CN104001479A - Inorganic mineral water treatment agent and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of inorganic water treatment agents, in particular to a fibrous porous zeolite water treatment agent and a preparation method thereof, which consists of 50-60 parts of natural zeolite, 25-30 parts of red volcanic stone, 8-15 parts of natural fiber, 3- It consists of 4 parts of ferrous salt and 1-2 parts of 35% H ₂ O ₂ aqueous solution; its preparation method is: mixing natural zeolite and volcanic stone, after crushing, acid washing, infrared light irradiation, etc., and then natural Fiber, zeolite and volcanic stone mixture are mixed under vacuum conditions, soluble ferrous solution is added, and H ₂ O ₂ aqueous solution is added later, stirred and dried, calcined at high temperature, cooled and dried, which is the inorganic mineral water treatment agent of the present invention. The water treatment agent has relatively large adsorption space and adsorption force, and can solve the problems that the existing water treatment agents have no obvious treatment effect on sewage with complex components, environmental pollution and the like. The water treatment agent of the invention is easy to regenerate, does not cause secondary pollution, and can be widely used in the purification treatment of various sewage.

Description

A kind of inorganic mineral water treatment agent and preparation method thereof

technical field

The invention relates to the field of water treatment agents, in particular to an inorganic mineral water treatment agent with natural zeolite and natural fibers as main raw materials and a preparation method thereof.

Background technique

Water treatment agents are chemical agents that must be used in the process of industrial water, domestic water, and wastewater treatment. The use of these chemicals makes the water meet certain quality requirements. Its main function is to control the formation of scale and sludge, reduce foam, reduce corrosion of materials in contact with water, remove suspended solids and toxic substances in water, deodorize, decolorize, soften, stabilize water quality and desalinate seawater, etc. The material basis for the development of the water treatment industry itself is also taken from the environment. Many of its products do not meet the requirements of environmental protection, such as toxic, high phosphorus, and heavy metal agents or formula products. The current technology cannot meet the requirements of water treatment. Therefore, the water treatment industry itself is also facing problems such as technological innovation and development needs, and develops low-toxic, even non-toxic and environmentally friendly green water treatment products and reasonable, economical and safe green water treatment processes , is an urgent need in the field of water treatment. Zeolite has the properties of adsorption, ion exchange, catalysis, acid resistance and heat resistance, etc. It can be used as adsorbent, ion exchanger and catalyst for sewage treatment, etc., and has broad market application prospects.

The silicon-oxygen structure on the surface of natural zeolite is extremely hydrophilic, and the cations outside the structure are easily hydrolyzed, resulting in extremely poor performance of natural zeolite in adsorbing organic matter, and the silicon-aluminum structure itself is negatively charged, so it is difficult for natural zeolite to remove anionic pollutants in water . Therefore, modifying natural zeolite to improve its adsorption capacity for organic matter and anions can make natural zeolite more widely used in the field of water treatment. After modification of natural zeolite, its porosity and surface activity can be significantly improved, and the adsorption capacity can be improved. Performance, ion exchange performance and exchange capacity, etc., thereby improving its use value. Modified zeolite covers a wide range, and the products obtained from simple ion exchange treatment to the complete collapse of the structure belong to the scope of modified zeolite.

Porous zeolite material is a crystalline zeolite rich in pores, which not only retains the excellent acidity and hydrothermal stability of zeolite materials, but also improves its adsorption and diffusion properties for macromolecules due to the introduction of new pores. Molecular catalytic reactions are extremely promising materials. The early synthesis methods of porous zeolites mainly used post-treatment, including hydrothermal treatment, acid treatment or alkali treatment. In recent years, the use of templates has become the main method for the synthesis of porous zeolites, mainly including mesoporous carbon templates, polymers, organosilanes, and nano-inorganic substances. However, the existing template method has disadvantages such as large environmental pollution, high cost, and long crystallization time, so it is not suitable for widespread use.

Chinese patent application Nos. 201210382889.5, 201210010532.4 and 201310414937.9 improve the effect of adsorption and precipitation through coagulation adsorption or metal modification of zeolite and other blends. The addition of metal substances can change the activity of water quality, but the adsorbents used are all natural substances. The performance is limited, and after metal modification, the adsorption object is single, and the pollutants such as organic matter and metal can only be partially adsorbed, and the addition of metal active substances will cause secondary pollution to the water body, and the sludge after adsorption is troublesome and easy to use The environment causes secondary pollution.

Chinese patent application numbers 201310543704.9 and 200810143851.6, through zeolite alkali treatment and surface modification, but the adsorption selectivity of the modifier can only adsorb certain or certain types of pollutants, so the treatment of sewage with complex components should be treated The agent has no noticeable effect. the

Chinese Patent Application Nos. 201210020674.9 and 201110321285.5, the zeolite is subjected to alkali treatment, microwave treatment, acid treatment, etc. to increase the effective pore size of the zeolite and promote the generation of mesoporous structure, but the treatment agents used are sodium hydroxide, lithium hydroxide, hydroxide Potassium, sulfuric acid, nitric acid and other strong bases and strong acids are highly dangerous in large-scale production, and wastewater discharge is likely to cause secondary pollution of water quality and air.

Chinese patent application Nos. 200810080287.8 and 200810080287.8 use the template method to modify zeolite, so that the modified zeolite is an ordered porous material, but most of the template agents are non-green additives, which are easy to pollute the environment, and the crystallization time in the manufacturing process Long, so that the production cost is higher.

Zeolite is widely used in sewage treatment, but the existing technology has problems such as poor treatment effect on sewage with complex components, the additives used are likely to cause secondary pollution to water sources, high production cost, and complicated process flow.

Contents of the invention

Aiming at the problems of the existing inorganic water treatment agents such as low adsorption capacity, low adsorption force, environmental pollution, high production cost and complicated process, the present invention provides a fibrous porous inorganic mineral water treatment agent mainly composed of natural zeolite and natural fiber. agent.

The present invention further provides a preparation method of an inorganic mineral water treatment agent. The method crushes natural zeolite, micronizes natural fiber substances, and uniformly mixes the two substances under vacuum conditions. After burning at high temperature, the natural fibers remain in the zeolite voids. In the process, the zeolite forms a fibrous porous structure, thereby improving the purification and treatment capacity of the zeolite for sewage.

An inorganic mineral water treatment agent of the present invention is characterized in that parts by weight consist of: 50-60 parts of natural zeolite, 25-30 parts of red volcanic stone, 8-15 parts of natural fiber, 3-4 parts of ferrous salt and 1- 2 parts of _H2O2 aqueous solution with a mass concentration of 35%, wherein the natural zeolite is selected from at least one _of analcime, phillipsite, natrolite, heulandite, clinoptilolite, chabazite and faujasite , the natural fiber is selected from at least one of rice husk, straw, flax, kapok, and sugar cane, and the ferrous salt is selected from one of FeSO ₄ and FeCl ₂ .

The above-mentioned inorganic mineral water treatment agent is characterized in that the natural zeolite is preferably faujasite.

The above-mentioned inorganic mineral water treatment agent is characterized in that the mass ratio of the ferrous salt to H ₂ O ₂ is preferably m(Fe ²⁺ )/m(H ₂ O ₂ )=8.

A kind of preparation method of inorganic mineral water treatment agent of the present invention is characterized in that: carry out as follows:

1) Mix and crush 50-60 parts of natural zeolite and 25-30 parts of volcanic rock until the particle size is ≤50 μm, soak in ethylenediaminetetraacetic acid for 2-5 hours, then wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8- 10h, wash with distilled water, dry at 60~200°C for 24h, and irradiate with infrared light with a wavelength of 750nm for 3-6h, which is conducive to the formation of pores;

2) Fully micronize 8-15 parts of natural fiber materials, pass through 2000 mesh molecular sieves, and the length of the fiber strips is less than the particle diameter of the materials obtained after the treatment in 1);

3) Mix the material obtained from 1) and 2) uniformly under the vacuum condition of 1.5-2.5MPa, so that the natural fibers enter the gaps in the particles of the material obtained from 1), and calcinate at 700-1000℃ in a muffle furnace for 3h- 8h, so that 1) the obtained material forms a fibrous porous structure, and the fibrous porous zeolite matrix is formed;

4) Add the substance obtained in 3) into deionized water, then add 3-4 parts of ferrous salt, stir and mix, add 1-2 parts of 35% H ₂ O ₂ aqueous solution dropwise within 0.5h-1.5h, at a constant speed Stir and react at 40-100°C for 20 hours. After the reaction is completed, centrifuge and filter, and use the obtained precipitate as a blank, and pass it through a fluidized bed to prepare an inorganic mineral water treatment agent.

The above-mentioned preparation method of an inorganic mineral water treatment agent is characterized in that: in step 3) of the production process, the mixture is uniformly mixed in a vacuum mixer with a rotational speed of 120r/min.

The above method for preparing an inorganic mineral water treatment agent is characterized in that the volume of deionized water added in step 4) is 0.8-1.5 times the volume of the substance obtained in step 3).

The present invention uses natural zeolite and natural fiber to prepare a fibrous porous zeolite water treatment agent through processes such as infrared light irradiation, vacuum mixing, and high-temperature burning; the components used are low in cost, friendly to the environment, easy to recycle, and can be used in large quantities. mass production.

Compared with the prior art, the present invention has benefits mainly reflected in:

(1) Natural zeolite and natural fiber are modified and vacuum mixed to increase the adsorption capacity and adsorption capacity of zeolite to various pollutants;

(2) The modified zeolite and the micronized natural fiber are uniformly mixed under vacuum conditions, so that the fiber material enters the zeolite void, and then is fired at a high temperature to form a fiber-porous zeolite, which effectively increases the specific surface area. The pore size is changed, so that the molecular weight is small, and the substances that are not easy to be adsorbed can also be removed, so as to achieve the effect of high adsorption capacity for various pollutants;

(3) The preparation process of the present invention is simple, low in cost, easy to recycle, reusable, environmentally friendly, and suitable for large-scale production.

Description of drawings

Fig. 1 is the preparation flow chart of a kind of inorganic mineral water treatment agent of the present invention.

Detailed ways

The present invention will be further described in detail through specific embodiments below, but it should not be understood that the scope of the present invention is limited to the following examples. Without departing from the idea of the above-mentioned method of the present invention, various replacements or changes made according to common technical knowledge and conventional means in this field shall be included within the scope of the present invention.

Example 1

1) Mix and crush 10KG faujasite and 5KG red volcanic rock to a particle size of 40 μm, soak in ethylenediaminetetraacetic acid for 3 hours, wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8 hours, and wash with distilled water. Dry at 150°C for 24 hours, and irradiate with infrared light with a wavelength of 750nm for 6 hours, which is conducive to the formation of pores;

2) Fully micronize 2KG of dry straw, pass through a molecular sieve of 2000 mesh, and the length of the fiber strip is 30 μm;

3) The material obtained in 1) and 2) is uniformly mixed under the vacuum condition of 2.5MPa, and calcined in a muffle furnace at 800°C for 5 hours, so that a fibrous porous structure is formed in the material obtained in 1), and a fibrous porous zeolite matrix is formed;

4) Add the substance in 3) into deionized water whose volume is 1.5 times the total volume of the substance in step 3), then add 0.75KGFeSO ₄ , stir and mix, add 0.3KG of H with a mass concentration of 35% within 1 hour ₂ O ₂ aqueous solution; stir at a constant speed, react at 100°C for 20 hours; after the reaction is completed, centrifuge, filter, and use the obtained precipitate as a raw material, and pass it through a fluidized bed to prepare an inorganic mineral water treatment agent.

The water treatment agent obtained in Example 1 was added to the sewage at the entrance of a water treatment plant, and the water treatment agent of the present invention was added to the sewage at a rate of 0.30% of the quality of the water to be treated. The water quality indicators before and after treatment are as follows:

the Before treatment (mg/L) After treatment (mg/L) Biological Oxygen Demand (BOD ₅ ) 125 1.24 Chemical Oxygen Demand (COD _cr ) 157 0.21 Total nitrogen content (T-N) 25.4 0.62 Total phosphorus content (T-P) 3.1 Trace

Example 2

1) Mix and crush 5KG chabazite and 2.5KG red volcanic stone to a particle size of 40μm, soak in ethylenediaminetetraacetic acid for 3 hours, wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8 hours, and then wash with distilled water. Dry at 150°C for 24 hours, and irradiate with infrared light with a wavelength of 750nm for 6 hours, which is conducive to the formation of pores;

2) Fully micronize 2KG dry sugarcane stems, pass through 2000 mesh molecular sieves, and the length of the fiber strips is 35μm;

3) The material obtained in 1) and 2) is uniformly mixed under the vacuum condition of 2.5MPa, and calcined in a muffle furnace at 800°C for 5 hours, so that a fibrous porous structure is formed in the material obtained in 1), and a fibrous porous zeolite matrix is formed;

4) Add the substance in 3) into deionized water whose volume is 0.9 times the total volume of the substance in step 3), then add 0.45KGFeSO ₄ , stir and mix, add 0.15KG of H with a mass concentration of 35% within 1 hour ₂ O ₂ aqueous solution; stir at a constant speed, react at 100°C for 20 hours; after the reaction is completed, centrifuge, filter, and use the obtained precipitate as a raw material, and pass it through a fluidized bed to prepare an inorganic mineral water treatment agent.

The water treatment agent obtained in Example 2 was added to the sewage of a paper mill, and the water treatment agent of the present invention was added to the sewage according to 0.95% of the quality of the water to be treated. The water quality indicators before and after treatment are as follows:

the Before treatment (mg/L) After treatment (mg/L) Suspended solids (SS) in water quality 1067 25.7 Chemical Oxygen Demand (CODcr) 4800 34 Volatile phenol 1.7 Trace Sulfide 15.1 Trace Chroma 96 8

Example 3

1) Mix and crush 6KG sodium zeolite and 3KG red volcanic rock to a particle size of 40 μm, soak in ethylenediaminetetraacetic acid for 3 hours, wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8 hours, and then wash with distilled water. Dry at ℃ for 24 hours, and irradiate with infrared light with a wavelength of 750nm for 6 hours, which is conducive to the formation of pores;

2) Fully micronize 2KG dry sugarcane stems, pass through 2000 mesh molecular sieves, and the length of the fiber strips is 35μm;

3) The material obtained in 1) and 2) is uniformly mixed under the vacuum condition of 2.5MPa, and calcined in a muffle furnace at 800°C for 5 hours, so that a fibrous porous structure is formed in the material obtained in 1), and a fibrous porous zeolite matrix is formed;

4) Add the substance in 3) into deionized water whose volume is 0.8 times the total volume of the substance in step 3), then add 1.8KGFeSO ₄ , stir and mix, and add 0.2KG of H with a mass concentration of 35% within 1 hour ₂ O ₂ aqueous solution; stir at a constant speed, react at 100°C for 20 hours; after the reaction is completed, centrifuge, filter, and use the obtained precipitate as a raw material, and pass it through a fluidized bed to prepare an inorganic mineral water treatment agent.

 The water treatment agent obtained in Example 3 was added to the sewage of a steel mine, and the water treatment agent was added to the sewage according to 5% of the quality of the water to be treated. The water quality indicators before and after treatment are as follows:

the Cu (mg/L) Fe (mg/L) Cd (mg/L) Pb (mg/L) Zn (mg/L) As (mg/L) pH content before treatment 6294 26858 7 0.97 133 33 <1.5 Content after treatment Trace 0.01 Trace Trace Trace Trace 6.5

Example 4

1) Mix and crush 3KG chabazite, 3KG heulandite and 3KG red volcanic stone to a particle size of 50μm, soak in ethylenediaminetetraacetic acid for 3 hours, wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8 hours, and then wash with distilled water Clean, dry at 200°C for 24 hours, and irradiate with infrared light with a wavelength of 750nm for 6 hours, which is conducive to the formation of pores;

2) Fully micronize 1KG flax and 1KG kapok, pass through 2000 mesh molecular sieve, and the fiber length is 40μm;

3) Mix the material obtained from 1) and 2) uniformly under 2 MPa vacuum conditions, and calcinate in a muffle furnace at 1000°C for 5 hours, so that a fibrous porous structure is formed in the material obtained in 1), and a fibrous porous zeolite matrix is formed;

4) Add the substance in 3) into deionized water whose volume is 0.8 times the total volume of the substance in step 3), then add 0.5KGFeCl ₂ , stir and mix, and add 0.25KG of H with a mass concentration of 35% in 0.5h ₂ O ₂ aqueous solution; stir at a constant speed, and react at 80°C for 20 hours; after the reaction is completed, centrifuge, filter, and use the obtained precipitate as a raw material, and pass it through a fluidized bed to prepare an inorganic mineral water treatment agent.

Example 5

1) Mix and crush 15KG phillipsite and 15KG clinoptilolite with 20KG red volcanic rock until the particle size is 50 μm, soak in ethylenediaminetetraacetic acid for 3 hours, wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8 hours, and then use Wash with distilled water, dry at 180°C for 24 hours, and irradiate with infrared light with a wavelength of 750nm for 6 hours, which is conducive to the formation of pores;

2) Fully micronize 6KG rice husk and 5KG kapok, pass through 2000 mesh molecular sieve, and the fiber length is 35μm;

3) Mix the material obtained from 1) and 2) uniformly under 2 MPa vacuum conditions, and calcinate in a muffle furnace at 850°C for 8 hours to form a fibrous porous structure in the material obtained in 1), and form a fibrous porous zeolite matrix;

Add the substance in 3) into deionized water whose volume is 0.8 times the total volume of the substance in step 3), then add 1.0KG FeSO ₄ and 0.8 KG FeCl ₂ , stir and mix, add 1.5KG dropwise within 1.5h It is 35% H ₂ O ₂ aqueous solution; stir at a constant speed, and react at 100°C for 20 hours; after the reaction is completed, centrifuge, filter, and use the obtained precipitate as a raw material, and pass through a fluidized bed to obtain an inorganic mineral water treatment agent.

Claims (6)

1. An inorganic mineral water treatment agent is characterized in that parts by weight consist of: 50-60 parts of natural zeolite, 25-30 parts of red volcanic stone, 8-15 parts of natural fiber, 3-4 parts of ferrous salt and 1- 2 parts of _H2O2 aqueous solution with a mass concentration of 35%, wherein the natural zeolite is selected from at least one _of analcime, phillipsite, natrolite, heulandite, clinoptilolite, chabazite and faujasite , the natural fiber is selected from at least one of rice husk, straw, flax, kapok, and sugar cane, and the ferrous salt is selected from one of FeSO ₄ and FeCl ₂ . 2. A kind of inorganic mineral water treatment agent according to claim 1, characterized in that: said natural zeolite is preferably faujasite. 3. A kind of inorganic mineral water treatment agent according to claim 1, characterized in that: the mass ratio of the ferrous salt to H ₂ O ₂ is preferably m(Fe ²⁺ )/m(H ₂ O ₂ )=8. 4. a preparation method of inorganic mineral water treatment agent, is characterized in that: carry out as follows: 1) Mix and crush 50-60 parts of natural zeolite and 25-30 parts of volcanic rock until the particle size is ≤50 μm, soak in ethylenediaminetetraacetic acid for 2-5 hours, then wash with hydrochloric acid with a concentration of 6M/L, heat and reflux for 8- 10h, wash with distilled water, dry at 60~200°C for 24h, and irradiate with infrared light with a wavelength of 750nm for 3-6h, which is conducive to the formation of pores; 2) Fully micronize 8-15 parts of natural fiber materials, pass through a 2000-mesh molecular sieve, and the length of the fiber strips is less than the particle diameter of the materials obtained after the treatment in 1); 3) Mix 1) and 2) uniformly under vacuum condition of 1.5-2.5MPa, make the natural fibers enter the gaps in the particles of 1) and calcinate in muffle furnace at 700-1000℃ for 3h- 8h, so that 1) the obtained material forms a fibrous porous structure, and the fibrous porous zeolite matrix is formed; 4) Add the substance obtained in 3) into deionized water, then add 3-4 parts of ferrous salt, stir and mix, add 1-2 parts of 35% H ₂ O ₂ aqueous solution dropwise within 0.5h-1.5h, stir at a constant speed, React at 40-100°C for 20 hours, after the reaction is completed, centrifuge, filter, and use the obtained precipitate as a blank, and pass it through a fluidized bed to prepare an inorganic mineral water treatment agent. 5. The preparation method of an inorganic mineral water treatment agent according to claim 3, characterized in that: in step 3) of the production process, the mixture is uniformly mixed in a vacuum mixer with a rotational speed of 120r/min. 6. The preparation method of an inorganic mineral water treatment agent according to claim 4, characterized in that: the volume of deionized water added in step 4) in the production process is 0.8-1.5 of the volume of the substance obtained in step 3). times.