CN112279386B - Non-phosphorus scale inhibitor and preparation method and application thereof - Google Patents
Non-phosphorus scale inhibitor and preparation method and application thereof Download PDFInfo
- Publication number
- CN112279386B CN112279386B CN202010899225.0A CN202010899225A CN112279386B CN 112279386 B CN112279386 B CN 112279386B CN 202010899225 A CN202010899225 A CN 202010899225A CN 112279386 B CN112279386 B CN 112279386B
- Authority
- CN
- China
- Prior art keywords
- scale inhibitor
- phosphorus
- water
- reverse osmosis
- dendritic polymer
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a non-phosphorus scale inhibitor, which comprises the following components in percentage by weight: 50-85% of dendritic polymer, 5-10% of terpolymer and the balance of water. Also discloses a preparation method thereof and application of the phosphorus-free scale inhibitor in treating sewage by using a membrane. The dendritic polymer in the scale inhibitor has huge internal and external surface areas and huge terminal functional groups, can provide higher scale inhibition load than other scale inhibitors, can control various metal ions, organic and inorganic molecules, has good dispersion effect on high-salinity sewage by the terpolymer, and can inhibit the influence of the heavy metal ions on the dendritic polymer. The scale inhibitor does not contain any organic phosphine or inorganic phosphate in molecules, so that the danger of microbial pollution of a membrane system and the pollution discharge influence on the environment are reduced. The scale inhibitor overcomes the defects of the conventional scale inhibitor, and is particularly suitable for treating high-salinity mine sewage by using a reverse osmosis membrane.
Description
Technical Field
The invention relates to a phosphorus-free scale inhibitor, a preparation method thereof and application of the phosphorus-free scale inhibitor in sewage treatment by using a membrane, belonging to the technical field of water treatment.
Background
Reverse osmosis is a water treatment technology adopting membrane separation, utilizes a reverse osmosis principle, adopts a reverse osmosis membrane with high selective permeability, makes a part of feed water pass through the membrane in a direction perpendicular to the membrane to prepare desalted water, concentrates salts and colloidal substances in the water on the surface of the membrane, and takes away the concentrated substances in the rest of feed water in a direction parallel to the membrane. The method can lead the removal rate of inorganic salt, hardness ions, organic matters, bacteria and the like in water to reach 97-98 percent, and the reverse osmosis technology is more and more widely applied because of the characteristics of environmental protection, energy conservation, high efficiency, simple operation and maintenance, stable system performance and the like. The method is widely applied to various fields such as pure water preparation, wastewater treatment, drinking water and beverage, and chemical product concentration and recovery processes in the industries such as medicine, electronics, food, chemical industry and the like.
Scientists find through the research of bionics that a membrane capable of effectively separating salt is a semi-permeable membrane, and a salt solution has an osmosis phenomenon on the semi-permeable membrane side, wherein the osmosis phenomenon is caused by osmotic pressure, and reverse osmosis is a reverse osmosis process in which salt-containing water is applied with external driving force to overcome osmotic pressure so as to enable water molecules to pass through the membrane, and bears a main desalination task.
In order to prevent the scaling problem caused by the increase of ion concentration caused by concentration in the membrane, the high-efficiency scale inhibitor is adopted for treatment. For high-hardness, high-alkalinity and high-chlorination mine water of a coal mine sewage treatment plant, the conductivity is usually 10000 mu s/cm, the sulfate content is about 2000mg/L, and the chloride is about 2000 mg/L. The scale inhibition performance of the scale inhibitor is very high. However, the conventional medicament is easy to cause physical and chemical pollution on the membrane surface in the operation process, and the water inlet channel is dirty and blocked, so that the operation pressure of the system and the pressure difference between sections are increased, the water yield or the desalination rate of the system is reduced, even if careful or frequent online chemical cleaning is carried out, the conventional medicament sometimes does not help, and even membrane elements are scrapped in advance.
In order to ensure the economic, safe and smooth operation of the reverse osmosis system, besides the reliable design, reasonable configuration and perfect and thorough operation management of the device, the selection of a proper special medicament for the membrane system and professional maintenance are important to prevent the chemical pollution of the reverse osmosis system caused by the continuous concentration of raw water.
Disclosure of Invention
The invention aims to provide a phosphorus-free scale inhibitor and a preparation method thereof and application of the phosphorus-free scale inhibitor in membrane treatment of sewage, aiming at solving the problems in the prior art. The scale inhibitor overcomes the defects of the conventional scale inhibitor, and is particularly suitable for treating high-salinity mine sewage by using a reverse osmosis membrane.
The invention provides a phosphorus-free scale inhibitor, which comprises the following components in percentage by weight: 50-85% of dendritic polymer, 5-10% of terpolymer and the balance of water.
According to a preferred embodiment of the present invention, the weight percentage of dendritic polymer in the phosphorus-free scale inhibitor is 60-75%, preferably 65-70%.
According to a preferred embodiment of the present invention, the weight percentage of the terpolymer in the phosphorus-free scale inhibitor is 6-9%, preferably 7-8%.
According to a preferred embodiment of the invention, the dendritic polymer comprises the reaction product of diethylenetriaminepentaacetic acid and/or ethylenediamine tetraacetic acid with polyamidoamine.
According to a preferred embodiment of the present invention, the dendrimer is a dendrimer compound (DTPA-PAMAM) obtained by linking diethylenetriaminepentaacetic acid (DTPA) to Polyamidoamine (PAMAM) dendrimers, the molar ratio of DTPA to PAMAM being 1: 5-1: 8, prepared by the following method:
adding chloroacetic acid into a reaction kettle, adding distilled water, stirring and dissolving, dropwise adding a 40% NaOH solution at 15 ℃, dropwise adding diethylenetriamine under stirring, and controlling the temperature to be about 20 ℃ in the dropwise adding process. Under the conditions of cooling and stirring, polyamide amine (PAMAM) is slowly added dropwise, and the temperature is controlled to be less than 40 ℃ during dropwise addition. After the dripping is finished, the temperature is raised to 70-80 ℃, and the temperature is kept for 5-6 hours. Then heating to reflux, concentrating the reaction mixture, and concentrating for 2-3 hours. And after the concentration is finished, cooling to normal temperature to obtain clear amber liquid with the solid content of 40-44%, namely the DTPA-PAMAM product.
The DTPA-PAMAM dendritic polymer used in the invention has huge internal and external surface areas and huge terminal functional groups, can provide higher scale inhibition load than other scale inhibitors, and can control various metal ions, organic and inorganic molecules.
According to a preferred embodiment of the present invention, the terpolymer comprises a structural unit represented by formula I below, a structural unit represented by formula II below, and a structural unit represented by formula III below:
wherein M is 1 And M 2 Each independently selected from hydrogen, metals and alkylhydroxy groups containing 1 to 4 carbon atoms, preferably from hydrogen, alkali metals and ethylhydroxy groups, more preferably from hydrogen, lithium, potassium and sodium; x is selected from O and NH, preferably NH; r is selected from C 1 -C 6 Preferably selected from C 1 -C 4 More preferably selected from methyl, ethyl, propyl and butyl; a is an integer of 0 to 4; b is an integer of 1 to 4.
According to a preferred embodiment of the present invention, the structural unit represented by formula I includes, but is not limited to, the structural unit represented by formula (1):
according to a preferred embodiment of the present invention, the structural unit represented by formula II includes, but is not limited to, structural units represented by formulas (2) and (3):
according to a preferred embodiment of the present invention, the structural unit represented by formula III includes, but is not limited to, structural units represented by formulas (4) and (5):
in some embodiments, the molar ratio of the structural unit of formula I, the structural unit of formula II, and the structural unit of formula III is (1.5-3.0): (3.5-6.0): (2.0-4.0), preferably (2.0-2.5): (4.0-5.5): (2.2-2.8), more preferably 2.5: 4.8: 2.7.
according to a preferred embodiment of the invention, the terpolymer is an acrylic acid/acrylamidopropanesulfonic acid/hydroxypropyl acrylate (AA/AMPS/HPA) copolymer.
Compared with other copolymers, such as conventional binary copolymer and homopolymer, the terpolymer used in the invention has better dispersing performance, has good dispersing effect on high-salinity sewage, and can inhibit the influence of heavy metal ions on the dendritic polymer.
In some embodiments, the terpolymer is the polymerization product of monomer a, monomer B, and monomer C:
wherein M is 1 -M 2 Each independently selected from hydrogen, metal and alkylhydroxy groups containing 1 to 4 carbon atoms, preferably from hydrogen, alkali metal and ethylhydroxy groups, more preferably from hydrogen, lithium, potassium and sodium; x is selected from O and NH, preferably NH; r is selected from C 1 -C 6 Preferably selected from C 1 -C 4 More preferably selected from methyl, ethyl, propyl and butyl; a is an integer of 0 to 4; b is an integer of 1 to 4.
In some embodiments, the monomer a may be a carboxylic acid-containing unsaturated monomer and salts thereof, preferably including acrylic acid.
In some embodiments, the monomer B may be acrylamidopropanesulfonic acid in the free acid form or as a salt of the free acid.
In some embodiments, the monomer C may be an unsaturated monomer containing a hydroxyl group and salts thereof, preferably including hydroxypropyl acrylate.
In some embodiments, the molar ratio of monomer a, monomer B, and monomer C is (1.5-3.0): (3.5-6.0): (2.0-4.0), preferably (2.0-2.5): (4.0-5.5): (2.2-2.8), more preferably 2.5: 4.8: 2.7.
according to some embodiments of the invention, the monomer a, the monomer B, and the monomer C are copolymerized in the presence of an initiator and a chain transfer agent to provide a polymerization product.
According to some embodiments of the present invention, the initiator may be a conventional initiator known in the field of high molecular polymerization, and may be selected from one of azo-type initiators, peroxide or peroxy ester-type initiators, and oxidation-reduction initiators, for example.
In some embodiments, the azo-type initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyramidine hydrochloride, or azobisisobutyrimidazoline hydrochloride.
In some embodiments, the peroxide or peroxyester initiator comprises one or more of ammonium persulfate, benzoyl peroxide, dibenzoyl peroxide, benzoyl t-butyl peroxide, or methyl ethyl ketone peroxide.
In some embodiments, the oxidizing agent in the oxidation-reduction initiation system comprises one or more of hydrogen peroxide, a persulfate, such as potassium persulfate, and the reducing agent comprises one or more of sodium sulfite, sodium bisulfite, a thiosulfate, and ascorbic acid.
In the invention, an ascorbic acid-hydrogen peroxide initiation system is preferably used, the initiator can ensure that impurities are not introduced in the process of initiating the polymerization reaction, the activity is higher, and the polymerization reaction can be completed at lower temperature.
In some embodiments, the molar ratio of the initiator to the total amount of monomers is 1: (100-200), preferably 1: (100-150).
In some embodiments of the present invention, the chain transfer agent can be a commonly used chain transfer agent known in the art of high molecular polymerization, for example, including one or more of sodium methallylsulfonate, thioglycolic acid, mercaptopropionic acid, isopropanol, sodium bisulfite, preferably mercaptopropionic acid.
In some embodiments of the invention, the molar ratio of the chain transfer agent to the total amount of monomers is 1: (40-60).
The invention also provides a preparation method of the phosphorus-free scale inhibitor, which comprises the following steps: and mixing the dendritic polymer, the terpolymer and water to obtain the phosphorus-free scale inhibitor.
In some embodiments, the method of making comprises:
s1 obtaining dendritic polymer;
s2 obtaining a terpolymer;
s3, under the stirring condition, adding the terpolymer and the dendritic polymer into water, stirring and mixing, standing and cooling to obtain the phosphorus-free scale inhibitor.
According to a preferred embodiment of the present invention, the step S1 includes:
adding chloroacetic acid into a reaction kettle, adding distilled water, stirring and dissolving, dropwise adding 40% NaOH solution at 15 ℃, dropwise adding diethylenetriamine under stirring, and controlling the temperature to be about 20 ℃ in the dropwise adding process. Under the conditions of cooling and stirring, polyamide amine (PAMAM) is slowly added dropwise, and the temperature is controlled to be less than 40 ℃ during dropwise addition. After the dripping is finished, the temperature is raised to 70-80 ℃, and the temperature is kept for 5-6 hours. Then heating to reflux, concentrating the reaction mixture, and concentrating for 2-3 hours. And after the concentration is finished, cooling to normal temperature to obtain clear amber liquid with the solid content of 40-44%, namely the DTPA-PAMAM product.
According to a preferred embodiment of the present invention, the step S3 includes:
adding a certain amount of water into a reaction kettle, stirring, heating the water to 30 +/-5 ℃, adding a certain amount of terpolymer and a certain amount of dendritic polymer, stirring for 15 +/-5 minutes, standing for 5 +/-2 minutes, and cooling to room temperature to obtain the phosphorus-free scale inhibitor.
Another aspect of the present invention provides a use of the phosphorus-free scale inhibitor according to the first aspect or the phosphorus-free scale inhibitor prepared according to the method of the second aspect in treating sewage using a membrane.
According to some embodiments of the invention, the membrane comprises a reverse osmosis membrane.
According to some embodiments of the invention, the contaminated water comprises mine water, in particular high salinity mine water, in particular complex high salinity mine water.
According to a preferred embodiment of the invention, the high-salinity mine water has the following characteristics: the conductivity is 9000-12000 mu s/cm, the sulfate content is about 1500-2200mg/L, and the chloride content is about 1800-2500 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
1. the dendritic polymer used in the invention has huge internal and external surface area and huge terminal functional groups, and can provide higher scale inhibition load than other scale inhibitors, so that the dendritic polymer can control various metal ions, organic and inorganic molecules.
2. Compared with other copolymers, the terpolymer used in the invention has better dispersion performance, has good dispersion effect on high-salinity sewage, and can inhibit the influence of heavy metal ions on the dendritic polymer.
3. The scale inhibitor molecule does not contain any organic phosphine or inorganic phosphate, so that the risk of microbial pollution of a membrane system can be reduced, and the pollution discharge influence on the environment is also reduced.
4. The scale inhibitor is small in dosage which is 1/10-1/15 of the traditional scale inhibitor, once the dosage of the conventional medicament in reverse osmosis exceeds 5ppm, the scale inhibitor can pollute a membrane system, and the scale inhibitor is absolutely safe for the membrane due to the small dosage of the scale inhibitor and the use of a novel dendritic polymer.
5. Under the condition of high salt content, the influence of osmotic pressure is reduced due to the special high stability of the dendritic polymer, and the scale inhibition activity of the dendritic molecular structure is enhanced, so that the scale inhibitor has a better effect on high-salt sewage.
6. The scale inhibitor containing the dendritic polymer directly controls inorganic salt ions or organic molecules in water in the original state in the water by depending on the dendritic branched structure and the terminal functional group, prevents the generation of microcrystals and realizes complete scale inhibition in the real sense.
7. The invention effectively solves the problems that the activity of the conventional scale inhibitor for the mine water reverse osmosis membrane is reduced and the scale inhibition efficiency of the functional group is rapidly reduced along with the increase of the salt content under the condition of high salt content.
8. The invention effectively solves the problem of the conventional medicament pair CaCO 3 、CaSO 4 、BaSO 4 、SrSO4、SiO 2 The scale inhibition performance of the equal scales is lack of broad spectrum.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
The dendritic polymers used in the embodiments 1-4 of the present application are all DTPA-PAMAM, wherein the mole ratio of DTPA to PAMAM is 1:6, the terpolymers used are all AA/AMPS/HPA, and the mole ratio of the DTPA to PAMAM is 2.5: 4.8: 2.7.
example 1
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 75% of dendritic polymer (DTPA-PAMAM), 10% of terpolymer (AA/AMPS/HPA) and 15% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 150kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 100kg of terpolymer, adding 750kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of the mine water is 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, the silicate content is 17.4mg/L, the use period is 3 months, the pressure difference, the water yield and the water yield conductivity before and after the reverse osmosis membrane basically keep unchanged, and the excellent scale inhibition performance is shown.
Example 2
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 80% of dendritic polymer (DTPA-PAMAM), 8% of terpolymer (AA/AMPS/HPA) and 12% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 120kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 80kg of terpolymer, adding 800kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite high-salinity mine water reverse osmosis membrane phosphorus-free scale inhibitor.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.35 mg/L. The conductivity of the mine water is 8000-8500 mu s/cm, the sulfate content is 1560mg/L, the chloride content is 1500mg/L, the silicate content is 17.2mg/L, the reverse osmosis membrane is used for 3 months, the pressure difference, the water yield and the water yield conductivity before and after the reverse osmosis membrane are basically kept unchanged, and the excellent scale inhibition performance is shown.
Example 3
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 85% of dendritic polymer (DTPA-PAMAM), 5% of terpolymer (AA/AMPS/HPA) and 10% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: firstly, adding 100kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 50kg of terpolymer, then adding 850kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite high-salinity mine water reverse osmosis membrane phosphorus-free scale inhibitor.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of mine water is between 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, and the silicate content is 17.4mg/L, the pressure difference, the water yield and the water yield conductivity before and after the reverse osmosis membrane are basically kept unchanged after the reverse osmosis membrane is used for 3 months, and the excellent scale inhibition performance is shown.
Example 4
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 50% of dendritic polymer (DTPA-PAMAM), 10% of terpolymer (AA/AMPS/HPA) and 40% of water.
The preparation process of the composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 400kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 100kg of terpolymer, adding 500kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of the mine water is 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, the silicate content is 17.4mg/L, the use period is 3 months, the pressure difference, the water yield and the water yield conductivity before and after the reverse osmosis membrane basically keep unchanged, and the excellent scale inhibition performance is shown.
Comparative example 1
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 30% of dendritic polymer (DTPA-PAMAM), 55% of terpolymer (AA/AMPS/HPA) and 15% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 150kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 550kg of terpolymer, adding 300kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of the mine water is 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, the silicate content is 17.4mg/L, the use lasts for 3 months, the pressure difference between the front and the back of the reverse osmosis membrane is slightly increased, the water yield is slightly reduced, and the conductivity of the water yield is slightly increased.
Comparative example 2
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 30% of dendritic polymer (DTPA-PAMAM), 10% of terpolymer (AA/AMPS/HPA) and 60% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 600kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 100kg of terpolymer, adding 300kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of the mine water is 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, and the silicate content is 17.4mg/L, and the reverse osmosis membrane is used for 3 months, the pressure difference before and after the reverse osmosis membrane is slightly increased, the water yield is slightly reduced, and the conductivity of the water yield is slightly increased.
Comparative example 3
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 75% of dendritic polymer (EDA-PAMAM, the molar ratio is 1:6), 10% of terpolymer (AA/AMPS/HPA) and 15% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 150kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 550kg of terpolymer, adding 300kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of mine water is between 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, and the silicate content is 17.4mg/L, and the pressure difference before and after the reverse osmosis membrane is slightly increased, the water yield is slightly reduced, and the water yield conductivity is increased after the reverse osmosis membrane is used for 3 months.
Comparative example 4
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 75% of dendritic polymer (DTPA-PAMAM), 10% of terpolymer (AA/AMPS/TBAM, molar ratio of 2.5: 4.8: 2.7) and 15% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 150kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 100kg of terpolymer, adding 750kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of the mine water is 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, and the silicate content is 17.4mg/L, and the reverse osmosis membrane is used for 3 months, the pressure difference before and after the reverse osmosis membrane is slightly increased, the water yield is slightly reduced, and the conductivity of the water yield is slightly increased.
Comparative example 5
The composite non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following components in percentage by weight: 75% of dendritic polymer (DTPA-PAMAM), 10% of binary copolymer (AA/AMPS, molar ratio of 2.5:4.8) and 15% of water.
The preparation process of the composite type non-phosphorus scale inhibitor for the reverse osmosis membrane of the high-salinity mine water comprises the following steps: adding 150kg of water into a reaction kettle, stirring, heating the water to 30 ℃, adding 100kg of binary copolymer, adding 750kg of dendritic polymer, stirring for 15 minutes, standing for 5 minutes, and cooling to room temperature to obtain the composite type phosphorus-free scale inhibitor for the high-salinity mine water reverse osmosis membrane.
The obtained composite type high-salinity mine water reverse osmosis membrane non-phosphorus scale inhibitor is applied to a mine water reverse osmosis membrane system of a certain coal mine sewage treatment plant, and the addition amount is 0.4 mg/L. The conductivity of the mine water is 9000-10000 mu s/cm, the sulfate content is about 1777mg/L, the chloride content is about 2160mg/L, the silicate content is 17.4mg/L, and the reverse osmosis membrane is used for 3 months, the pressure difference before and after the reverse osmosis membrane is slightly increased, the water yield is slightly reduced, and the conductivity of the water yield is increased.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (7)
1. A non-phosphorus scale inhibitor comprises the following components in percentage by weight: 50-85% of dendritic polymer, 5-10% of terpolymer and the balance of water; the terpolymer is acrylic acid/acrylamido propanesulfonic acid/hydroxypropyl acrylate copolymer;
the dendritic polymer is a dendritic polymer compound obtained by connecting diethylene triamine pentaacetic acid to polyamidoamine dendrimer, and the molar ratio of the diethylene triamine pentaacetic acid to the polyamidoamine is 1: 5-1: 8.
2. the phosphorus-free scale inhibitor of claim 1, wherein the terpolymer is a polymerization product of a monomer acrylic acid, a monomer acrylamidopropanesulfonic acid, and a monomer hydroxypropyl acrylate.
3. The phosphorus-free scale inhibitor according to claim 1 or 2, wherein the molar ratio of the monomeric acrylic acid, the monomeric acrylamidopropanesulfonic acid and the monomeric hydroxypropyl acrylate is (1.5-3.0): (3.5-6.0): (2.0-4.0).
4. The phosphorus-free scale inhibitor according to claim 3, wherein the molar ratio of the monomeric acrylic acid, the monomeric acrylamidopropanesulfonic acid, and the monomeric hydroxypropyl acrylate is 2.5: 4.8: 2.7.
5. the method of preparing the phosphorus-free scale inhibitor of any one of claims 1-4, comprising: and mixing the dendritic polymer, the terpolymer and water to obtain the phosphorus-free scale inhibitor.
6. Use of a phosphorus-free scale inhibitor according to any one of claims 1-4 or prepared according to the method of claim 5 in the treatment of sewage with a membrane.
7. The use of claim 6, the membrane comprising a reverse osmosis membrane; and/or the sewage comprises high salinity mine water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010899225.0A CN112279386B (en) | 2020-08-31 | 2020-08-31 | Non-phosphorus scale inhibitor and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010899225.0A CN112279386B (en) | 2020-08-31 | 2020-08-31 | Non-phosphorus scale inhibitor and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112279386A CN112279386A (en) | 2021-01-29 |
| CN112279386B true CN112279386B (en) | 2022-09-27 |
Family
ID=74420865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010899225.0A Active CN112279386B (en) | 2020-08-31 | 2020-08-31 | Non-phosphorus scale inhibitor and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112279386B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087169A (en) * | 2021-05-25 | 2021-07-09 | 上绍同烯达(绍兴)新材料科技有限公司 | Phosphorus-free scale inhibitor and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006088958A2 (en) * | 2005-02-15 | 2006-08-24 | Dendritic Nanotechnologies, Inc. | Encapsulated (chelate or ligand) dendritic polymers |
| CN101973643B (en) * | 2010-09-27 | 2012-12-05 | 同济大学 | Dendrimer and sodium polyepoxysuccinate composite scale inhibitor for inhibiting silica scale deposition in water |
| CN105709606A (en) * | 2016-02-03 | 2016-06-29 | 青岛科润生物科技有限公司 | Environment-friendly reverse osmosis membrane scale inhibiting and dispersing agent and preparation method thereof |
| CN107151059A (en) * | 2016-03-02 | 2017-09-12 | 上海丰信环保科技有限公司 | Hinder carbonate, sulfate and iron, the Phosphateless environmentally friendly reverse osmosis antisludging agent of manganese |
| CN109264876B (en) * | 2018-10-12 | 2021-12-14 | 山东理工大学 | Non-phosphorus reverse osmosis scale inhibitor EDA-PAMAM and preparation method thereof |
| CN110143678A (en) * | 2019-06-13 | 2019-08-20 | 科得邦（江苏）环境科技有限公司 | A kind of Phosphateless environmentally friendly MVR evaporator antisludging agent and preparation method thereof |
| CN110548407A (en) * | 2019-09-16 | 2019-12-10 | 新疆水处理工程技术研究中心有限公司 | Reverse osmosis scale inhibitor for inhibiting silica scale |
-
2020
- 2020-08-31 CN CN202010899225.0A patent/CN112279386B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112279386A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101372524B (en) | Process for producing cation polyacrylamide | |
| CN103319648A (en) | Modified ternary copolymer, preparation method and applications thereof | |
| CN112279386B (en) | Non-phosphorus scale inhibitor and preparation method and application thereof | |
| CN101318730B (en) | Inorganic-organic composite chemical dephosphorization agent preparation method | |
| CN116075530A (en) | Polymers of 2-acrylamido-2-methylpropanesulfonic acid or salts thereof | |
| EP0079165B1 (en) | (meth) acrylic acid/itaconic acid copolymers, their preparation and use as antiscalants | |
| CN112480310A (en) | Cross-linked cationic polyacrylamide sludge dehydrating agent and preparation method thereof | |
| CN102863582A (en) | Preparation method of ultra-high molecular weight cationic polyacrylamide | |
| CN107261855A (en) | A kind of reverse osmosis antisludging agent | |
| US20210253770A1 (en) | High melt index thermoplastic elastomer and preparation method therefor | |
| KR101635620B1 (en) | Scale Preventing Agent Including Phosphorus and Method of Producing the Same | |
| CN1583811A (en) | Preparation for water soluble high-molecular weight cationic polymer | |
| CN107555567A (en) | A kind of composite polyacrylamide for sewage disposal | |
| EP2298704A1 (en) | Scale and corrosion inhibitors for high temperature and pressure conditions | |
| JPH04505276A (en) | Use of water-soluble copolymers consisting of monoethylenically unsaturated carboxylic acids and vinylimidazole (derivatives) as water treatment agents | |
| EP2734556B1 (en) | Process for producing maleic acid-isoprenol copolymers | |
| CN1295257C (en) | Method for preparing high molecular weight cation type polyacrylamide | |
| CN111690084B (en) | Preparation method of polyacrylic acid and salt thereof | |
| CN1597550A (en) | Cation type polymer flocculating agent and its preparation method | |
| CN102775551B (en) | Random copolymer, preparation method and application thereof | |
| CN111908578A (en) | Preparation method of natural modified flocculant for treating heavy metal wastewater | |
| CN107746446B (en) | Preparation method of ternary copolymerization amphoteric polyacrylamide | |
| JP4889237B2 (en) | Method for producing cationic copolymer | |
| CN113816506B (en) | Reverse osmosis scale inhibitor and preparation method thereof | |
| KR101635622B1 (en) | Scale Preventing Agent not Including Phosphorus and Method of Producing the Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |