Multifunctional non-phosphorus boiler water treatment agent and preparation method thereof

Abstract

The application relates to the technical field of boiler water treatment agents, in particular to a multifunctional phosphorus-free boiler water treatment agent and a preparation method thereof. The multifunctional phosphorus-free boiler water treatment agent comprises a first microporous membrane and a second microporous membrane, the first microporous membrane is located inside the second microporous membrane, and a first microporous channel is formed in the first microporous membrane; the first microporous membrane is filled with a composite water treatment agent; a filling layer is formed between the second microporous membrane and the first microporous membrane; the filling layer is filled with multifunctional fillers; the pore diameter of the first microporous channel is smaller than the particle diameter of the multifunctional fillers; the multifunctional fillers in the filling layer are coated on the outer wall of the first microporous membrane and located inside the second microporous membrane; a second microporous channel for water body flow is formed in the second microporous membrane, and the pore diameter of the second microporous channel is smaller than the particle diameter of the multifunctional fillers. The application does not contain phosphorus elements, has good environmental protection performance, and has good scale inhibition and corrosion inhibition effects, so that the safe operation of a boiler system can be guaranteed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of boiler water treatment agents, in particular to a multifunctional phosphorus-free boiler water treatment agent and a preparation method thereof. BACKGROUND

[0002] Boilers are widely used in the industrial field as heat exchange equipment, which transfers heat released by fuel to water to form high-temperature steam, and then supplies the downstream equipment. Water quality is very important for the safe operation of boilers, and the most common and most harmful problem is the scaling of boiler water, especially for hard water with high calcium and magnesium ion content, which can greatly reduce the heat transfer efficiency of the boiler, and even cause pipe blockage and explosion. Therefore, treating the water entering the boiler system is an important measure to ensure the safe operation of the boiler system. SUMMARY

[0003] In order to solve the above technical problems, the present application provides a preparation method of a multifunctional phosphorus-free boiler water treatment agent.

[0004] The multifunctional phosphorus-free boiler water treatment agent provided by the present application is realized by the following technical scheme:

[0005] A multifunctional phosphorus-free boiler water treatment agent comprises a first microporous membrane and a second microporous membrane, the first microporous membrane has a first microporous channel formed therein for water body to flow through; the first microporous membrane is filled with a composite water treatment agent; the first microporous membrane is located inside the second microporous membrane, and a filling layer is formed between the second microporous membrane and the first microporous membrane; the filling layer is filled with multifunctional fillers; the pore size of the first microporous channel is smaller than the particle size of the multifunctional fillers; the multifunctional fillers in the filling layer are coated on the outer wall of the first microporous membrane and located inside the second microporous membrane; the second microporous membrane has a second microporous channel formed therein for water body to flow through, and the pore size of the second microporous channel is smaller than the particle size of the multifunctional fillers; during the boiler water treatment process, the multifunctional fillers are always located between the first microporous membrane and the second microporous membrane.

[0006] The multifunctional phosphorus-free boiler water treatment agent provided by the present application does not contain phosphorus elements, has good environmental protection performance, and has good scale inhibition and corrosion inhibition effects, which can ensure the safe operation of the boiler system and meet the current environmental protection development trend of boiler water treatment agents.

[0007] Preferably, the membrane thickness of the first microporous membrane and the second microporous membrane is controlled to be 0.10-0.25mm.

[0008] Preferably, the multifunctional fillers comprise at least one of calcium carbonate, porous zeolite powder, activated carbon, quartz powder, diatomite, and activated carbon fiber powder.

[0009] Preferably, the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder; the mass ratio of calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder is (0.8-1):(0.8-1):(0.8-1):(0.2-0.5).

[0010] By adopting the above technical solution, the solid slag formed by adsorbing calcium and magnesium ions and the composite water treatment agent can improve the scale inhibition and corrosion inhibition performance of the prepared multifunctional phosphorus-free boiler water treatment agent, and ensure the safe operation of the boiler system.

[0011] Preferably, the multifunctional filler includes a porous composite and an amino acid metal complex fixedly connected to the porous composite, the porous composite is made of calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder; the metal elements in the amino acid metal complex are fixedly connected to the porous composite in the form of a chemical bond; and the amino acids in the amino acid metal complex include one or more combinations of alliin, aspartic acid, arginine, and glycine.

[0012] Preferably, the porous composite is made of calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder at a mass ratio of 1:1:0.8:0.2; the metal elements in the amino acid metal complex are iron elements; and the amino acids in the amino acid metal complex are composed of alliin, aspartic acid, and glycine at a mass ratio of (0.8-1):(0.8-1):(0.8-1).

[0013] Preferably, the preparation method of the multifunctional filler includes the following steps:

[0014] S1, preparation of a porous composite: uniformly mix calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder according to the ratio, and then place them in a muffle furnace for calcination treatment at a temperature of 80-120°C for 8-24h; grind and crush the obtained solid material to obtain porous composite particles with a suitable particle size;

[0015] Meanwhile, a transition metal ligand is configured: accurately measure the amino acid, add it to deionized water, and stir until uniform; the mass ratio of the amino acid to deionized water is (3-6):100; then place it in a 50°C water bath for heating while stirring at a speed of 400-600rpm until the amino acid is completely dissolved to obtain an amino acid solution; then add ferric sulfate to the amino acid solution, the iron content in the ferric sulfate is 0.8-1.2 times the amino acid content, and continue to heat in a 50°C water bath and stir at a speed of 400-600rpm for 4-8h to allow the amino acid and iron to fully combine and coordinate to obtain a transition metal ligand;

[0016] S2, the porous composite particles obtained in S1 are added to the transition metal ligand at 5-10 g / min, the mass ratio of the porous composite particles to the transition metal ligand is (20-40):100, ultrasonic dispersion treatment is performed for 1-2 h, then magnetic stirring is performed for 12-24 h, sufficient washing with deionized water is performed until neutral, filtration is performed, drying at 80-85℃ for 8-12 h, and cooling to room temperature to obtain a solid product;

[0017] S3, the solid product obtained in S2 is heated to 180-220℃ at a heating rate of 4-6℃ / min under an argon atmosphere, and held for 6-8 h, the obtained solid product is subjected to ball milling treatment in a planetary ball mill, and screening treatment to obtain a multifunctional filler with a suitable particle size.

[0018] By adopting the technical scheme, the multifunctional phosphorus-free boiler water treatment agent prepared has good scale inhibition, corrosion inhibition and environmental protection performance, and can effectively disinfect and sterilize the water body, further ensuring safe operation of the boiler system.

[0019] Preferably, the composite water treatment agent is mainly prepared from the following raw materials by weight: 10-20 parts of a scale remover, 0.5-2 parts of sodium D-erythorbate, 1-3 parts of 1-amino-4-methyl piperazine, 1-3 parts of N,N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, and 1-3 parts of 3-acrylamide dopamine, the scale remover being a terpolymer prepared from N-methyl acryloyl glycine, 2-methyl-2-acrylamide propyl sulfonic acid and hydroxypropyl acrylate; the first microporous membrane and the second microporous membrane are thermoplastic polyolefin membranes, reducing the probability of chemical reaction between the first microporous membrane, the second microporous membrane and the composite water treatment agent.

[0020] Preferably, the composite water treatment agent is mainly prepared from the following raw materials by weight: 16-18 parts of a scale remover, 1.2-1.6 parts of sodium D-erythorbate, 2.0-2.6 parts of 1-amino-4-methyl piperazine, 1.5-2.4 parts of N,N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, and 2-3 parts of 3-acrylamide dopamine.

[0021] By adopting the technical scheme, the multifunctional phosphorus-free boiler water treatment agent has excellent scale inhibition and corrosion inhibition performance.

[0022] The application provides a preparation method of a multifunctional phosphorus-free boiler water treatment agent.

[0023] The preparation method of the multifunctional phosphorus-free boiler water treatment agent comprises the following steps:

[0024] Step one, preparation of a multifunctional filler and a composite water treatment agent;

[0025] Step two, taking the thermoplastic polyolefin film as the first microporous membrane, the prepared composite water treatment agent is coated in the first microporous membrane by using the laundry bead automatic packaging machine to prepare the semi-finished water treatment granular preparation with a particle size of 8-16mm;

[0026] Step three, the multifunctional filler in step one is mixed with water-soluble glue to prepare a multifunctional filler film layer, and the multifunctional filler film layer is coated on the outer wall of the semi-finished water treatment granular preparation obtained in step two, so as to prepare a semi-finished product.

[0027] Step four, taking the thermoplastic polyolefin film as the second microporous membrane, the second microporous membrane is coated on the outer wall of the semi-finished product, i.e. the outer wall of the multifunctional filler film layer, by using the laundry bead automatic packaging machine, so as to prepare the multifunctional phosphorus-free boiler water treatment agent.

[0028] The preparation method provided in the application is relatively simple, has relatively low implementation difficulty, and is convenient for realizing industrialized batch manufacturing.

[0029] Preferably, in step three, the multifunctional filler in step one is mixed with water-soluble glue at a mass ratio of (0.8-0.9):(0.1-0.2) to prepare a multifunctional filler film layer with a thickness of 0.5-1.0mm.

[0030] By using the above technical solution, the scale inhibition and corrosion inhibition performance of the prepared multifunctional phosphorus-free boiler water treatment agent can be improved.

[0031] In summary, the application has the following advantages:

[0032] 1. The application does not contain phosphorus elements, has good environmental protection performance, and has good scale inhibition and corrosion inhibition effects, so as to ensure the safe operation of the boiler system and meet the environmental protection development trend of the current boiler water treatment agent.

[0033] 2. The self-prepared multifunctional filler in the application not only gives the prepared multifunctional phosphorus-free boiler water treatment agent good scale inhibition, corrosion inhibition and environmental protection performance, but also effectively disinfects and sterilizes the water body, further ensuring the safe operation of the boiler system.

[0034] 3. The preparation method provided in the application is relatively simple, has relatively low implementation difficulty, and is convenient for realizing industrialized batch manufacturing. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 is a schematic diagram of the overall structure in the embodiment of the application.

[0036] In the figure, 1 is a first microporous membrane; 11 is a first microporous channel; 12 is a composite water treatment agent; 2 is a second microporous membrane; 21 is a filler layer; 22 is a multifunctional filler; and 23 is a second microporous channel. DETAILED DESCRIPTION

[0037] In order to further illustrate the present application, the preferred embodiments of the present application are described below in conjunction with the examples, but it should be understood that these descriptions are only intended to further illustrate the features and advantages of the present application, and are not intended to limit the scope of the claims. Those skilled in the art can modify the process parameters according to the content described herein, as appropriate. It is particularly pointed out that all such similar alternatives and modifications as would be apparent to those of ordinary skill in the art are intended to be encompassed within the present application. The methods and applications of the present application have been described by way of preferred embodiments, and those skilled in the art can obviously make modifications or appropriate changes and combinations to the methods and applications described herein without departing from the content, spirit and scope of the present application, to realize and apply the present application. Although the following terms are believed to be well understood by those of ordinary skill in the art, the following definitions are set forth to facilitate the understanding of the subject matter disclosed herein.

[0038] As used herein, the term "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. "Comprising" is a term of art that is used in the claims to mean that the composition or method includes the recited elements, but not excluding others.

[0039] Embodiment

[0040] Reference Figure 1 A multifunctional phosphorus-free boiler water treatment agent includes a first microporous membrane 1 and a second microporous membrane 2, the first microporous membrane 1 is inside the second microporous membrane 2. A first microporous channel 11 for water body flow is formed in the first microporous membrane 1, and a second microporous channel 23 for water body flow is formed in the second microporous membrane 2. The first microporous membrane 1 is filled with a composite water treatment agent 12. A filling layer 21 is formed between the second microporous membrane 2 and the first microporous membrane 1, and the filling layer 21 is filled with multifunctional filler 22. The pore size of the first microporous channel 11 is smaller than the particle size of the multifunctional filler 22. The multifunctional filler 22 in the filling layer 21 is coated on the outer wall of the first microporous membrane 1 and inside the second microporous membrane 2, and the pore size of the second microporous channel 23 is smaller than the particle size of the multifunctional filler 22. In the process of boiler water treatment, the multifunctional filler 22 is always between the first microporous membrane 1 and the second microporous membrane 2, and the multifunctional filler 22 adsorbs the solid slag formed by the calcium and magnesium ions and the composite water treatment agent, which can improve the scale inhibition and corrosion inhibition performance of the multifunctional phosphorus-free boiler water treatment agent prepared, and ensure the safe operation of the boiler system.

[0041] Preferably, the multifunctional filler includes at least one of calcium carbonate, porous zeolite powder, activated carbon, quartz powder, diatomite, and activated carbon fiber powder.

[0042] Preferably, the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder, and the mass ratio of the calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder is (0.8-1):(0.8-1):(0.8-1):(0.2-0.5).

[0043] Preferably, the multifunctional filler comprises a porous composite and an amino acid metal complex fixedly connected to the porous composite, and the porous composite is formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder at a mass ratio of 1:1:0.8:0.2. The metal element in the amino acid metal complex is fixedly connected to the porous composite in the form of a chemical bond. The amino acid in the amino acid metal complex comprises one or more combinations of alliin, aspartic acid, arginine, and glycine. Further, the metal element in the amino acid metal complex is iron, and the amino acid in the amino acid metal complex is composed of alliin, aspartic acid, and glycine at a mass ratio of (0.8-1):(0.8-1):(0.8-1).

[0044] The preparation method of the multifunctional filler comprises the following steps:

[0045] S1, preparation of a porous composite: uniformly mix calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder according to the proportion, and then place them in a muffle furnace for calcination treatment at a temperature of 80-120°C for 8-24h, and then grind and crush the obtained solid to obtain porous composite particles of a suitable particle size;

[0046] Meanwhile, a transition metal ligand is configured: accurately measure the amino acid, and then add it to deionized water and stir until uniform, wherein the mass ratio of the amino acid to the deionized water is (3-6):100, and then place it in a 50°C water bath for heating while stirring at a speed of 400-600rpm until the amino acid is completely dissolved to obtain an amino acid solution, and then add ferric sulfate to the amino acid solution, wherein the iron content in the ferric sulfate is 0.8-1.2 times the amino acid content, and then continue to heat in the 50°C water bath and stir at a speed of 400-600rpm for 4-8h to allow the amino acid and the iron to fully combine and coordinate to obtain a transition metal ligand;

[0047] S2, add the porous composite particles obtained in S1 to the transition metal ligand at a rate of 5-10g / min, wherein the mass ratio of the porous composite particles to the transition metal ligand is (20-40):100, and then perform ultrasonic dispersion treatment for 1-2h, and then perform magnetic stirring for 12-24h, and then wash with deionized water until neutral, and then filter, and then dry at 80-85°C for 8-12h, and then cool to room temperature to obtain a solid;

[0048] The solid obtained in S3 and S2 is heated to 180-220℃ at a heating rate of 4-6℃ / min under an argon atmosphere for 6-8h, and the solid product obtained is placed in a planetary ball mill for ball milling treatment, and then is sieved to obtain multifunctional fillers with a suitable particle size.

[0049] The composite water treatment agent 12 is mainly prepared from the following raw materials by weight: 10-20 parts of a scale remover, 0.5-2 parts of sodium D-isoascorbate, 1-3 parts of 1-amino-4-methylpiperazine, 1-3 parts of N,N-dicarboxylic acid amino-2-hydroxypropane sodium sulfonate, and 1-3 parts of 3-acrylamidodopamine. The scale remover is a terpolymer prepared from N-methyl acryloyl glycine, 2-methyl-2-acrylamidopropyl sulfonic acid, and hydroxypropyl acrylate.

[0050] Preferably, the composite water treatment agent is mainly prepared from the following raw materials by weight: 16-18 parts of a scale remover, 1.2-1.6 parts of sodium D-isoascorbate, 2.0-2.6 parts of 1-amino-4-methylpiperazine, 1.5-2.4 parts of N,N-dicarboxylic acid amino-2-hydroxypropane sodium sulfonate, and 2-3 parts of 3-acrylamidodopamine.

[0051] Preferably, the first microporous membrane 1 and the second microporous membrane 2 are thermoplastic polyolefin membranes, so as to reduce the probability of chemical reaction between the first microporous membrane 1 and the second microporous membrane 2 and the composite water treatment agent 12.

[0052] The preparation method of the multifunctional phosphorus-free boiler water treatment agent comprises the following steps

[0053] Step one, preparation of the multifunctional filler 22 and the composite water treatment agent 12;

[0054] Step two, the thermoplastic polyolefin membrane is used as the first microporous membrane 1, and the prepared composite water treatment agent 12 is coated in the first microporous membrane 1 by using a laundry bead automatic packaging machine to prepare a semi-finished water treatment granular preparation with a particle size of 8-16mm.

[0055] Step three, the multifunctional filler 22 in step one is mixed with water-soluble glue at a mass ratio of (0.8-0.9):(0.1-0.2) to prepare a multifunctional filler film layer with a thickness of 0.5-1.0mm, and the multifunctional filler film layer is coated on the outer wall of the semi-finished water treatment granular preparation obtained in step two, so as to prepare a semi-finished product.

[0056] Step four, the thermoplastic polyolefin membrane is used as the second microporous membrane 2, and the second microporous membrane 2 is coated on the outer wall of the semi-finished product, i.e. the outer wall of the multifunctional filler film layer, by using a laundry bead automatic packaging machine, so as to prepare a multifunctional phosphorus-free boiler water treatment agent.

[0057] Example 1: A multifunctional phosphorus-free boiler water treatment agent disclosed in the present application comprises a first microporous membrane 1 and a second microporous membrane 2, the first microporous membrane 1 is inside the second microporous membrane 2. The first microporous membrane 1 is formed with a first microporous channel 11 for water body flow, the first microporous membrane 1 is a PP microporous membrane material with a thickness of 120 microns, the pore size of the first microporous channel 11 is in the range of 45 microns, and it is customized by Jiangsu Green Alliance Scientific Instrument Co., Ltd., model RMF50P1. The second microporous membrane 2 is formed with a second microporous channel 23 for water body flow, the second microporous membrane 2 is a PP microporous membrane material with a thickness of 120 microns, the pore size of the second microporous channel 23 is in the range of 45 microns, and it is customized by Jiangsu Green Alliance Scientific Instrument Co., Ltd., model RMF50P1.

[0058] The first microporous membrane 1 is filled with a composite water treatment agent 12. The composite water treatment agent 12 is made of the following weight parts of raw materials: 16.8 parts of scale remover, 1.5 parts of sodium D-isoascorbate, 2.4 parts of 1-amino-4-methyl piperazine, 2.0 parts of N,N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, and 2.5 parts of 3-acrylamidodopamine. The scale remover is a terpolymer made of N-methyl acryloyl glycine, 2-methyl-2-acrylamidopropyl sulfonic acid, and hydroxypropyl acrylate in a molar ratio of 1:1:1.

[0059] A filling layer 21 is formed between the second microporous membrane 2 and the first microporous membrane 1, and the filling layer 21 is filled with multifunctional filler 22. The multifunctional filler 22 is 4A zeolite powder (from Lingshou County Yongbuzhichu Mineral Products Operating Department) sieved out by 200-2500 mesh.

[0060] The pore size (45 microns) of the first microporous channel 11 is smaller than the particle size (200-2500 mesh, i.e. 58-74 microns) of the multifunctional filler 22. The multifunctional filler 22 located in the filling layer 21 is coated on the outer wall of the first microporous membrane 1 and inside the second microporous membrane 2, and the pore size (45 microns) of the second microporous channel 23 is smaller than the particle size (i.e. 58-74 microns) of the multifunctional filler 22.

[0061] In the process of boiler water treatment, the multifunctional filler 22 is always between the first microporous membrane 1 and the second microporous membrane 2, and the multifunctional filler 22 adsorbs the solid slag formed by calcium and magnesium ions and the composite water treatment agent, which can improve the scale inhibition and corrosion inhibition performance of the prepared multifunctional phosphorus-free boiler water treatment agent, and ensure the safe operation of the boiler system.

[0062] A preparation method of a multifunctional phosphorus-free boiler water treatment agent, comprising the following steps

[0063] Step one, preparation of multifunctional filler: 200-2500 mesh sieved 4A zeolite powder is activated at 120°C for 4h;

[0064] Preparation of the composite water treatment agent: 168 g of the scale inhibitor, 15 g of D-sodium isoascorbic acid, 24 g of 1-amino-4 methyl piperazine, 20 g of N, N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, 25 g of 3-acrylamido dopamine were weighed and mixed in a 500 mL beaker to obtain the finished product of the composite water treatment agent;

[0065] Step two, using PP microporous membrane material as the first microporous membrane, the composite water treatment agent prepared in step one was coated in the first microporous membrane by using a laundry bead automatic packaging machine to prepare a semi-finished water treatment granular preparation with a particle size of 15±0.2 mm.

[0066] Step three, the 4A zeolite powder activated in step one and PVA (polyvinyl alcohol) adhesive (viscosity 600, Jinan Wangtian Chemical Co., Ltd., industrial grade) were mixed in a mass ratio of 88:12 to prepare a multifunctional filler film layer with a thickness of 0.60 mm, and the multifunctional filler film layer was coated on the outer wall of the semi-finished water treatment granular preparation obtained in step two to obtain a semi-finished product.

[0067] Step four, using PP microporous membrane material as the second microporous membrane, the second microporous membrane was coated on the outer wall of the semi-finished product, i.e. the outer wall of the multifunctional filler film layer, to prepare a multifunctional phosphorus-free boiler water treatment agent.

[0068] The difference between Example 2 and Example 1 is that the composite water treatment agent 12 is prepared from the following weight parts of raw materials: 10 parts of scale inhibitor, 0.6 parts of D-sodium isoascorbic acid, 1.2 parts of 1-amino-4 methyl piperazine, 1.0 parts of N, N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, 1.2 parts of 3-acrylamido dopamine.

[0069] The difference between Example 3 and Example 1 is that the composite water treatment agent 12 is prepared from the following weight parts of raw materials: 20 parts of scale inhibitor, 1.8 parts of D-sodium isoascorbic acid, 3.0 parts of 1-amino-4 methyl piperazine, 3.0 parts of N, N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, 3.0 parts of 3-acrylamido dopamine.

[0070] The difference between Example 4 and Example 1 is that the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, and diatomite in a mass ratio of 1:1:1. The preparation method of the porous composite is as follows: the calcium carbonate, porous zeolite powder, and diatomite are mixed in the ratio and then calcined in a muffle furnace at a temperature of 85℃ for 12 h. The obtained solid is ground and crushed to obtain a porous composite particle with a particle size of 200-250 mesh.

[0071] The difference between Example 5 and Example 41 is that the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder in a mass ratio of 1:1:1:0.1.

[0072] The difference between Example 6 and Example 4 is that the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder in a mass ratio of 1:1:1:0.2.

[0073] The difference between Example 7 and Example 4 is that the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder in a mass ratio of 1:1:1:0.35.

[0074] The difference between Example 8 and Example 4 is that the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder in a mass ratio of 1:1:1:0.5.

[0075] The difference between Example 9 and Example 4 is that the multifunctional filler is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder in a mass ratio of 1:1:1:0.6.

[0076] The difference between Example 10 and Example 1 is that the multifunctional filler includes a porous composite and an amino acid metal complex fixedly connected to the porous composite, and the porous composite is a porous composite formed by calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder in a mass ratio of 1:1:1:0.2. The metal element iron in the amino acid metal complex is fixedly connected to the porous composite in the form of a chemical bond. The amino acid in the amino acid metal complex is composed of alliin, aspartic acid, and glycine in a mass ratio of 1:1:1.

[0077] The preparation method of the multifunctional filler includes the following steps:

[0078] S1, preparation of a porous composite: uniformly mix calcium carbonate, porous zeolite powder, diatomite, and activated carbon fiber powder according to the ratio, and then place them in a muffle furnace for calcination treatment at a temperature of 85°C for 12 hours. Grind and crush the obtained solid to obtain porous composite particles with a particle size of 200-250 mesh.

[0079] Meanwhile, a transition metal ligand is configured: accurately measure the amino acid, add it to deionized water, and stir until uniform. The mass ratio of the amino acid to the deionized water is 5:100. Then, heat in a 50°C water bath while stirring at a speed of 400 rpm until the amino acid is completely dissolved to obtain an amino acid solution. Then, add iron sulfate to the amino acid solution, and the iron content in the iron sulfate is 1.05 times the amino acid content. Continue heating in a 50°C water bath and stirring at a speed of 40 rpm for 8 hours to allow the amino acid and iron to fully combine and coordinate to obtain a transition metal ligand.

[0080] S2, the porous composite particles obtained in S1 were added to the transition metal ligand at a mass ratio of porous composite particles to transition metal ligand of 32:100, and ultrasonic dispersion treatment was performed for 2 h, followed by magnetic stirring for 24 h, washing with deionized water until neutral, filtration, drying at 85°C for 8 h, and cooling to room temperature to obtain a solid product;

[0081] S3, the solid product obtained in S2 was heated to 220°C at a heating rate of 5°C / min under an argon atmosphere and held for 6.0 h, the obtained solid product was subjected to ball milling treatment in a planetary ball mill, and sieving treatment was performed to obtain a multifunctional filler with a particle size of 200-250 mesh.

[0082] Example 11 differs from Example 10 in that the multifunctional filler comprises a porous composite and a single-atom iron fixedly connected to the porous composite, and the porous composite is formed from calcium carbonate, porous zeolite powder, and diatomite at a mass ratio of 1:1:1.

[0083] A method for preparing a multifunctional filler, comprising the following steps:

[0084] S1, preparation of a porous composite: calcium carbonate, porous zeolite powder, and diatomite were mixed at a predetermined ratio and then placed in a muffle furnace for calcination treatment at a temperature of 85°C for 12 h, and the obtained solid product was ground and broken to obtain porous composite particles with a particle size of 200-250 mesh;

[0085] S2, the porous composite particles were added to a 5 g / L iron sulfate solution at a mass ratio of carrier to transition metal of 20:1, the obtained solution was uniformly dispersed by ultrasonic treatment at 100 kHz for 30 min at room temperature, and then stirring was performed using a stirrer at 400 r / min for 16 h, the mixed solution was heated to the boiling point of water, high-temperature volatilization was performed, the solvent was evaporated, and the obtained solid product was cooled to room temperature;

[0086] S3, the solid product obtained in S2 was heated to 200°C at a heating rate of 5°C / min under an argon atmosphere and held for 6.0 h, the solid product was subjected to ball milling treatment in a planetary ball mill, and sieving treatment was performed to obtain a multifunctional filler with a particle size of 200-250 mesh.

[0087] Example 12 differs from Example 11 in that the porous composite in the multifunctional filler is replaced by 4A zeolite powder with a particle size of 200-2500 mesh.

[0088] Comparative Example 1 differs from Example 1 in that the outer wall of the first microporous membrane of the multifunctional phosphorus-free boiler water treatment agent is not provided with a second microporous membrane and a multifunctional filler.

[0089] Comparative Example 2 differs from Example 1 in that the ALB-625 boiler water comprehensive treatment agent is commercially available.

[0090] Comparative Example 3 differs from Example 1 in that the composite water treatment agent is made from the following raw materials by weight: 16.8 parts of scale inhibitor 2-methyl-2-propenoylamino propyl sulfonic acid, 1.5 parts of sodium D-isoascorbate, 2.4 parts of 1-amino-4-methyl piperazine, 2.0 parts of N,N-dicarboxylic acid amino-2-hydroxy propane sodium sulfonate, 2.5 parts of 3-acrylamido dopamine.

[0091] In addition, in order to adapt to the use of the multifunctional phosphorus-free boiler water treatment agent in the present application, the present application relates to a porous ceramic water treatment column for multifunctional phosphorus-free boiler water treatment agent. The porous ceramic water treatment column is a porous water-permeable ceramic column made of silicon carbide by a foaming ceramic process. The silicon carbide porous ceramic column is made of a plurality of silicon carbide porous ceramic unit columns. The single silicon carbide porous ceramic unit column comprises a first silicon carbide porous ceramic half column and a second silicon carbide porous ceramic half column, and the first silicon carbide porous ceramic half column and the second silicon carbide porous ceramic half column are inserted. A plurality of spherical cavities are formed between the inserted first silicon carbide porous ceramic half column and the second silicon carbide porous ceramic half column in a lattice distribution, the diameter of the spherical cavities is 20 mm, and the multifunctional phosphorus-free boiler water treatment agent prepared in the present application is placed in the spherical cavities. The boiler water is circulated through the porous ceramic water treatment column for filtration, which can effectively ensure the safe operation of the boiler system.

[0092] Performance test 1, corrosion inhibition performance test method: according to the standard of GB / T16811-2018 Industrial boiler water treatment facilities operation effect and monitoring, the water treatment agent sample is tested, then the corrosion inhibition rate is detected, and the water treatment agent sample dosage is 15 mg / L. 2, pressure boiler simulation test method: the performance of the agent is evaluated using a laboratory medium pressure boiler simulation device, the boiler feed water uses secondary reverse osmosis + electric desalination process water, the measured conductivity is 0.62 μs / cm, the equipment operating pressure is 3.6 MPa, the dosage is 20 g / t according to the feed water, and the carbon steel monitoring hanging piece in the furnace cavity, steam pocket and condenser pipeline is checked and recorded after continuous operation for 2 weeks. 3, deoxidation effect test method: the temperature of the deaerator is controlled at 104℃, the pressure is 0.02 MPa, the water treatment agent is added to the boiler water, the addition amount is 15 mg / L, the blank group does not add the water treatment agent, after 24 h treatment, the dissolved oxygen content in the boiler water is measured by using the dissolved oxygen tester.

[0093] Table 1 is the test parameter table of the multifunctional phosphorus-free boiler water treatment agent in Examples 1-12 and Comparative Examples 1-3

[0094]

[0095]

[0096]

[0097] As can be seen from Examples 1-12 and Comparative Examples 1-3 and Table 1, the difference between Example 1 and Comparative Example 1 is relatively small in terms of scale inhibition and oxygen removal performance, and the main difference between them is the corrosion inhibition performance. In the present application, the multifunctional filler is compounded between the first microporous membrane and the second microporous membrane, which not only improves the overall scale inhibition, oxygen removal and corrosion inhibition performance, but also stores the solid residue formed by the adsorption of calcium and magnesium ions and the multifunctional water treatment agent between the first microporous membrane and the second microporous membrane. The boiler water treated by the multifunctional phosphorus-free boiler water treatment agent combined with the porous ceramic water treatment column in the present application does not need to be subjected to secondary floating residue filtration as in the prior art, which shortens the water treatment section, improves the water treatment efficiency, reduces labor costs, and achieves the development goal of improving quality and efficiency.

[0098] As can be seen from Examples 1-12 and Comparative Examples 1-3 and Table 1, the multifunctional phosphorus-free boiler water treatment agent provided in the present application has better overall performance than the commercially available phosphorus boiler water treatment agent in the prior art. In addition, the multifunctional phosphorus-free boiler water treatment agent in the present application is combined with a slow-release technology to provide long-lasting scale inhibition, oxygen removal and corrosion inhibition.

[0099] As can be seen from Examples 1-12 and Comparative Examples 1-3 and Table 1, the combination of the composite water treatment agent provided in the present application can give the multifunctional phosphorus-free boiler water treatment agent better scale inhibition, oxygen removal and corrosion inhibition. Preferably, the composite water treatment agent is made of the following raw materials in parts by weight: 16-18 parts of scale remover, 1.2-1.6 parts of D-sodium isoascorbate, 2.0-2.6 parts of 1-amino-4-methyl piperazine, 1.5-2.4 parts of N,N-dicarboxylic acid amino-2-hydroxy propane sulfonic acid sodium, and 2-3 parts of 3-acrylamido dopamine.

[0100] As can be seen from Examples 1-12 and Comparative Examples 1-3 and Table 1, the multifunctional filler formed by calcium carbonate, porous zeolite powder, diatomite and activated carbon fiber powder in a mass ratio of (0.8-1):(0.8-1):(0.8-1):(0.2-0.5) has relatively good scale inhibition, oxygen removal and corrosion inhibition performance, and can also purify and disinfect water quality.

[0101] It can be seen from the combination of embodiments 1-12 and comparative examples 1-3 and table 1 that, compared with embodiments 10-12, the multifunctional filler prepared in embodiment 10 has relatively better scale inhibition, oxygen removal and corrosion inhibition, and can further purify and disinfect water quality, and the amino acid metal complex contained therein can better adjust the pH value of water quality.

[0102] The porous ceramic water treatment column provided in the present application is used in combination with the multifunctional phosphorus-free boiler water treatment agent, which not only effectively ensures better scale inhibition, oxygen removal and corrosion inhibition of the multifunctional phosphorus-free boiler water treatment agent, but also does not need to be subjected to the secondary floating sludge filtration involved in the prior art, and only needs to be regularly maintained to fully play its functions, shortens the water treatment section, is beneficial to improving the water treatment efficiency, simultaneously reduces the labor cost, and achieves the development purpose of improving the quality and efficiency of enterprises.

[0103] The multifunctional phosphorus-free boiler water treatment agent in embodiment 10 is subjected to a durability test in the present application, and still has excellent corrosion resistance and scale inhibition performance after continuous operation for 5 weeks under the pressure boiler simulation experiment test, the surface of the test piece is bright, and no dirt is attached.

[0104] In summary, the multifunctional phosphorus-free boiler water treatment agent in the present application has good environmental protection performance, and simultaneously has good scale inhibition and corrosion inhibition effects, can guarantee the safe operation of the boiler system, and meets the current environmental protection development trend of the boiler water treatment agent.

[0105] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A multifunctional, non-phosphorus, boiler water treatment agent, characterized in that: The invention comprises a first microporous membrane (1) and a second microporous membrane (2), wherein a first microporous channel (11) for water circulation is formed in the first microporous membrane (1); a composite water treatment agent (12) is filled in the first microporous membrane (1); the first microporous membrane (1) is located inside the second microporous membrane (2), and a filling layer (21) is formed between the second microporous membrane (2) and the first microporous membrane (1); the filling layer (21) is filled with a multifunctional filler (22); the first microporous membrane (1) and the second microporous membrane (2) are thermoplastic polyolefin membranes, so as to reduce the probability of chemical reaction between the first microporous membrane (1) and the second microporous membrane (2) and the composite water treatment agent (12); The pore size of the first microporous channel (11) is smaller than the particle size of the multifunctional filler (22); the multifunctional filler (22) in the filling layer (21) is coated on the outer wall of the first microporous membrane (1) and is located inside the second microporous membrane (2); a second microporous channel (23) for water circulation is formed in the second microporous membrane (2), and the pore size of the second microporous channel (23) is smaller than the particle size of the multifunctional filler (22); During the boiler water treatment process, the multifunctional filler (22) is always located between the first microporous membrane (1) and the second microporous membrane (2); The multifunctional filler (22) comprises a porous composite and an amino acid metal complex fixedly connected to the porous composite, wherein the porous composite is made of calcium carbonate, porous zeolite powder, diatomaceous earth and activated carbon fiber powder; the metal element in the amino acid metal complex is fixedly connected to the porous composite in the form of a chemical bond; the amino acids in the amino acid metal complex are composed of alliin, aspartic acid and glycine in a mass ratio of (0.8-1):(0.8-1):(0.8-1); the metal element in the amino acid metal complex is iron; the mass ratio of the calcium carbonate, porous zeolite powder, diatomaceous earth and activated carbon fiber powder is (0.8-1):(0.8-1):(0.8-1):(0.2-0.5); The composite water treatment agent (12) is mainly made of the following raw materials in parts by weight: 10-20 parts of a descaling agent, 0.5-2 parts of sodium D-isoascorbate, 1-3 parts of 1-amino-4-methylpiperazine, 1-3 parts of sodium N,N-dicarboxylic acid amino-2-hydroxypropyl sulfonate and 1-3 parts of 3-acrylamidopamine, wherein the descaling agent is a terpolymer made of N-methylacryloylglycine, 2-methyl-2-acrylamidopropyl sulfonic acid and hydroxypropyl acrylate.

2. A multifunctional phosphorous-free boiler water treatment agent according to claim 1, characterized in that: The porous composite is made of calcium carbonate, porous zeolite powder, diatomaceous earth and activated carbon fiber powder in a mass ratio of 1:1:0.8:0.

2.

3. A multifunctional phosphorous-free boiler water treatment agent according to claim 2, characterized in that: The preparation method of the multifunctional filler (22) comprises the following steps: S1, preparation of porous composite: calcium carbonate, porous zeolite powder, diatomaceous earth and activated carbon fiber powder are uniformly mixed according to the proportions and then calcined in a muffle furnace at a temperature of 80-120° C. for 8-24 hours. The resulting solid is ground and crushed to obtain porous composite particles of suitable particle size; Simultaneous configuration of transition metal ligand: accurately metered amino acid is added to deionized water and stirred until uniform, the mass ratio of the amino acid to deionized water is (3-6):100, then placed in a 50℃ water bath to heat, while stirring at a speed of 400-600 rpm until the amino acid is completely dissolved, obtaining an amino acid solution, then adding ferric sulfate to the amino acid solution, the iron content of the ferric sulfate is equal to 0.8-1.2 times the amino acid content, continue to stir at 400-600 rpm for 4-8 h under a 50℃ water bath to allow the amino acid to fully combine with iron to form a transition metal ligand; S2, the porous composite particles obtained in S1 are added to the transition metal ligand at a rate of 5-10 g / min, the mass ratio of the porous composite particles to the transition metal ligand is (20-40):100, ultrasonic dispersion treatment is performed for 1-2 h, then magnetic stirring is performed for 12-24 h, washed with deionized water until neutral, filtered, dried at 80-85℃ for 8-12 h, and cooled to room temperature to obtain a solid product; S3, the solid product obtained in S2 is heated to 180-220℃ at a heating rate of 4-6℃ / min under an argon atmosphere and held for 6-8 h, the obtained solid product is placed in a planetary ball mill for ball milling treatment, and sieving treatment is performed to obtain a multifunctional filler with a suitable particle size.

4. A multifunctional phosphorous-free boiler water treatment agent according to claim 3, characterized in that: The composite water treatment agent (12) is mainly prepared from the following raw materials in parts by weight: 16-18 parts of a scale remover, 1.2-1.6 parts of sodium D-erythorbate, 2.0-2.6 parts of 1-amino-4-methylpiperazine, 1.5-2.4 parts of N,N-dicarboxylic acid amino-2-hydroxypropane sodium sulfonate, and 2-3 parts of 3-acrylamidodopamine.

5. A process for the preparation of the multifunctional phosphorus-free boiler water treatment agent according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: Step one, preparation of the multifunctional filler (22) and the composite water treatment agent (12); Step two, a thermoplastic polyolefin film is used as the first microporous film (1), and the prepared composite water treatment agent (12) is coated in the first microporous film (1) by using a laundry bead automatic packaging machine to obtain a semi-finished water treatment particle preparation with a particle size of 8-16 mm; Step three, the multifunctional filler (22) in step one is mixed with water-soluble glue to form a multifunctional filler film layer, and the multifunctional filler film layer is coated on the outer wall of the semi-finished water treatment particle preparation obtained in step two to obtain a semi-finished product; Step four, a thermoplastic polyolefin film is used as the second microporous film (2), and the second microporous film (2) is coated on the outer wall of the semi-finished product, i.e., the outer wall of the multifunctional filler film layer, by using a laundry bead automatic packaging machine to obtain a multifunctional phosphorus-free boiler water treatment agent.

6. A process for the preparation of a multifunctional phosphorus-free boiler water treatment agent according to claim 5, characterized in that: In step three, the multifunctional filler (22) in step one is mixed with water-soluble glue at a mass ratio of (0.8-0.9):(0.1-0.2) to form a multifunctional filler film layer with a thickness of 0.5-1.0 mm.

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