized in that mixture be made up of sulfur oxychloride and pyridine described in step (2), calculating by volume, i.e. sulfur oxychloride: pyridine is 1:1.
8. using as the Scale inhibitors of calcium sulfate scale for the aqueous systems of calcium ions and sulfate ion for restraining the Scale inhibitors that calcium sulfate scale forms as described in as arbitrary in claim 1-5.
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