CN115072885B - Nanofiltration concentrated solution modifier and preparation method thereof - Google Patents
Nanofiltration concentrated solution modifier and preparation method thereof Download PDFInfo
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- CN115072885B CN115072885B CN202210823454.3A CN202210823454A CN115072885B CN 115072885 B CN115072885 B CN 115072885B CN 202210823454 A CN202210823454 A CN 202210823454A CN 115072885 B CN115072885 B CN 115072885B
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- 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
- C02F5/105—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 combined with inorganic substances
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- 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
- C02F5/125—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 combined with inorganic substances
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- 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
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention belongs to the field of landfill leachate wastewater treatment. The invention discloses a nanofiltration concentrate modifier and a preparation method thereof, wherein the nanofiltration concentrate modifier comprises the following components in parts by weight: 10-30 parts of modified landfill leachate concentrated solution extract, 2-5 parts of poly N-isopropyl acrylamide, 8-20 parts of S-carboxypropyl thiosuccinic acid, 5-10 parts of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 2-8 parts of acidic mucopolysaccharide modifier, 1-5 parts of sodium hydroxide and 22-72 parts of deionized water. Compared with the prior art, the invention has the following advantages: after the nano-filtration concentrate modifier is added into the nano-filtration concentrate to be treated, the membrane separation device can run more stably and orderly, the system load is reduced, the anti-fouling and anti-blocking effect is better, the membrane flux is effectively improved, the membrane cleaning frequency is reduced, the concentrate treatment capacity is improved, and the service life of the membrane is prolonged.
Description
Technical Field
The invention belongs to the field of landfill leachate wastewater treatment, and particularly relates to a nanofiltration concentrate modifier and a preparation method thereof.
Background
The landfill leachate is high-concentration wastewater generated in the stacking and landfill processes of the garbage, and has the characteristics of high organic matter concentration, high ammonia nitrogen content, high content, heavy metal and other toxic pollutants and the like. Therefore, the existence of the landfill leachate can cause serious pollution to underground water, surface water and soil, and great threat to ecological environment and human health is generated.
The pollution control of leachate in the municipal domestic waste incineration technology is a big technical problem in China, the treatment of leachate in incineration plants mostly adopts a combined process of pretreatment, anaerobism, MBR (membrane bioreactor), nanofiltration and reverse osmosis advanced treatment at present, and the effluent quality can reach the standard of municipal sewage recycling industrial water quality (GB/T19923-2005). In the combined process, the nanofiltration process can produce a certain amount of nanofiltration concentrated solution, which is about 15 to 20 percent of the scale of inlet water. The nanofiltration concentrated solution contains refractory high-concentration organic matters, calcium, magnesium ions, chloride ions and the like, the hardness, ammonia nitrogen, total nitrogen and salt content are high, macromolecular organic matters in the nanofiltration concentrated solution are extracted by the materials through a membrane separation device, membrane pores of a water treatment membrane assembly are easily blocked, the normal treatment capacity of the concentrated solution is influenced, the pressure of the membrane is increased in a short time, the bearing load of the membrane is improved, the production must be stopped for cleaning, and otherwise the membrane can be damaged irreversibly.
The existing nanofiltration additive or scale inhibitor usually adopts an organic phosphorus scale inhibitor, can be applied to the water quality of the conventional process, is not suitable for the garbage percolate concentrated solution with high COD, high ammonia nitrogen and high salt content, and can only relieve the inorganic substance scaling of the water treatment membrane component under the condition of higher addition amount, thus having poor effect of preventing and treating the organic substance fouling of the water treatment membrane component.
Disclosure of Invention
The invention provides a nanofiltration concentrate modifier and a preparation method thereof, which are used for solving the problems that the existing nanofiltration concentrate treatment process is poor in organic pollution blockage prevention effect, a membrane separation device is easy to cause membrane pore blockage, the cleaning frequency after membrane pore blockage is high, and the service life of a membrane is short.
The technical scheme of the invention is realized as follows:
the invention provides a nanofiltration concentrate modifier which is characterized by comprising the following components in parts by weight: 10-30 parts of modified landfill leachate concentrated solution extract, 2-5 parts of poly N-isopropylacrylamide, 8-20 parts of S-carboxypropylthiosuccinic acid, 5-10 parts of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 2-8 parts of acidic mucopolysaccharide modifier, 1-5 parts of sodium hydroxide and 22-72 parts of deionized water. After the nanofiltration concentrate modifier is added, various organic matters and inorganic matters in the material are orderly operated according to respective characteristic performances without reaction and adhesion, so that the membrane separation operation is more stable and ordered, the system load is reduced, the membrane cleaning frequency is reduced, the concentrate treatment capacity is improved, and the service life of the membrane is prolonged.
The nanofiltration concentrated solution contains high-concentration organic matters which are difficult to degrade, calcium, magnesium ions, chloride ions and the like, the hardness, ammonia nitrogen, total nitrogen and salt content are high, and the materials pass through a membrane separation device to extract macromolecular organic matters in the nanofiltration concentrated solution, namely the organic macromolecular extract of the nanofiltration concentrated solution.
The organic polymer extract of the modified landfill leachate concentrated solution contains various multifunctional polymer compounds, contains more active groups such as hydroxyl, quinonyl, phenolic group, methoxyl group and the like, has large internal surface area, has strong adsorption, exchange, complexation and chelation capacities, can adsorb heavy metal ions such as chelated calcium, magnesium, copper, iron and the like, can restrict and bind large and small molecules in a molecular structure, and contains nitrogen elements which can reduce ammonia nitrogen in water.
The acidic mucopolysaccharide modifier contains a large number of negative ion groups such as-COO-, -CO-, can wrap up small-molecule suspended matters, organic matters, inorganic salts and the like, and has repulsion with a membrane due to the fact that the acidic mucopolysaccharide modifier contains a large number of negative ion groups, so that membrane pores are not easy to adhere and block, and organic matter blocking is avoided.
The polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate contains hydroxyl, carboxyl, ether, sulfonic group and other groups, has high scale inhibiting and dispersing capacity, can raise the solubility of the compound effectively, form coordination compound on the surface of metal to produce chemical adsorption, strengthen the scale inhibiting performance, disperse soil, dust, humus and biological debris in water, realize the synergistic effect of several kinds of functional groups, no phosphorus and easy biodegradation.
Further, the nanofiltration concentrate modifier is characterized by comprising the following components in parts by weight: 25 parts of modified landfill leachate concentrated solution extract, 2 parts of poly N-isopropylacrylamide, 15 parts of S-carboxypropylthiosuccinic acid, 8 parts of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 5 parts of acidic mucopolysaccharide modifier, 2 parts of sodium hydroxide and 43 parts of deionized water.
Further, the acidic mucopolysaccharide modifier is a potassium salt of acidic mucopolysaccharide.
Further, the acidic mucopolysaccharide modifier is potassium hyaluronate.
Further, the preparation method of the modified landfill leachate concentrated solution extract comprises the following steps: adding potassium hydroxide into the organic polymer extract of the landfill leachate concentrated solution, adjusting the pH value to 11, heating to 90 ℃, stirring for 0.5h, then cooling to room temperature, adding water for centrifugal separation, and obtaining an upper layer product, namely the modified landfill leachate concentrated solution extract, without further refining.
Further, the S-carboxypropylthiosuccinic acid is obtained by performing addition reaction on 4-mercaptobutyric acid and anhydrous polymaleic anhydride, wherein the molar ratio of the 4-mercaptobutyric acid to the anhydrous polymaleic anhydride is 1:1.
further, the preparation method of the polyepoxysuccinic acid hydroxypropyl acrylate is as follows:
(1) Adding sodium epoxysuccinate and hydroxypropyl acrylate into a reactor, adjusting the pH value to 11, heating to 90 ℃ by taking benzoyl peroxide as an initiator, reacting for 3h, cooling to room temperature, and separating and purifying to obtain an epoxysuccinic acid-hydroxypropyl acrylate copolymer;
(2) And (2) adding a 40% sodium bisulfite aqueous solution into the epoxysuccinic acid-hydroxypropyl acrylate copolymer obtained in the step (1), stirring and mixing uniformly, heating to 97 ℃, and reacting for 3 hours to obtain polyepoxysuccinic acid hydroxypropyl acrylate.
The structural formula of the polyepoxysuccinic acid hydroxypropyl acrylate is as follows:
further, in the step (1), the mass ratio of the sodium epoxysuccinate to the hydroxypropyl acrylate is 5:1.
Further, in the step (1), the mass of the initiator accounts for 3% of the total weight of the epoxy sodium succinate and the hydroxypropyl acrylate mixture.
Further, in the step (2), the mass ratio of the epoxysuccinic acid-hydroxypropyl acrylate copolymer to the sodium bisulfite is 10.
Further, in the step (1), the reactor is a flask provided with a stirrer, a reflux condenser and a thermometer.
Further, the molecular weight of the polyepoxysuccinic acid hydroxypropyl acrylate is 2000-5000.
A method of preparing the nanofiltration concentrate modifier described above, the method comprising the steps of:
(a) Adding deionized water into a reaction kettle, then adding S-carboxypropyl thiosuccinic acid and polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, and stirring until the S-carboxypropyl thiosuccinic acid and the polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate are dissolved;
(b) Adding sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding the modified garbage percolate concentrated solution extract, poly N-isopropyl acrylamide and acidic mucopolysaccharide modifier, and stirring for 1h to obtain the nanofiltration concentrated solution modifier.
The application method of the nanofiltration concentrate modifier is characterized in that the nanofiltration concentrate modifier is added into the nanofiltration concentrate, and the addition amount of the nanofiltration concentrate modifier is 2-30ppm.
Furthermore, the addition amount of the nanofiltration concentrate modifier is 5ppm.
Furthermore, the using concentration of the nanofiltration concentrate modifier is 2-30mg/L.
Further, the nanofiltration concentrate modifier is diluted according to the proportion of 1 part of medicament and ten parts of water, and then is directly added into the nanofiltration concentrate, and then the nanofiltration concentrate enters a material separation membrane device.
Compared with the prior art, the invention has the following advantages:
(1) After the nanofiltration concentrated solution modifier is added into the nanofiltration concentrated solution to be treated, the membrane separation device operates more stably and orderly, the system load is reduced, the antifouling and blocking effect is better, the membrane flux is effectively improved, the membrane cleaning frequency is reduced, the concentrated solution treatment capacity is improved, and the service life of the water treatment membrane is prolonged. (2) The landfill leachate concentrated solution extract can be reused for landfill leachate nanofiltration concentrated solution without refining and purification after being modified, so that the waste recycling is realized, and the components of the nanofiltration concentrated solution are basically not changed after the nanofiltration concentrated solution modifier is added, so that the resource utilization of the waste is fully realized. (3) The preparation method has the advantages of simple production process, good stability and water solubility, biodegradable main components, no toxicity, no phosphorus, no pollution, no corrosiveness, small dosage and environmental friendliness.
Detailed Description
In order to make the preparation method of the present invention clearer and make the use effect and the product advantages clearer, the technical scheme of the present invention will be described in detail below. Next, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Examples to help explain and define the summary of the invention, other embodiments made by other researchers in the field without making a more prominent creative effort are within the scope of the present invention.
Example 1
The embodiment provides a nanofiltration concentrate modifier, which comprises the following components in parts by weight: 250g of modified landfill leachate concentrated solution extract, 20g of poly N-isopropylacrylamide, 150g of S-carboxypropylthiosuccinic acid, 80g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 50g of acidic mucopolysaccharide modified substance, 20g of sodium hydroxide and 430g of deionized water.
In this example, the preparation method of the nanofiltration concentrate modifier is as follows:
(a) Adding 430g of deionized water into a reaction kettle, then adding 150g of S-carboxypropylthiosuccinic acid and 80g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, and stirring until the solution is dissolved;
(b) Adding 20g of sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding 250g of modified landfill leachate concentrated solution extract, 20g of poly-N-isopropylacrylamide and 50g of acidic mucopolysaccharide modified substance, and stirring for 1h to obtain the nanofiltration concentrated solution modified agent.
In this embodiment, the acidic mucopolysaccharide modifier is potassium hyaluronate.
In this example, the preparation method of the modified landfill leachate concentrate extract is as follows: adding potassium hydroxide into the organic polymer extract of the landfill leachate concentrated solution, adjusting the pH value to 11, heating to 90 ℃, stirring for 0.5h, then cooling to room temperature, adding water with the same mass for centrifugal separation, and obtaining an upper-layer product, namely the modified landfill leachate concentrated solution extract, without further refining.
Preferably, the S-carboxypropylthiosuccinic acid is obtained by performing addition reaction on 4-mercaptobutyric acid and anhydrous polymaleic anhydride, and the molar ratio of the 4-mercaptobutyric acid to the anhydrous polymaleic anhydride is 1:1.
in this example, the preparation method of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate is as follows:
(1) Adding sodium epoxysuccinate into a reactor, adding hydroxypropyl acrylate, adjusting the pH value to 11, heating to 90 ℃ by taking benzoyl peroxide as an initiator, reacting for 3 hours, cooling to room temperature, and separating and purifying to obtain an epoxysuccinic acid-hydroxypropyl acrylate copolymer;
(2) And (2) adding a 40% sodium bisulfite aqueous solution into the epoxysuccinic acid-hydroxypropyl acrylate copolymer obtained in the step (1), stirring and mixing uniformly, heating to 97 ℃, and reacting for 3 hours to obtain polyepoxysuccinic acid hydroxypropyl acrylate.
Preferably, in the step (1), the mass ratio of the sodium epoxysuccinate to the hydroxypropyl acrylate is 5:1.
Preferably, in the step (1), the mass of the initiator accounts for 3% of the total weight of the epoxy sodium succinate and the hydroxypropyl acrylate mixture.
Preferably, in the step (2), the mass ratio of the epoxysuccinic acid-hydroxypropyl acrylate copolymer to the sodium bisulfite is 10.
Preferably, in the step (1), the reactor is a flask provided with a stirrer, a reflux condenser and a thermometer.
Example 2
The embodiment provides a nanofiltration concentrate modifier, which comprises the following components in parts by weight: 100g of modified landfill leachate concentrated solution extract, 20g of poly N-isopropylacrylamide, 80g of S-carboxypropylthiosuccinic acid, 50g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 20g of potassium hyaluronate, 10g of sodium hydroxide and 720g of deionized water.
In this example, the preparation method of the nanofiltration concentrate modifier is as follows:
(a) Adding 720g of deionized water into a reaction kettle, then adding 80g of S-carboxypropylthiosuccinic acid and 50g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, and stirring until the materials are dissolved;
(b) And (b) adding 10g of sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding 100g of modified landfill leachate concentrated solution extract, 20g of poly-N-isopropylacrylamide and 20g of potassium hyaluronate, and stirring for 1 hour to obtain the nanofiltration concentrated solution modifier.
In this example, the preparation method of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate is the same as that of example 1. The modified landfill leachate concentrate extract was prepared in the same manner as in example 1.
Example 3
The embodiment provides a nanofiltration concentrate modifier, which comprises the following components in parts by weight: 300g of modified landfill leachate concentrated solution extract, 40g of poly N-isopropylacrylamide, 180g of S-carboxypropylthiosuccinic acid, 80g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 80g of potassium hyaluronate, 33g of sodium hydroxide and 287g of deionized water.
In this example, the preparation method of the nanofiltration concentrate modifier is as follows:
(a) 287g of deionized water is added into a reaction kettle, then 180g of S-carboxypropyl thiosuccinic acid and 80g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate are added, and stirring is carried out until dissolution is carried out;
(b) Adding 33g of sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding 300g of modified landfill leachate concentrated solution extract, 40g of poly-N-isopropylacrylamide and 80g of potassium hyaluronate, and stirring for 1 hour to obtain the nanofiltration concentrated solution modifier.
In this example, the preparation method of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate is the same as that of example 1. The modified landfill leachate concentrate extract was prepared in the same manner as in example 1.
Example 4
The embodiment provides a nanofiltration concentrate modifier, which comprises the following components in parts by weight: 200g of modified landfill leachate concentrated solution extract, 50g of poly N-isopropylacrylamide, 200g of S-carboxypropylthiosuccinic acid, 100g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 60g of potassium hyaluronate, 40g of sodium hydroxide and 350g of deionized water.
In this example, the preparation method of the nanofiltration concentrate modifier is as follows:
(a) Adding 350g of deionized water into a reaction kettle, then adding 200g of S-carboxypropylthiosuccinic acid and 100g of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, and stirring until the solution is dissolved;
(b) And (b) adding 40g of sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding 200g of modified landfill leachate concentrated solution extract, 50g of poly-N-isopropylacrylamide and 60g of potassium hyaluronate, and stirring for 1 hour to obtain the nanofiltration concentrated solution modifier.
In this example, the preparation method of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate is the same as that of example 1. The modified landfill leachate concentrate extract was prepared in the same manner as in example 1.
Example 5
The embodiment provides a nanofiltration concentrate modifier, which comprises the following components in parts by weight: 300g of modified landfill leachate concentrated solution extract, 50g of poly N-isopropylacrylamide, 200g of S-carboxypropyl thiosuccinic acid, 100g of polyepoxysuccinic acid hydroxypropyl acrylate sulfonate, 80g of potassium hyaluronate, 50g of sodium hydroxide and 220g of deionized water.
In this example, the preparation method of the nanofiltration concentrate modifier is as follows:
(a) Adding 220g of deionized water into a reaction kettle, then adding 200g of S-carboxypropyl thiosuccinic acid and 100g of polyepoxysuccinic acid hydroxypropyl acrylate, and stirring until the materials are dissolved;
(b) And (b) adding 50g of sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding 300g of modified landfill leachate concentrated solution extract, 50g of poly-N-isopropylacrylamide and 80g of potassium hyaluronate, and stirring for 1h to obtain the nanofiltration concentrated solution modifier.
In this example, the preparation method of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate is the same as that of example 1. The modified landfill leachate concentrate extract was prepared in the same manner as in example 1.
Example 6
The nanofiltration concentrate modifiers prepared in examples 1 to 5 were subjected to performance tests in a certain waste power plant in Shandong:
nanofiltration concentrated solution generated by a certain waste power plant in Shandong contains refractory high-concentration organic matters, calcium and magnesium ions, chloride ions and the like, the hardness and ammonia nitrogen are high, and the water quality data of the inlet water of the No. 1 unit is as follows: 19230 mu s/cm of conductivity, 15NTU of turbidity, 83mmol/L of total hardness, 42mmol/L of total alkalinity, 220.44mg/L of calcium, 875.16mg/L of magnesium, 4748.1mg/L of chloride ions, 620mg/L of COD and 2500mg/L of ammonia nitrogen.
Diluting the nanofiltration concentrate modifier according to the proportion of 1 part of medicament and ten parts of water, directly adding the diluted nanofiltration concentrate modifier into the nanofiltration concentrate, then adding the nanofiltration concentrate with the nanofiltration concentrate modifier into a material separation membrane device, and comparing the nanofiltration concentrate with a control group which is not added with the modifier and is only added with the organophosphorus scale inhibitor, wherein the addition amount of the nanofiltration concentrate modifier is 5ppm, and the initial membrane flux is 220L/(m parts of water) 2 H) when the pressure difference between membrane sections is more than 0.3MPa, cleaning. For convenience of comparison with the blank, and measurement of the membrane flux data on the tenth day of operation, the experimental comparison results are as follows:
table 1:
| blank space | Organic phosphorus scale inhibition agent | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Addition amount (ppm) | 0 | 5 | 5 | 5 | 5 | 5 | 5 |
| Membrane flux L/(m) after 10 days 2 ·h） | 81 | 120 | 200 | 188 | 192 | 202 | 205 |
| Cleaning cycle, day | 10 | 15 | 25 | 20 | 23 | 26 | 27 |
As can be seen from Table 1, the addition of the modifier to the nanofiltration concentrate results in at least a 1-fold increase in the wash cycle compared to the absence of the modifier; compared with the conventional organic phosphorus scale inhibitor, the nano-filtration concentrated solution modifier is added for use, so that the membrane cleaning frequency can be reduced, the inhibition effect on membrane pollution is very obvious, the antifouling and blocking effects are good, the membrane flux is effectively improved, and the treatment capacity of the landfill leachate is increased.
Example 7
The inlet water conductivity of the unit No. 2 in the same plant is 19390 mu s/cm, the turbidity is 15NTU, the total hardness is 85mmol/L, the total alkalinity is 42mmol/L, the calcium is 260.1mg/L, the magnesium is 875.16mg/L, the chloride ion is 4763mg/L, the COD is 615mg/L, and the ammonia nitrogen is 2380mg/L.
Diluting the nanofiltration concentrate modifier according to the proportion of 1 part of medicament and ten parts of water, directly adding the diluted nanofiltration concentrate modifier into the nanofiltration concentrate, then adding the nanofiltration concentrate with the nanofiltration concentrate modifier into a material separation membrane device, and comparing the nanofiltration concentrate with a control group which is not added with the modifier and is only added with the organophosphorus scale inhibitor, wherein the addition amount of the nanofiltration concentrate modifier is 10ppm, and the initial membrane flux is 220L/(m parts of water) 2 H) when the pressure difference between membrane sections is more than 0.3MPa, cleaning. For convenience of comparison with the blank, and measurement of the membrane flux data on the tenth day of operation, the experimental comparison results are as follows:
table 2:
| blank space | Organic phosphorus scale inhibition agent | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Addition amount (ppm) | 0 | 10 | 10 | 10 | 10 | 10 | 10 |
| Membrane flux L/(m) after 10 days 2 ·h） | 82 | 125 | 202 | 191 | 193 | 203 | 205 |
| Cleaning cycle, day | 10 | 17 | 25 | 22 | 23 | 27 | 27 |
As can be seen from Table 2, the addition of the modifier to the nanofiltration concentrate results in at least 1-fold longer wash cycle than the absence of the modifier; compared with the conventional organic phosphorus scale inhibitor, the nano-filtration concentrated solution modifier is added for use, so that the membrane cleaning frequency can be reduced, the inhibition effect on membrane pollution is very obvious, the antifouling and blocking effects are good, the membrane flux is effectively improved, and the treatment capacity of the landfill leachate is increased.
Example 8
The conductivity of inlet water of a unit No. 3 in the same factory is 20120 mu s/cm, the turbidity is 14.6NTU, the total hardness is 85.5mmol/L, the total alkalinity is 42.4mmol/L, the calcium is 260.1mg/L, the magnesium is 881.23mg/L, the chloride ion is 4913mg/L, the COD is 595mg/L and the ammonia nitrogen is 2392mg/L.
Diluting the nanofiltration concentrate modifier according to the proportion of 1 part of medicament and ten parts of water, directly adding the diluted nanofiltration concentrate modifier into the nanofiltration concentrate, then adding the nanofiltration concentrate with the nanofiltration concentrate modifier into a material separation membrane device, and comparing the nanofiltration concentrate with a control group which is not added with the modifier and is only added with the organophosphorus scale inhibitor, wherein the addition amount of the nanofiltration concentrate modifier is 20ppm, and the initial membrane flux is 220L/(m parts of water) 2 H) when the pressure difference between membrane sections is more than 0.3MPa, cleaning is carried out. For convenience of comparison with the blank, and measurement of the membrane flux data on the tenth day of operation, the experimental comparison results are as follows:
table 3:
| blank space | Organic phosphorus scale inhibition agent | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Addition amount (ppm) | 0 | 20 | 20 | 20 | 20 | 20 | 20 |
| Membrane flux L/(m) after 10 days 2 ·h） | 81 | 125 | 203 | 195 | 196 | 204 | 204 |
| Cleaning cycle, day | 10 | 17 | 26 | 23 | 24 | 27 | 27 |
As can be seen from Table 3, the addition of the modifier to the nanofiltration concentrate results in at least a 1-fold increase in the wash cycle compared to the absence of the modifier; compared with the conventional organic phosphorus scale inhibitor, the nano-filtration concentrate modifier is added for use, so that the membrane cleaning frequency can be reduced, the inhibition effect on membrane pollution is very obvious, the antifouling and blocking effects are good, the membrane flux is effectively improved, and the treatment capacity of landfill leachate is increased.
It can be seen from the table 1, table 2 and table 3 in the comprehensive examples 6 to 8 that the flux of the organophosphorus scale inhibitor is slightly increased from 5ppm to 10ppm after the dosing concentration is increased, the cleaning period is prolonged by two days, the flux is unchanged when the concentration is continuously increased to 20ppm, and the cleaning period is not prolonged; after the nanofiltration concentrate modifier is added, the dosing concentration is increased, the flux is slightly increased, and the continuous increase and improvement are small, which indicates that 5ppm of the water quality can achieve good effect and good economical efficiency. Has the advantages of less dosage and environmental protection.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention, and the technical solutions are all covered in the scope of the claims and the specification of the present invention; it will be apparent to those skilled in the art that any alternative modifications or variations to the embodiments of the present invention may be made within the scope of the present invention.
The details of the present invention are not described in detail, but are known to those skilled in the art.
Claims (2)
1. The nanofiltration concentrate modifier is characterized by comprising the following components in parts by weight: 10-30 parts of modified landfill leachate concentrated solution extract, 2-5 parts of poly N-isopropylacrylamide, 8-20 parts of S-carboxypropylthiosuccinic acid, 5-10 parts of polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, 2-8 parts of acidic mucopolysaccharide modifier, 1-5 parts of sodium hydroxide and 22-72 parts of deionized water;
the acidic mucopolysaccharide modifier is potassium hyaluronate;
the preparation method of the modified landfill leachate concentrated solution extract comprises the following steps: adding potassium hydroxide into the organic polymer extract of the landfill leachate concentrated solution, adjusting the pH to 11, heating to 90 ℃, stirring for 0.5h, then cooling to room temperature, adding water for centrifugal separation to obtain an upper layer product, namely the modified landfill leachate concentrated solution extract, without further refining;
the S-carboxypropyl thiosuccinic acid is obtained by performing addition reaction on 4-mercaptobutyric acid and anhydrous polymaleic anhydride, wherein the molar ratio of the 4-mercaptobutyric acid to the anhydrous polymaleic anhydride is 1:1;
the preparation method of the polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate comprises the following steps:
(1) Adding sodium epoxysuccinate and hydroxypropyl acrylate into a reactor, adjusting the pH value to 11, heating to 90 ℃ by taking benzoyl peroxide as an initiator, reacting for 3h, cooling to room temperature, and separating and purifying to obtain an epoxysuccinic acid-hydroxypropyl acrylate copolymer;
(2) And (2) adding a 40% sodium bisulfite aqueous solution into the epoxysuccinic acid-hydroxypropyl acrylate copolymer obtained in the step (1), stirring and mixing uniformly, heating to 97 ℃, and reacting for 3 hours to obtain polyepoxysuccinic acid hydroxypropyl acrylate.
2. A method of preparing the nanofiltration concentrate modifier of claim 1, comprising the steps of:
(a) Adding deionized water into a reaction kettle, then adding S-carboxypropyl thiosuccinic acid and polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate, and stirring until the S-carboxypropyl thiosuccinic acid and the polyepoxysuccinic acid acrylic acid hydroxypropyl sulfonate are dissolved;
(b) Adding sodium hydroxide into the solution obtained in the step (a) to adjust the pH value to 12, cooling to room temperature, adding the modified garbage percolate concentrated solution extract, poly N-isopropyl acrylamide and acidic mucopolysaccharide modifier, and stirring for 1h to obtain the nanofiltration concentrated solution modifier.
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