CN113955836A - Polyaluminium chloride medicament composition and preparation method thereof - Google Patents
Polyaluminium chloride medicament composition and preparation method thereof Download PDFInfo
- Publication number
- CN113955836A CN113955836A CN202111562367.9A CN202111562367A CN113955836A CN 113955836 A CN113955836 A CN 113955836A CN 202111562367 A CN202111562367 A CN 202111562367A CN 113955836 A CN113955836 A CN 113955836A
- Authority
- CN
- China
- Prior art keywords
- solution
- chitosan
- chloride
- polyaluminium
- acid
- 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.)
- Pending
Links
Classifications
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Biochemistry (AREA)
- Dispersion Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to the technical field of water purifying agent preparation, and discloses a polyaluminium chloride medicament composition and a preparation method thereof, wherein the polyaluminium chloride medicament composition comprises the following raw materials in parts by weight: 30-40 parts of polyaluminium chloride, 10-15 parts of polyaluminium sulfate and 10-15 parts of ferric sulfate; the polyaluminium chloride medicament composition is prepared by microencapsulating polyaluminium chloride, polyaluminium sulfate and ferric sulfate by using a chitosan solution, wherein the chitosan solution is formed by dissolving modified chitosan in an acetic acid solution; arc pair electrons on nitrogen in modified chitosan molecules are chemically adsorbed with monovalent copper ions on a copper pipeline to form a protective film, meanwhile, metal ions and triazole ring electrons form sigma coordination bonds, and a full d track of the metal ions provides electrons to a symmetrical empty track of triazole to form feedback pi bonds, so that a crystal field is split, the molecular track energy is reduced, the stability of the protective film is improved, further, the corrosion of the copper pipeline is prevented, and the corrosion of a water pipe caused by overhigh corrosivity of polyaluminium chloride is avoided.
Description
Technical Field
The invention relates to the technical field of water purifying agent preparation, and particularly relates to a polyaluminium chloride medicament composition and a preparation method thereof.
Background
The lack of water resources is a big problem in China all the time, especially along with the rapid development of domestic economy in recent years, the water consumption rises rapidly, the pollution of water resources is becoming more and more serious, and the industrial water treatment technology has important significance for saving water resources, reducing water pollution, prolonging the service life of equipment and the like;
therefore, with the continuous improvement of industrial water treatment and environmental protection requirements, the water treatment agent in China is rich in varieties, the performance is continuously improved, the water treatment agent products are various in variety, and the water treatment agent is diversified from low molecules to high molecules, from inorganic to organic, and from single to composite, and in specific practical application cases, the water treatment agent adopts comprehensive application formula modes such as synergistic interaction, multiple effects of one agent, multiple compounding and the like;
however, in the process of using various water treatment agents with good performance, the water treatment agents have certain corrosivity, so that equipment and pipelines are corroded to different degrees, the cost of water treatment is greatly improved, meanwhile, the effect of water treatment is general, the standard can be reached by multiple treatments, and the treatment efficiency is greatly reduced.
Disclosure of Invention
The invention aims to provide a polyaluminium chloride medicament composition and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a polyaluminium chloride medicament composition comprises the following raw materials in parts by weight: 30-40 parts of polyaluminium chloride, 10-15 parts of polyaluminium sulfate and 10-15 parts of ferric sulfate;
the polyaluminium chloride medicament composition is prepared by the following steps:
step S1: uniformly mixing polyaluminium chloride, polyaluminium sulfate and ferric sulfate to prepare a mixture;
step S2: dissolving the modified chitosan in an acetic acid solution to prepare a chitosan solution, uniformly mixing the gelatin solution, the chitosan solution and the mixture, stirring at the rotation speed of 200-300r/min, the temperature of 50-55 ℃ and the pH value of 6-6.5 for 20-30min, cooling to the temperature of 30-35 ℃, adding glutaraldehyde, reacting for 1-1.5h, filtering to remove filtrate, and drying filter cakes to prepare the polyaluminium chloride medicament composition.
Furthermore, the dosage ratio of the modified chitosan to the acetic acid solution is 1g to 20mL, and the mass fraction of the acetic acid solution is 1%.
Further, the modified chitosan is prepared by the following steps:
step A1: adding 3, 5-dimethylbenzoic acid, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, dimethylaminoethanol, p-toluenesulfonic acid and N, N-dimethylformamide, reacting for 6-8h at the rotation speed of 150-200r/min and the temperature of 100-110 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, hexamethylenetetramine, deionized water and ethanol, refluxing for 2-3h at the rotation speed of 200-300r/min and the temperature of 80-90 ℃, cooling to room temperature, adding concentrated sulfuric acid, continuously refluxing for 1-1.5h at the temperature of 110-120 ℃, to prepare an intermediate 3;
the reaction process is as follows:
step A2: uniformly mixing 3, 4-diaminobenzoic acid, ethanol and concentrated sulfuric acid, performing reflux reaction for 1-2h at the temperature of 100-110 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, hydrazine hydrate and ethanol, performing reflux reaction for 2-4h at the temperature of 90-100 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium hydroxide and ethanol, stirring and dropwise adding carbon disulfide at the rotation speed of 150-200r/min, reacting for 1-2h, adding diethyl ether, continuously reacting for 1-1.5h, filtering to remove filtrate, adding a filter cake into hydrazine hydrate, performing reflux reaction for 3-5h at the temperature of 120-130 ℃, adjusting the pH value of the reaction solution to be 3, and standing for 10-15h to obtain an intermediate 6;
the reaction process is as follows:
step A3: uniformly mixing the intermediate 6, deionized water and glacial acetic acid, stirring and dripping sodium nitrite solution under the conditions of a rotation speed of 150-, distilling to remove the solvent, uniformly mixing the substrate, the hydrogen bromide solution and the acetic acid, and carrying out reflux reaction for 3-5h at the temperature of 120-130 ℃ to prepare an intermediate 9;
the reaction process is as follows:
step A4: dissolving an intermediate 7 in tetrahydrofuran, adding triethylamine, stirring and adding an intermediate 9 under the conditions that the rotation speed is 200-300r/min and the temperature is 1-3 ℃, heating to the temperature of 20-25 ℃, reacting for 8-10h, adding dibromoethane and sodium carbonate, continuing to react for 3-5h to obtain an intermediate 10, dissolving chitosan in an acetic acid solution, adding an intermediate 3, ethanol and magnesium chloride, stirring and refluxing for 3-5h under the conditions that the rotation speed is 200-300r/min and the temperature is 70-80 ℃, adding an intermediate 10 and acetone, and refluxing for 6-8h under the condition that the temperature is 55-60 ℃ to obtain pre-modified chitosan;
the reaction process is as follows:
step A5: dissolving pre-modified chitosan into hydrochloric acid solution, adding acrylic acid and ferric trichloride, reacting for 8-10h at the rotation speed of 150-.
The reaction process is as follows:
further, the amount ratio of the 3, 5-dimethylbenzoic acid, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride in the step A1 is 0.1mol:0.1mol:0.15:200mL, the amount molar ratio of the intermediate 1 to the dimethylaminoethanol is 1:1, the amount molar ratio of the intermediate 2, the hexamethylenetetramine, the ethanol and the concentrated sulfuric acid is 1:1.5:4:2.5, and the mass fraction of the concentrated sulfuric acid is 98%.
Further, the molar ratio of the 3, 4-diaminobenzoic acid to ethanol in the step A2 is 1:1, the molar ratio of the intermediate 4 to hydrazine hydrate is 1:1.1, and the molar ratio of the intermediate 5, potassium hydroxide, carbon disulfide and hydrazine hydrate is 1:5:2: 3.
Further, the using amount ratio of the intermediate 6, the deionized water, the glacial acetic acid and the sodium nitrite solution in the step A3 is 0.1:30:0.2:15, the mass fraction of the sodium nitrite solution is 50%, the using amount molar ratio of the hydroxymalonic acid to the dimethyl sulfate is 1:1, the using amount ratio of the intermediate 8, the thionyl chloride and the hydrogen bromide solution is 0.01:0.02:20mL, and the mass fraction of the hydrogen bromide solution is 45%.
Further, the molar ratio of the intermediate 7, triethylamine, the intermediate 9, dibromoethane and sodium carbonate in the step A4 is 2:2:1:1:2, and the molar ratio of chitosan, the intermediate 3, magnesium chloride and the intermediate 10 is 1:1.5:0.3: 1.2.
Further, the mass ratio of the pre-modified chitosan, the acrylic acid, the dimethyl diallyl ammonium chloride and the potassium persulfate in the step A5 is 1:2:3: 0.05.
The invention has the following beneficial effects:
the polyaluminium chloride medicament composition prepared by the invention has good adsorption, condensation and precipitation effects by compounding polyaluminium chloride, polyaluminium sulfate and ferric sulfate, but the polyaluminium chloride has poor stability, the polyaluminium chloride is not deteriorated by microencapsulation treatment, a chitosan solution is added in the microencapsulation treatment process, the chitosan solution takes modified chitosan as a raw material, the modified chitosan takes 3, 5-dimethylbenzoic acid as a raw material to carry out bromination treatment to prepare an intermediate 1, the intermediate 1 is reacted with dimethylaminoethanol to prepare an intermediate 2, the intermediate 2 is further treated to prepare an intermediate 3, the 3, 4-diaminobenzoic acid is reacted with ethanol to prepare an intermediate 4, the intermediate 4 is reacted with hydrazine hydrate to prepare an intermediate 5, the intermediate 5 is further treated, preparing an intermediate 6, treating the intermediate 6 with sodium nitrite to prepare an intermediate 7, performing hydroxyl protection on hydroxymalonic acid with dimethyl sulfate to prepare an intermediate 8, reacting the intermediate 8 with thionyl chloride, performing deprotection to prepare an intermediate 9, reacting the intermediate 7 with the intermediate 9 to prepare an intermediate 10, reacting chitosan with the intermediate 3 to react amino on chitosan with aldehyde groups on the intermediate 3, then reacting with the intermediate 10 to prepare pre-modified chitosan, performing esterification reaction on the pre-modified chitosan and acrylic acid, polymerizing with dimethyl diallyl ammonium chloride to prepare modified chitosan, adding gelatin into water to dissolve the polyaluminium chloride medicament composition, opening the microcapsule to release polyaluminium chloride, polyaluminium sulfate and ferric sulfate, and simultaneously performing chemical adsorption on arc pair electrons on nitrogen in modified chitosan molecules on a copper pipeline to form a protective film with monovalent copper ions, meanwhile, the metal ions and electrons of the triazole ring form sigma coordination bonds, the d track filled with the metal ions provides electrons to the symmetrical empty track of the triazole to form feedback pi bonds, so that the crystal field is split, the molecular track energy is reduced, the stability of the protective film is improved, further, the corrosion of a copper pipeline is prevented, the corrosion of a water pipe caused by overhigh corrosivity of polyaluminium chloride is avoided, and the modified chitosan molecules are cationic quaternary ammonium salts and can play a role in charge neutralization and adsorption bridging with particles in water, so that the particles in the system are destabilized and flocculated to facilitate sedimentation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A polyaluminium chloride medicament composition comprises the following raw materials in parts by weight: 30 parts of polyaluminium chloride, 10 parts of polyaluminium sulfate and 10 parts of ferric sulfate;
the polyaluminium chloride medicament composition is prepared by the following steps:
step S1: uniformly mixing polyaluminium chloride, polyaluminium sulfate and ferric sulfate to prepare a mixture;
step S2: dissolving the modified chitosan in an acetic acid solution to prepare a chitosan solution, uniformly mixing the gelatin solution, the chitosan solution and the mixture, stirring at the rotation speed of 200r/min, the temperature of 50 ℃ and the pH value of 6 for 20min, cooling to the temperature of 30 ℃, adding glutaraldehyde, reacting for 1h, filtering to remove filtrate, and drying a filter cake to prepare the polyaluminium chloride medicament composition.
The modified chitosan is prepared by the following steps:
step A1: adding 3, 5-dimethylbenzoic acid, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, dimethylaminoethanol, p-toluenesulfonic acid and N, N-dimethylformamide, reacting for 6 hours at the rotation speed of 150r/min and the temperature of 100 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, hexamethylenetetramine, deionized water and ethanol, refluxing for 2 hours at the rotation speed of 200r/min and the temperature of 80 ℃, cooling to room temperature, adding concentrated sulfuric acid, and continuously refluxing for 1 hour at the temperature of 110 ℃ to obtain an intermediate 3;
step A2: uniformly mixing 3, 4-diaminobenzoic acid, ethanol and concentrated sulfuric acid, performing reflux reaction for 1h at the temperature of 100 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, hydrazine hydrate and ethanol, performing reflux reaction for 2h at the temperature of 90 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium hydroxide and ethanol, stirring and dropwise adding carbon disulfide at the rotation speed of 150r/min, reacting for 1h, adding diethyl ether, continuously reacting for 1h, filtering to remove filtrate, adding a filter cake into hydrazine hydrate, performing reflux reaction for 3h at the temperature of 120 ℃, adjusting the pH value of the reaction solution to be 3, and standing for 10h to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, deionized water and glacial acetic acid, stirring and dropwise adding a sodium nitrite solution under the conditions of the rotation speed of 150r/min and the temperature of 1 ℃, heating to the temperature of 70 ℃ to react for 2h, adding deionized water, filtering to remove filtrate to obtain an intermediate 7, uniformly mixing hydroxymalonic acid, potassium carbonate, dimethyl sulfate and acetone, stirring and refluxing for 3h under the conditions of the rotation speed of 150r/min and the temperature of 90 ℃ to obtain an intermediate 8, dissolving the intermediate 8 in N, N-dimethylformamide, stirring and dropwise adding thionyl chloride under the conditions of the rotation speed of 120r/min, heating to the temperature of 135 ℃, performing reflux reaction for 3h, distilling to remove a solvent, uniformly mixing a substrate, a hydrogen bromide solution and acetic acid, performing reflux reaction for 3h under the temperature of 120 ℃, to prepare an intermediate 9;
step A4: dissolving an intermediate 7 in tetrahydrofuran, adding triethylamine, stirring and adding an intermediate 9 under the conditions that the rotation speed is 200r/min and the temperature is 1 ℃, heating to the temperature of 20 ℃, reacting for 8 hours, adding dibromoethane and sodium carbonate, continuing to react for 3 hours to obtain an intermediate 10, dissolving chitosan in an acetic acid solution, adding an intermediate 3, ethanol and magnesium chloride, stirring and refluxing for 3 hours under the conditions that the rotation speed is 200r/min and the temperature is 70 ℃, adding an intermediate 10 and acetone, and refluxing for 6 hours under the conditions that the temperature is 55 ℃ to obtain pre-modified chitosan;
step A5: dissolving pre-modified chitosan in a hydrochloric acid solution, adding acrylic acid and ferric trichloride, reacting for 8 hours at the rotation speed of 150r/min and the temperature of 110 ℃, adding dimethyldiallylammonium chloride and potassium persulfate, reacting for 1 hour at the temperature of 50 ℃, heating to 80 ℃, and continuing to react for 2 hours to obtain the modified chitosan.
Example 2
A polyaluminium chloride medicament composition comprises the following raw materials in parts by weight: 35 parts of polyaluminium chloride, 13 parts of polyaluminium sulfate and 13 parts of ferric sulfate;
the polyaluminium chloride medicament composition is prepared by the following steps:
step S1: uniformly mixing polyaluminium chloride, polyaluminium sulfate and ferric sulfate to prepare a mixture;
step S2: dissolving the modified chitosan in an acetic acid solution to prepare a chitosan solution, uniformly mixing the gelatin solution, the chitosan solution and the mixture, stirring for 25min at the conditions of the rotation speed of 300r/min, the temperature of 53 ℃ and the pH value of 6.3, cooling to the temperature of 33 ℃, adding glutaraldehyde, reacting for 1.3h, filtering to remove filtrate, and drying a filter cake to prepare the polyaluminium chloride medicament composition.
The modified chitosan is prepared by the following steps:
step A1: adding 3, 5-dimethylbenzoic acid, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 9 hours at the temperature of 85 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, dimethylaminoethanol, p-toluenesulfonic acid and N, N-dimethylformamide, reacting for 7 hours at the rotation speed of 180r/min and the temperature of 105 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, hexamethylenetetramine, deionized water and ethanol, refluxing for 2.5 hours at the rotation speed of 300r/min and the temperature of 85 ℃, cooling to room temperature, adding concentrated sulfuric acid, and continuously refluxing for 1.3 hours at the temperature of 115 ℃ to obtain an intermediate 3;
step A2: uniformly mixing 3, 4-diaminobenzoic acid, ethanol and concentrated sulfuric acid, carrying out reflux reaction for 1.5h at the temperature of 105 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, hydrazine hydrate and ethanol, carrying out reflux reaction for 3h at the temperature of 95 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium hydroxide and ethanol, stirring and dropwise adding carbon disulfide at the rotation speed of 180r/min, reacting for 1.5h, adding diethyl ether, continuously reacting for 1.5h, filtering to remove filtrate, adding a filter cake into hydrazine hydrate, carrying out reflux reaction for 4h at the temperature of 125 ℃, adjusting the pH value of a reaction solution to be 3, and standing for 13h to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, deionized water and glacial acetic acid, stirring and dropwise adding a sodium nitrite solution under the conditions of a rotation speed of 180r/min and a temperature of 2 ℃, heating to a temperature of 75 ℃ for reaction for 3h, adding deionized water, filtering to remove filtrate to obtain an intermediate 7, uniformly mixing hydroxymalonic acid, potassium carbonate, dimethyl sulfate and acetone, stirring and refluxing for 4h under the conditions of a rotation speed of 180r/min and a temperature of 95 ℃ to obtain an intermediate 8, dissolving the intermediate 8 in N, N-dimethylformamide, stirring and dropwise adding thionyl chloride under the conditions of a rotation speed of 150r/min, heating to a temperature of 138 ℃, performing reflux reaction for 4h, distilling to remove a solvent, uniformly mixing a substrate, a hydrogen bromide solution and acetic acid, performing reflux reaction for 4h under the condition of a temperature of 125 ℃, to prepare an intermediate 9;
step A4: dissolving an intermediate 7 in tetrahydrofuran, adding triethylamine, stirring and adding an intermediate 9 under the conditions that the rotation speed is 200r/min and the temperature is 2 ℃, heating to the temperature of 23 ℃, reacting for 9 hours, adding dibromoethane and sodium carbonate, continuing to react for 4 hours to obtain an intermediate 10, dissolving chitosan in an acetic acid solution, adding an intermediate 3, ethanol and magnesium chloride, stirring and refluxing for 4 hours under the conditions that the rotation speed is 300r/min and the temperature is 75 ℃, adding an intermediate 10 and acetone, and refluxing for 7 hours under the condition that the temperature is 58 ℃ to obtain pre-modified chitosan;
step A5: dissolving pre-modified chitosan in a hydrochloric acid solution, adding acrylic acid and ferric trichloride, reacting for 9 hours at the rotation speed of 180r/min and the temperature of 115 ℃, adding dimethyldiallylammonium chloride and potassium persulfate, reacting for 2 hours at the temperature of 55 ℃, heating to 83 ℃, and continuing to react for 3 hours to obtain the modified chitosan.
Example 3
A polyaluminium chloride medicament composition comprises the following raw materials in parts by weight: 40 parts of polyaluminium chloride, 15 parts of polyaluminium sulfate and 15 parts of ferric sulfate;
the polyaluminium chloride medicament composition is prepared by the following steps:
step S1: uniformly mixing polyaluminium chloride, polyaluminium sulfate and ferric sulfate to prepare a mixture;
step S2: dissolving the modified chitosan in an acetic acid solution to prepare a chitosan solution, uniformly mixing the gelatin solution, the chitosan solution and the mixture, stirring for 30min at the conditions of the rotation speed of 300r/min, the temperature of 55 ℃ and the pH value of 6.5, cooling to the temperature of 35 ℃, adding glutaraldehyde, reacting for 1.5h, filtering to remove filtrate, and drying a filter cake to prepare the polyaluminium chloride medicament composition.
The modified chitosan is prepared by the following steps:
step A1: adding 3, 5-dimethylbenzoic acid, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into a reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 1, uniformly mixing the intermediate 1, dimethylaminoethanol, p-toluenesulfonic acid and N, N-dimethylformamide, reacting for 8 hours at the rotation speed of 200r/min and the temperature of 110 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, hexamethylenetetramine, deionized water and ethanol, refluxing for 3 hours at the rotation speed of 300r/min and the temperature of 90 ℃, cooling to room temperature, adding concentrated sulfuric acid, and continuously refluxing for 1.5 hours at the temperature of 120 ℃ to obtain an intermediate 3;
step A2: uniformly mixing 3, 4-diaminobenzoic acid, ethanol and concentrated sulfuric acid, performing reflux reaction for 2 hours at the temperature of 110 ℃ to obtain an intermediate 4, uniformly mixing the intermediate 4, hydrazine hydrate and ethanol, performing reflux reaction for 4 hours at the temperature of 100 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium hydroxide and ethanol, stirring and dropwise adding carbon disulfide at the rotation speed of 200r/min, reacting for 2 hours, adding diethyl ether, continuously reacting for 1.5 hours, filtering to remove filtrate, adding a filter cake into hydrazine hydrate, performing reflux reaction for 5 hours at the temperature of 130 ℃, adjusting the pH value of a reaction solution to be 3, and standing for 15 hours to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, deionized water and glacial acetic acid, stirring and dropwise adding a sodium nitrite solution under the conditions of a rotation speed of 200r/min and a temperature of 3 ℃, heating to a temperature of 80 ℃ to react for 3h, adding deionized water, filtering to remove filtrate to obtain an intermediate 7, uniformly mixing hydroxymalonic acid, potassium carbonate, dimethyl sulfate and acetone, stirring and refluxing for 5h under the conditions of a rotation speed of 200r/min and a temperature of 100 ℃ to obtain an intermediate 8, dissolving the intermediate 8 in N, N-dimethylformamide, stirring and dropwise adding thionyl chloride under the conditions of a rotation speed of 150r/min, heating to a temperature of 140 ℃, performing reflux reaction for 5h, distilling to remove a solvent, uniformly mixing a substrate, a hydrogen bromide solution and acetic acid, performing reflux reaction for 5h under the condition of a temperature of 130 ℃, to prepare an intermediate 9;
step A4: dissolving an intermediate 7 in tetrahydrofuran, adding triethylamine, stirring and adding an intermediate 9 under the conditions that the rotation speed is 300r/min and the temperature is 3 ℃, heating to the temperature of 25 ℃, reacting for 10 hours, adding dibromoethane and sodium carbonate, continuing to react for 5 hours to obtain an intermediate 10, dissolving chitosan in an acetic acid solution, adding an intermediate 3, ethanol and magnesium chloride, stirring and refluxing for 5 hours under the conditions that the rotation speed is 300r/min and the temperature is 80 ℃, adding an intermediate 10 and acetone, and refluxing for 8 hours under the condition that the temperature is 60 ℃ to obtain pre-modified chitosan;
step A5: dissolving pre-modified chitosan in a hydrochloric acid solution, adding acrylic acid and ferric trichloride, reacting for 10 hours at the rotation speed of 200r/min and the temperature of 120 ℃, adding dimethyldiallylammonium chloride and potassium persulfate, reacting for 3 hours at the temperature of 60 ℃, heating to 85 ℃, and continuing to react for 5 hours to obtain the modified chitosan.
Comparative example 1
This comparative example did not microencapsulate the mixture compared to example 1.
Comparative example 2
This comparative example is a polyaluminium chloride pharmaceutical composition disclosed in chinese patent CN 104276639A.
Comparative example 3
This comparative example is a polyaluminium chloride pharmaceutical composition disclosed in chinese patent CN 107983312A.
The polyaluminum chloride chemical compositions prepared in examples 1-3 and comparative examples 1-3 were added into wastewater at a rate of 10g/L, and after adsorption treatment was carried out at a rotation speed of 200-300r/min and a temperature of 25 ℃ for 3 hours, the metal ion concentration was measured, and 50 times of adsorption treatment was carried out to observe whether corrosion occurred on the surface of the copper tube, the results are shown in the following table:
from the above table, it can be seen that the polyaluminum chloride pharmaceutical compositions prepared in examples 1-3 have good metal ion adsorption effect, and do not corrode copper pipes after being used for many times, thereby reducing the water treatment cost.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A polyaluminum chloride pharmaceutical composition, characterized by: the feed comprises the following raw materials in parts by weight: 30-40 parts of polyaluminium chloride, 10-15 parts of polyaluminium sulfate and 10-15 parts of ferric sulfate;
the polyaluminium chloride medicament composition is prepared by microencapsulating polyaluminium chloride, polyaluminium sulfate and ferric sulfate by using a chitosan solution, wherein the chitosan solution is formed by dissolving modified chitosan in an acetic acid solution;
the modified chitosan is prepared by the following steps:
step A1: mixing 3, 5-dimethylbenzoic acid, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride for reaction to prepare an intermediate 1, mixing the intermediate 1, dimethylaminoethanol, p-toluenesulfonic acid and N, N-dimethylformamide for reaction to prepare an intermediate 2, mixing and refluxing the intermediate 2, hexamethylenetetramine, deionized water and ethanol, cooling to room temperature, adding concentrated sulfuric acid, and performing reflux reaction to prepare an intermediate 3;
step A2: mixing 3, 4-diaminobenzoic acid, ethanol and concentrated sulfuric acid for reflux to obtain an intermediate 4, mixing the intermediate 4, hydrazine hydrate and ethanol for reflux to obtain an intermediate 5, uniformly mixing the intermediate 5, potassium hydroxide and ethanol, stirring, dropwise adding carbon disulfide, reacting, adding diethyl ether for continuous reaction, filtering to remove filtrate, adding a filter cake into hydrazine hydrate, performing reflux reaction, adjusting the pH value of a reaction solution, and standing to obtain an intermediate 6;
step A3: uniformly mixing the intermediate 6, deionized water and glacial acetic acid, stirring and dropwise adding a sodium nitrite solution, heating for reaction, adding deionized water, filtering to remove filtrate to obtain an intermediate 7, mixing and refluxing hydroxymalonic acid, potassium carbonate, dimethyl sulfate and acetone to obtain an intermediate 8, dissolving the intermediate 8 in N, N-dimethylformamide, stirring and dropwise adding thionyl chloride, distilling to remove a solvent after reflux reaction, mixing and refluxing a substrate, a hydrogen bromide solution and acetic acid to obtain an intermediate 9;
step A4: dissolving the intermediate 7 in tetrahydrofuran, adding triethylamine, stirring, adding the intermediate 9, heating to react, adding dibromoethane and sodium carbonate, continuing to react to obtain an intermediate 10, dissolving chitosan in an acetic acid solution, adding the intermediate 3, ethanol and magnesium chloride, stirring and refluxing, adding the intermediate 10 and acetone, and performing reflux reaction to obtain pre-modified chitosan;
step A5: dissolving pre-modified chitosan, dissolving cross-linked chitosan in hydrochloric acid solution, adding acrylic acid and ferric trichloride, reacting, adding dimethyldiallylammonium chloride and potassium persulfate, reacting, heating, and continuing to react to obtain the modified chitosan.
2. The polyaluminum chloride pharmaceutical composition of claim 1, wherein: the using amount ratio of the 3, 5-dimethylbenzoic acid, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride in the step A1 is 0.1mol:0.1mol:0.15:200mL, the using amount molar ratio of the intermediate 1 to the dimethylaminoethanol is 1:1, the using amount molar ratio of the intermediate 2, the hexamethylenetetramine, the ethanol and the concentrated sulfuric acid is 1:1.5:4:2.5, and the mass fraction of the concentrated sulfuric acid is 98%.
3. The polyaluminum chloride pharmaceutical composition of claim 1, wherein: the molar ratio of the 3, 4-diaminobenzoic acid to the ethanol in the step A2 is 1:1, the molar ratio of the intermediate 4 to the hydrazine hydrate is 1:1.1, and the molar ratio of the intermediate 5, the potassium hydroxide, the carbon disulfide and the hydrazine hydrate is 1:5:2: 3.
4. The polyaluminum chloride pharmaceutical composition of claim 1, wherein: the using amount ratio of the intermediate 6, the deionized water, the glacial acetic acid and the sodium nitrite solution in the step A3 is 0.1:30:0.2:15, the mass fraction of the sodium nitrite solution is 50%, the using amount molar ratio of the tartronic acid to the dimethyl sulfate is 1:1, the using amount ratio of the intermediate 8, the thionyl chloride and the hydrogen bromide solution is 0.01:0.02:20mL, and the mass fraction of the hydrogen bromide solution is 45%.
5. The polyaluminum chloride pharmaceutical composition of claim 1, wherein: the molar ratio of the intermediate 7, the triethylamine, the intermediate 9, the dibromoethane and the sodium carbonate in the step A4 is 2:2:1:1:2, and the molar ratio of the chitosan, the intermediate 3, the magnesium chloride and the intermediate 10 is 1:1.5:0.3: 1.2.
6. The polyaluminum chloride pharmaceutical composition of claim 1, wherein: the mass ratio of the pre-modified chitosan, the acrylic acid, the dimethyl diallyl ammonium chloride and the potassium persulfate in the step A5 is 1:2:3: 0.05.
7. The method of claim 1, wherein the pharmaceutical composition comprises: the method specifically comprises the following steps:
step S1: uniformly mixing polyaluminium chloride, polyaluminium sulfate and ferric sulfate to prepare a mixture;
step S2: dissolving the modified chitosan in an acetic acid solution to prepare a chitosan solution, uniformly mixing the gelatin solution, the chitosan solution and the mixture, stirring at the rotation speed of 200-300r/min, the temperature of 50-55 ℃ and the pH value of 6-6.5 for 20-30min, cooling to the temperature of 30-35 ℃, adding glutaraldehyde, reacting for 1-1.5h, filtering to remove filtrate, and drying filter cakes to prepare the polyaluminium chloride medicament composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111562367.9A CN113955836A (en) | 2021-12-20 | 2021-12-20 | Polyaluminium chloride medicament composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111562367.9A CN113955836A (en) | 2021-12-20 | 2021-12-20 | Polyaluminium chloride medicament composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113955836A true CN113955836A (en) | 2022-01-21 |
Family
ID=79473401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111562367.9A Pending CN113955836A (en) | 2021-12-20 | 2021-12-20 | Polyaluminium chloride medicament composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113955836A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05317890A (en) * | 1992-05-18 | 1993-12-03 | Osaka Prefecture | Water treatment |
| CN102671633A (en) * | 2012-05-07 | 2012-09-19 | 浙江大学 | Preparation method, product and application of chitosan aluminum-iron composite adsorbent |
| CN104229961A (en) * | 2014-09-15 | 2014-12-24 | 武汉理工大学 | Compound tap water flocculating agent of environment-friendly chitosan quaternary ammonium salt and aluminum polychloride |
| CN107552014A (en) * | 2017-10-30 | 2018-01-09 | 陈云 | A kind of Universal Dye waste water treating agent |
| CN109769808A (en) * | 2019-02-13 | 2019-05-21 | 河海大学 | A kind of load medicine chitosan/gelatin sustained-release microparticle algae-inhibiting agent and preparation method |
-
2021
- 2021-12-20 CN CN202111562367.9A patent/CN113955836A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05317890A (en) * | 1992-05-18 | 1993-12-03 | Osaka Prefecture | Water treatment |
| CN102671633A (en) * | 2012-05-07 | 2012-09-19 | 浙江大学 | Preparation method, product and application of chitosan aluminum-iron composite adsorbent |
| CN104229961A (en) * | 2014-09-15 | 2014-12-24 | 武汉理工大学 | Compound tap water flocculating agent of environment-friendly chitosan quaternary ammonium salt and aluminum polychloride |
| CN107552014A (en) * | 2017-10-30 | 2018-01-09 | 陈云 | A kind of Universal Dye waste water treating agent |
| CN109769808A (en) * | 2019-02-13 | 2019-05-21 | 河海大学 | A kind of load medicine chitosan/gelatin sustained-release microparticle algae-inhibiting agent and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 严莲荷: "《水处理药剂及配方手册》", 31 January 2004, 中国石化出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107098485B (en) | Wastewater treatment agent and wastewater treatment method thereof | |
| CN112499780B (en) | High-temperature-resistant scale inhibition and dispersion agent and preparation method thereof | |
| CN107114407B (en) | Preparation method and application of nano copper-zinc composite antibacterial material | |
| CN104722279B (en) | A kind of method that sodium alginate/glutin cladding nano zero valence iron removes heavy metal cadmium, land pollutant in water removal | |
| CN111302464B (en) | Preparation method of polyaluminum sulfatochloride flocculant | |
| CN116768379B (en) | High-temperature-resistant corrosion-resistant scale inhibitor, and preparation method and application thereof | |
| CN102702367B (en) | Method for preparing cationic cross-linked starch xanthate | |
| CN104310552A (en) | Flocculant for waste water treatment and waste water treatment method using flocculant | |
| CN108046392B (en) | Sewage treatment agent | |
| CN103112893B (en) | Preparation method of bismuth hydroxide | |
| CN115160929A (en) | Corrosion-resistant steel strand and preparation method thereof | |
| CN113955836A (en) | Polyaluminium chloride medicament composition and preparation method thereof | |
| CN112777758A (en) | Environment-friendly corrosion and scale inhibitor and preparation method thereof | |
| CN112499777A (en) | High-efficiency low-phosphorus scale and corrosion inhibitor and preparation method thereof | |
| CN107628682B (en) | Magnetic complexing agent for strengthening nitrogen and phosphorus removal of SBR (sequencing batch reactor) and preparation method thereof | |
| CN115108645A (en) | Carboxylic acid chitosan modified material with double functions of corrosion inhibition and scale inhibition and preparation method thereof | |
| CN113860417A (en) | Industrial wastewater treating agent and preparation method thereof | |
| CN113896306A (en) | Polyaluminum ferric chloride flocculant and preparation method thereof | |
| CN113999398A (en) | Fe-MOF composite polymer targeted flocculant, preparation method and application | |
| CN112723511A (en) | High-salt-content desulfurization wastewater treatment flocculant for power plant | |
| CN111039376A (en) | Composite efficient phosphorus removal agent applied to sewage treatment field and preparation method thereof | |
| CN111908653B (en) | Slow-release arsenic and antimony removal medicament, preparation method thereof and method for deeply treating heavy metal wastewater by adopting slow-release arsenic and antimony removal medicament | |
| CN115094406B (en) | Phosphorus-free prefilming agent and preparation method and application thereof | |
| CN112023886A (en) | Environment-friendly adsorbent for aluminum ions in concentrated alkaline water and preparation method thereof | |
| CN117165130B (en) | Processing technology of high-strength nut |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220121 |