CN103804562A - Non-phosphorus copolymer antiscale dispersant and preparation method thereof - Google Patents
Non-phosphorus copolymer antiscale dispersant and preparation method thereof Download PDFInfo
- Publication number
- CN103804562A CN103804562A CN201210460375.7A CN201210460375A CN103804562A CN 103804562 A CN103804562 A CN 103804562A CN 201210460375 A CN201210460375 A CN 201210460375A CN 103804562 A CN103804562 A CN 103804562A
- Authority
- CN
- China
- Prior art keywords
- acid
- reagent
- virahol
- preparation
- dissolved
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to a non-phosphorus copolymer antiscale dispersant which is prepared by carrying out one-step polymerization on 5-15% of C16-C24 unsaturated fatty acid and 85-95% of C3-C8 unsaturated carboxylic acid in an organic solvent under the initiation action of inorganic peroxide. The invention also discloses a preparation method of the copolymer antiscale dispersant. The molecular structure of the copolymer antiscale dispersant contains carboxyl groups and long carbon chains; and thus, the copolymer antiscale dispersant has certain surface activity and stripping property on the premise of having favorable calcium carbonate scale inhibition property and dispersibility, and especially has better antiscale effect than common antiscale dispersants in a water body with higher oil content. The copolymer antiscale dispersant has the advantages of simple preparation method, low cost, low consumption and favorable antiscale and dispersion effects, is free of phosphorus, is green and environment-friendly, can be widely used in an industrial circulating cooling water system, and has higher economic benefit and social benefit.
Description
Technical field
The present invention relates to circulating cooling water treatment field, more specifically relate to a kind of without phosphorus copolymer anti-scale disperser and preparation method thereof.
Background technology
Along with the sharply increase of industrial mass-producing and population, water resources is seriously deficient.Circulating cooling water consumption accounts for 60 ~ 70% of process water, rationally saves recirculated cooling water and be the direct way of reduction industrial water consumption.The main method of saving recirculated cooling water is to improve the cyclic utilization rate of recirculated cooling water, both strengthened cycles of concentration, but this can bring serious corrosion and scale problems to circulating water system again, and water technology is had higher requirement.In order to guarantee circulating water system normally operation under the conditions such as high rigidity, high Cl-concentration, high organic concentration, it is very crucial that water treatment agent seems.
Dirt dispersion agent is common circulating water treatment water quality stabilizer, especially polycarboxylic acid salt's dirt dispersion agent, it can make to cause dirty salt in water and on metallic surface, not deposit, and can stop again particulate matter in water to assemble sedimentation simultaneously, and maintain its suspended state, play the double effects of scale inhibition, dispersion.
Both at home and abroad about the patent of polycarboxylic acid salt's dirt dispersion agent is a lot, as CN01123146 " lower molecular weight (methyl) vinylformic acid (salt) based polymer and its production and use ", CN94194415.8 " copolymers of unsaturated carboxylic acids and its preparation method and application " etc., but along with continually developing of industrial circulating cooling water treatment process, complicacy and the polytropy of circulating water system situation are deepened gradually, and the adaptability of water treatment agent is had higher requirement.Especially the frequent generation of material from leakage, make oily substance enter into recirculated water, the indexs such as the COD of recirculated water, turbidity, oil-contg, suspended substance are higher, the effectiveness that conventional corrosion inhibiting and descaling agent is difficult to bring into normal play, can only strengthen the consumption of corrosion inhibiting and descaling agent, or blowdown is replaced continually, greatly increase the expense of circulating water treatment, also increase the weight of the complicated property of circulating water treatment.In addition, the dirt dispersion agent majority of having published and apply is phosphorous, and this type of dirt dispersion agent enters into bacterium and the algae that circulating water system can be water abundant nutrition is provided, and is easily decomposed, and can strengthen the difficulty of circulating water system sterilization algae removal, affect circulating water system steady running.
Summary of the invention
In order to address the above problem, the invention provides a kind of copolymer anti-scale disperser, it is without phosphorus copolymer anti-scale disperser, there is good resistance calcium carbonate scale performance, dispersing property, surfactivity and stripping performance, especially in the circulating water system that exists oily substance to leak, as the COD of recirculated water, turbidity, oil-contg, the indexs such as suspended substance are higher, when effectiveness that conventional corrosion inhibiting and descaling agent is difficult to bring into normal play, copolymer anti-scale disperser provided by the invention can be under the guarantee of its good surface activity, bring into play better the effect of scale inhibition and dispersion, scale inhibition dispersion effect exceedes existing conventional dirt dispersion agent.
A preparation method for without phosphorus copolymer anti-scale disperser, comprises the following steps:
1) solution preparation:
The unsaturated carboxylic acid that is 3 ~ 8 by carbonatoms and inorganic reducing agent are dissolved in organic solvent, form reagent I; Inorganic oxidizer is dissolved in organic solvent, forms reagent II; The unsaturated fatty acids that is 16 ~ 24 by carbonatoms, is dissolved in organic solvent, forms reagent III;
2) polyreaction:
Reagent I is warming up to 45 ~ 65 ℃, adds reagent II and reagent III;
After, being heated to solvent boiling, described reagent I, reagent II, reagent III are at the boiling temperature polymerization reaction take place of organic solvent, and the reaction times is 1 ~ 5h;
Wherein, in described polyreaction, the add-on of reactant is:
Unsaturated carboxylic acid 5 ~ 15wt%
Unsaturated fatty acids 85 ~ 95wt%;
Inorganic reducing agent and inorganic oxidizer add-on are respectively 8 ~ 14% of unsaturated carboxylic acid and unsaturated fatty acids total mass;
3) by cooling the product obtaining, obtain copolymer anti-scale disperser.
It is 1 ~ 3h that the total time that described reagent II and reagent III add is controlled.At least one in the preferred oleic acid of described unsaturated fatty acids, linolic acid, linolenic acid, arachidonic acid; At least one in the preferred vinylformic acid of described unsaturated carboxylic acid, toxilic acid, methylene-succinic acid.
Alcohols or the organic solvent of ketone of the preferred boiling point of described organic solvent between 70 ~ 90 ℃, more preferably ethanol, Virahol or butanone.
Described inorganic reducing agent is pyrosulfite or sulphite, is preferably Sodium Pyrosulfite or potassium pyrosulfite, S-WAT or potassium sulfite.
Described inorganic oxidizer is persulphate, is preferably ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
Organic solvent in described reagent I, reagent II and reagent III is same.
A kind of without phosphorus copolymer anti-scale disperser, the molecular weight ranges of this copolymer anti-scale disperser is 4000 ~ 12000, contains carboxyl, long carbochain in molecular structure; The monomer of this dirt dispersion agent and proportioning are:
Carbonatoms is 16 ~ 24 unsaturated fatty acids, and mass percent is 5 ~ 15%;
Carbonatoms is 3 ~ 8 unsaturated carboxylic acid, and mass percent is 85 ~ 95%.
The application of without phosphorus copolymer anti-scale disperser in the higher water body of oil-contg, the using dosage of this dirt dispersion agent is calculated as 6 ~ 30mg/L by effective concentration, resistance CaCO
3dirt and steady ferrum property are higher than the commercially available conventional dirt dispersion agent of existing use.
Vinylformic acid is the simplest unsaturated carboxylic acid, is made up of a vinyl and a carboxyl.Toxilic acid is maleic acid, has two keys and two carboxyls in molecule.Methylene-succinic acid formal name used at school is methene succsinic acid, methylene-succinic acid, and because intramolecule contains two active carboxyls and a two key, two keys and carboxyl are conjugate relation, make its character very active.Easy monomer generation association response, addition reaction, functional group reactions and the transesterification reaction with thering is two keys and carboxyl functional group of these unsaturated carboxylic acids above, for the preparation of many rings and heterogeneous ring compound, also can with other monomer polymerizations of different numbers, carry out various addition reactions, esterification and polyreaction are the important source material of chemosynthesis industry.Unsaturated fatty acids refers to that carbochain is completely unsaturated by hydrogen atom institute, contains the lipid acid of one or more unsaturated link(age)s.Unsaturated fatty acids is according to the difference of two key numbers, be divided into monounsaturated fatty acids and polyunsaturated fatty acid, wherein monounsaturated fatty acids has oleic acid, oleic acid is a two key, a carboxyl, polyunsaturated fatty acid has linolic acid, linolenic acid, arachidonic acid, wherein, linolic acid is two two keys, a carboxyl; Linolenic acid is three two keys, and carboxyl, an arachidonic acid are four two keys, a carboxyl etc.
Beneficial effect of the present invention:
Method and the product in prior art, prepared about polycarboxylic acid salt's dirt dispersion agent are a lot, but are mostly in the aqueous solution, to carry out polyreaction, and the monomer that participates in polymerization mostly also is the small molecules unsaturated carboxylic acid of carbonatoms between 3 ~ 10.The present invention uses organism boiling point backflow polymerization technique, the macromole unsaturated fatty acids and the water-soluble good small molecules unsaturated carboxylic acid that are insoluble in water are condensed together, the method can make product have hydroxy-acid group and long carbochain concurrently simultaneously, in thering is good resistance calcium carbonate scale performance and dispersing property, have again certain surfactivity and stripping performance concurrently, especially in the higher water body of oil-contg, scale inhibition performance is higher by 15 ~ 30% than conventional dirt dispersion agent, with the obvious advantage.Preparation method is simple for this copolymer anti-scale disperser, and cost is low, and dosage is few, and scale inhibition dispersion effect is good, and not phosphorous, and environmental protection can be widely used in industrial circulating cooling water system, has higher economic benefit and social benefit.
Embodiment
The following examples will contribute to illustrate the present invention, but not limit to its scope.
The Reliable Evaluating Methods of Their Performance of multipolymer is as follows:
Resistance calcium carbonate scale performance: get the former water of test, adding diesel oil to diesel oil concentration in former water is 30mg/L, makes it molten altogether by ultrasonic wave, and by the Ca in former water
2+, HCO
3 -mend 800mg/L (with CaCO
3meter) form test water, add copolymer anti-scale disperser, make its effective concentration meter reach 20mg/L, in 80 ± 1 ℃ of waters bath with thermostatic control, insulation 10h, remains Ca in cooling rear sampling analysis water
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) × 100%
C: actual measurement Ca
2+concentration
C
0: the Ca of blank sample
2+concentration
C
1: the Ca in former water
2+concentration
Sear dirt performance: get the former water of test, adding diesel oil to diesel oil concentration in former water is 30mg/L, makes it molten altogether by ultrasonic wave, and by the Ca in former water
2+, HCO
3 -mend 600mg/L (with CaCO
3meter), total iron mends 5 mg/L (in Fe) and forms test water, add copolymer anti-scale disperser, make its effective concentration reach 12mg/L, insulation 10h in 80 ± 1 ℃ of waters bath with thermostatic control, in cooling rear sampling analysis water, remain iron ion content, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) × 100%
C: actual measurement total iron content
C
0: the total iron content of blank sample
C
1: the total iron content in former water
Analytical procedure
The measuring method of effective content is got copolymer anti-scale disperser, weighs at 1.0000g to 105 ± 5 ℃ in the furnace pot of constant weight on ten thousand/balance, then moves in the loft drier of 105 ± 5 ℃ and dries to constant weight.
The calculation formula of effective content is: effective content=(W
2-W
1) × 100/W
0%
W
0: the quality of copolymer anti-scale disperser, g
W
1: the weight of furnace pot and residue, g
W
2: the weight of clean furnace pot, g
Method of calculation effective concentration=commodity concentration × effective content of effective concentration.
Ca
2+method for measurement of concentration is with reference to Ca in " boiler feed water and water coolant analytical procedure " GB 6905.3-86
2+the measuring method of concentration; Total iron determination method is with reference to the measuring method of total concentration of iron in " China Petrochemical Industry's water coolant is analyzed and test method " Q/SH 3155.S08.005-2006.
Test raw water quality is in table 1.
Table 1 is tested water quality
| Title | Ca 2+ | Total alkalinity | Cl - | SO 4 2- | pH | Positive phosphorus | Zn 2+ | Total iron | SiO 2 |
| Reuse water | 284 | 247 | 208 | 270 | 8.13 | 0.39 | 0.14 | 0.52 | 69 |
Note: pH is without unit, and its counit is mg/L, Ca
2+, total alkalinity, total hardness be all with CaCO
3meter, positive phosphorus is with PO
4meter, Zn
2+in Zn, total iron is in Fe, lower same.
Embodiment 1
Take vinylformic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 2
Take vinylformic acid 95g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 5g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 3
Take toxilic acid 94g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolic acid 6g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and linolic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 4
Take methylene-succinic acid 86g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolenic acid 14g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and linolenic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 5
Take vinylformic acid 85g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 15g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 6
Take vinylformic acid 90g, S-WAT 8g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take Sodium Persulfate 8g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take arachidonic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 50 ℃, drips ammonium persulphate and arachidonic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 7
Take toxilic acid 90g, potassium sulfite 14g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take Potassium Persulphate 14g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 55 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 8
Take methylene-succinic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 45 ℃, drips ammonium persulfate solution and linolic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 9
Take vinylformic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolenic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 65 ℃, drips ammonium persulfate solution and linolenic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 10
Take toxilic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take arachidonic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and arachidonic acid solution; Control and drip as 1h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 11
Take methylene-succinic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 3h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 12
Take vinylformic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and linolic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at Virahol boiling point place's polymerization 1h; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 13
Take toxilic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolenic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and linolenic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at Virahol boiling point place's polymerization 5h; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 14
Take methylene-succinic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 5g, arachidonic acid 5g, is dissolved in 50ml Virahol, mixes, and adds constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and unsaturated fatty acids mixing solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 15
Take vinylformic acid 90g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 3g, linolenic acid 3g, linolic acid 4g, is dissolved in 50ml Virahol, mixes, and adds constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and unsaturated fatty acids mixing solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 16
Take vinylformic acid 45g, toxilic acid 45g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 17
Take vinylformic acid 30g, toxilic acid 30g, methylene-succinic acid 30g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take linolic acid 10g, be dissolved in 50ml Virahol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and linolic acid solution; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 18
Take vinylformic acid 45g, methylene-succinic acid 45g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 5g, linolic acid 5g, is dissolved in 50ml Virahol, mixes, and adds constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and unsaturated fatty acids mixing solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 19
Take vinylformic acid 30g, toxilic acid 30g, methylene-succinic acid 30g, Sodium Pyrosulfite 11g, measures 110ml Virahol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml Virahol, add constant pressure funnel I; Take oleic acid 3g, arachidonic acid 3g, linolenic acid 4g, is dissolved in 50ml Virahol, mixes, and adds constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and unsaturated fatty acids mixing solutions; Control and drip as 2h; Dropwise, be heated to Virahol boiling, at the polyase 13 h of Virahol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 20
Take vinylformic acid 90g, Sodium Pyrosulfite 11g, measures 110ml ethanol, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml ethanol, add constant pressure funnel I; Take oleic acid 10g, be dissolved in 50ml ethanol, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to ethanol boiling, at the polyase 13 h of ethanol boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Embodiment 21
Take vinylformic acid 90g, Sodium Pyrosulfite 11g, measures 110ml butanone, stirs it is dissolved, and adds in the four-hole boiling flask that agitator, reflux exchanger, constant pressure funnel and thermometer are housed; Take ammonium persulphate 11g, be dissolved in 40ml butanone, add constant pressure funnel I; Take oleic acid 10g, be dissolved in 50ml butanone, mix, add constant pressure funnel II; Heat temperature raising, treats that temperature is raised to 60 ℃, drips ammonium persulfate solution and oleic acid solutions; Control and drip as 2h; Dropwise, be heated to butanone boiling, at the polyase 13 h of butanone boiling point place; Cooling product, the resistance CaCO of product of obtaining
3dirt rate and steady iron rate are in table 2.
Comparative example 1
Vinylformic acid/Propylene glycol monoacrylate multipolymer, purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark T225.
Comparative example 2
Vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, purchased from Hangzhou Tuo Mu Science and Technology Ltd., trade mark lov166.
Embodiment and the comparative example scale-inhibiting properties in test water is in table 2.
The scale-inhibiting properties of table 2 embodiment and comparative example
| Resistance CaCO 3Dirt rate, % | Steady iron rate, % | |
| Embodiment 1 | 77.2 | 68.1 |
| Embodiment 2 | 74.2 | 64.8 |
| Embodiment 3 | 75.4 | 66.9 |
| Embodiment 4 | 78.1 | 70.1 |
| Embodiment 5 | 78.1 | 70.2 |
| Embodiment 6 | 77.3 | 68.0 |
| Embodiment 7 | 76.7 | 68.2 |
| Embodiment 8 | 77.2 | 68.3 |
| Embodiment 9 | 76.8 | 68.1 |
| Embodiment 10 | 75.2 | 65.6 |
| Embodiment 11 | 77.5 | 68.6 |
| Embodiment 12 | 74.5 | 64.7 |
| Embodiment 13 | 77.4 | 68.4 |
| Embodiment 14 | 73.2 | 63.8 |
| Embodiment 15 | 69.3 | 59.9 |
| Embodiment 16 | 79.2 | 70.6 |
| Embodiment 17 | 77.1 | 68.0 |
| Embodiment 18 | 73.8 | 64.1 |
| Embodiment 19 | 69.5 | 60.1 |
| Embodiment 20 | 76.8 | 67.6 |
| Embodiment 21 | 76.9 | 67.7 |
| Comparative example 1 | 57.7 | 52.3 |
| Comparative example 2 | 54.2 | 50.3 |
Above embodiment and comparative example explanation, copolymer anti-scale disperser of the present invention, in the higher water body of oil-contg, has excellent resistance CaCO
3the performance of dirty and stable molysite, scale inhibition dispersion effect is better than conventional dirt dispersion agent.
Claims (9)
1. a preparation method for without phosphorus copolymer anti-scale disperser, comprises the following steps:
1) solution preparation:
The unsaturated carboxylic acid that is 3 ~ 8 by carbonatoms and inorganic reducing agent are dissolved in organic solvent, form reagent I; Inorganic oxidizer is dissolved in organic solvent, forms reagent II; The unsaturated fatty acids that is 16 ~ 24 by carbonatoms is dissolved in organic solvent, forms reagent III;
2) polyreaction:
Reagent I is warming up to 45 ~ 65 ℃, adds reagent II and reagent III, after, being heated to solvent boiling, described reagent I, reagent II, reagent III are at the boiling temperature polymerization reaction take place of described organic solvent, and the reaction times is 1 ~ 5h;
Wherein, in described polyreaction, the add-on of reactant is:
Unsaturated carboxylic acid 5 ~ 15wt%
Unsaturated fatty acids 85 ~ 95wt%;
Inorganic reducing agent add-on is 8 ~ 14% of unsaturated carboxylic acid and unsaturated fatty acids total mass,
Inorganic oxidizer add-on is 8 ~ 14% of unsaturated carboxylic acid and unsaturated fatty acids total mass;
3) by cooling the product obtaining, obtain copolymer anti-scale disperser.
2. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 1, is characterized in that, it is 1 ~ 3h that the total time that described reagent II and reagent III add is controlled.
3. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 2, is characterized in that, described unsaturated fatty acids is at least one in oleic acid, linolic acid, linolenic acid and arachidonic acid; Described unsaturated carboxylic acid is at least one in vinylformic acid, toxilic acid and methylene-succinic acid.
4. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 1, is characterized in that, described organic solvent is alcohol or the ketone of boiling point between 70 ~ 90 ℃.
5. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 4, is characterized in that, described alcohol is ethanol or Virahol; Described ketone is butanone.
6. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 1, is characterized in that, described inorganic reducing agent is pyrosulfite or sulphite, is preferably Sodium Pyrosulfite or potassium pyrosulfite, S-WAT or potassium sulfite.
7. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 1, is characterized in that, described inorganic oxidizer is persulphate, is preferably ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
8. the preparation method of without phosphorus copolymer anti-scale disperser as claimed in claim 1, is characterized in that, the organic solvent in described reagent I, reagent II and reagent III selects same.
9. the without phosphorus copolymer anti-scale disperser that prepared by the method as described in any one in claim 1 ~ 8, is characterized in that, the molecular weight ranges of this copolymer anti-scale disperser is 4000 ~ 12000, contains carboxyl, long carbochain in molecular structure;
The monomer of this dirt dispersion agent and proportioning are:
Carbonatoms is 16 ~ 24 unsaturated fatty acids, and mass percent is 5 ~ 15%;
Carbonatoms is 3 ~ 8 unsaturated carboxylic acid, and mass percent is 85 ~ 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210460375.7A CN103804562B (en) | 2012-11-15 | 2012-11-15 | A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210460375.7A CN103804562B (en) | 2012-11-15 | 2012-11-15 | A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103804562A true CN103804562A (en) | 2014-05-21 |
| CN103804562B CN103804562B (en) | 2015-10-07 |
Family
ID=50701990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210460375.7A Active CN103804562B (en) | 2012-11-15 | 2012-11-15 | A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804562B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512782A (en) * | 2016-06-17 | 2017-12-26 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN107601684A (en) * | 2016-07-12 | 2018-01-19 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN107686175A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of composite scale-inhibiting corrosion inhibitor and its application and the processing method of recirculated cooling water |
| CN111362545A (en) * | 2020-03-24 | 2020-07-03 | 成都科衡环保技术有限公司 | Oil-removing oxidant for waste oil-based mud in drilling as well as preparation method and application of oil-removing oxidant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674568A (en) * | 2012-06-13 | 2012-09-19 | 威海翔宇环保科技有限公司 | Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
| CN102730847A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment |
| CN102745823A (en) * | 2011-04-19 | 2012-10-24 | 南京林业大学 | Quadripolymer-type corrosion-inhibition scale inhibitor PMAHS and preparation method thereof |
-
2012
- 2012-11-15 CN CN201210460375.7A patent/CN103804562B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730847A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment |
| CN102745823A (en) * | 2011-04-19 | 2012-10-24 | 南京林业大学 | Quadripolymer-type corrosion-inhibition scale inhibitor PMAHS and preparation method thereof |
| CN102674568A (en) * | 2012-06-13 | 2012-09-19 | 威海翔宇环保科技有限公司 | Phosphate-free copolymer dirt dispersion agent and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512782A (en) * | 2016-06-17 | 2017-12-26 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN107601684A (en) * | 2016-07-12 | 2018-01-19 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN107686175A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of composite scale-inhibiting corrosion inhibitor and its application and the processing method of recirculated cooling water |
| CN111362545A (en) * | 2020-03-24 | 2020-07-03 | 成都科衡环保技术有限公司 | Oil-removing oxidant for waste oil-based mud in drilling as well as preparation method and application of oil-removing oxidant |
| CN111362545B (en) * | 2020-03-24 | 2022-02-08 | 成都科衡环保技术有限公司 | Oil-removing oxidant for waste oil-based mud in drilling as well as preparation method and application of oil-removing oxidant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103804562B (en) | 2015-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103803729B (en) | A kind of copolymer anti-scale disperser and preparation method thereof | |
| CN103803722B (en) | Non-phosphorus copolymer antiscale dispersant and preparation method thereof | |
| CN103804562B (en) | A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof | |
| CN101781028B (en) | High-efficiency low-phosphorous corrosion and scale inhibition dispersant as well as preparation method and application thereof | |
| CN102616946B (en) | Preparation method of biodegradable corrosion and scale inhibitor epoxy succinic acid copolymer | |
| CN102225976B (en) | Method for preparing polyacrylic acid dispersing agents by adopting acrylic acid waste water as raw material | |
| CN102689992A (en) | Terpolymer antisludging agent and preparation process thereof | |
| CN107010740A (en) | A kind of sewage disposal antisludging agent and preparation method thereof | |
| CN104045173A (en) | Novel non-phosphorus quadripolymer scale inhibitor and preparation method thereof | |
| CN105753183A (en) | Multiple composite corrosion inhibitor and preparation method thereof | |
| CN102745825A (en) | High-efficiency low-phosphorus corrosion and scale inhibiting dispersant and its preparation method | |
| CN103265125B (en) | Quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM and preparation method thereof | |
| CN104891682B (en) | Environment-friendly and efficient water treatment agent applicable to Cu-Fe sharing system | |
| CN104445645A (en) | Environment-friendly corrosion and scale inhibitor and preparation method thereof | |
| CN106957112A (en) | No-phosphate corrosion dirt dispersion agent and its preparation method and application | |
| CN103242476B (en) | A kind of preparation method with the acrylic polymers of fluorescent characteristic | |
| CN107686174A (en) | A kind of composite scale-inhibiting corrosion inhibitor and its application and the processing method of recirculated cooling water | |
| CN108017163A (en) | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water | |
| CN109626604A (en) | A kind of non-phosphate environment-friendly type imidazoline system's corrosion inhibiting and descaling agent and preparation method | |
| CN108059258A (en) | A kind of industrial circulation water treatment antisludging agent and preparation method thereof | |
| CN107601683A (en) | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water | |
| CN107686175A (en) | A kind of composite scale-inhibiting corrosion inhibitor and its application and the processing method of recirculated cooling water | |
| CN103804591B (en) | A kind of Phosphate-free copolymer dirt dispersion agent and preparation method thereof | |
| CN105949380A (en) | Ternary polymer diesel pour point reducer composition and preparation method thereof | |
| CN107601684A (en) | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |