CN110075782A - A kind of novel arsenic adsorbent material and preparation method thereof - Google Patents

Abstract

The invention discloses a novel arsenic adsorption material and a preparation method thereof. The invention adopts briquette cinders selected from solid waste as the main raw material, combines alum, stabilizer, organic ligand, adhesive and solvent, and soaks, passes The novel arsenic adsorption material is obtained through reaction steps such as sieving and stirring; the preparation process of the novel arsenic adsorption material of the present invention is simple, the raw material is cheap and easy to obtain, and the product of the present invention has a larger specific surface area and pore volume at the same time, and has better stability Non-toxic and environmentally friendly, it can meet the needs of industrial production.

Description

A new type of arsenic adsorption material and its preparation method

technical field

The invention belongs to the technical field of adsorption materials, and in particular relates to a novel arsenic adsorption material and a preparation method thereof.

Background technique

The present invention relates to recent years, with the vigorous development of industry, agriculture, mining, metallurgy and other industries, the pollution of water resources has been aggravated to a certain extent, resulting in serious excess of arsenic content in groundwater and surface water. High-arsenic water not only satisfies human water consumption, but also brings fatal harm to people, which is the so-called endemic arsenic poisoning. Endemic arsenic poisoning has plagued people for a long time, and the strong carcinogenicity of arsenic also reminds people that for the sake of human beings In order to improve the life, health and safety of human beings, it is necessary to develop efficient, economical and environmentally friendly arsenic removal processes for drinking water and industrial wastewater.

Therefore, in recent years, scholars from various countries have conducted a lot of research on arsenic removal technology. At present, the relatively mature arsenic removal technology mainly includes the following types: precipitation method, adsorption method, ion exchange method, membrane technology and biotechnology. The adsorption method is a method of fixing arsenic in water on the surface of the adsorbent through physical action, chemical action or ion exchange, so as to remove arsenic. Adsorption is a simple and easy water treatment technology, which is most widely used in our country. At present, the commonly used arsenic adsorbents in water treatment include activated alumina, activated carbon, zeolite and so on. Although activated alumina has a good removal effect on As(V), this effect can only be performed well when the pH value is about 5, which limits its application; while activated carbon and natural zeolite have a good adsorption capacity for arsenic. And quite limited. Therefore, it is an urgent technical problem to be solved by those skilled in the art to research novel and inexpensive adsorbents with excellent adsorption properties.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a novel arsenic adsorption material.

In order to achieve the above object, the present invention adopts the following technical solutions:

The new arsenic adsorption material is composed of the following raw materials in parts by weight: 30-50 parts of honeycomb cinder, 5-20 parts of alum, 5-15 parts of stabilizer, 10-20 parts of organic ligand, 2-10 parts of adhesive, solvent 40-70 servings.

Further, the above-mentioned stabilizer is one or more of magnesium sulfate, copper sulfate, sodium stannate, and organic phosphate;

Furthermore, the above-mentioned organic phosphate is methyl phosphate, ethyl phosphate or phenyl phosphate.

The further beneficial effect of adopting the above is that the stabilizer used in the present invention can improve the spatial structure of the briquette cinder, and make the organic ligands and other substances in the present invention form a stable adsorption structure with the briquette cinder, thereby enhancing the adsorption of the present invention. It also plays a role in maintaining the chemical balance between raw materials, reducing the surface tension of products, and effectively preventing light, thermal decomposition and oxidative decomposition.

Further, the above-mentioned organic ligand is ethylenediamine or phthalic acid.

The further beneficial effect of adopting the above is that the organic ligand used in the present invention can produce bonded molecules with briquette cinder and alum, thereby effectively improving the adsorption capacity and adsorption capacity of the adsorption material of the present invention, and simultaneously improving the solubility of the raw materials of the present invention , promotes the reaction rate, effectively shortens the preparation time, and simplifies the preparation process.

Further, the above-mentioned adhesive is water-based polyurethane or methacrylate.

The further beneficial effect of adopting the above is that the present invention utilizes the excellent physical and chemical properties of the adhesive to increase the viscosity of the solution through the adhesion and cohesion with the solvent, and at the same time enhance the effect of the van der Waals force between substances, The substance structure of the adsorption material of the present invention is improved, thereby enhancing the adsorption force of the adsorption material of the present invention.

Further, the above-mentioned solvent is composed of any one or a mixture of water, ethanol, acetone, dimethylformamide and isopropanol.

Further, the mass ratio of water, ethanol, acetone, dimethylformamide and isopropanol in the above solvent is preferably 1:0.5-1.5:0.1-0.5:0.3-0.8:1-2;

Furthermore, the mass ratio of water, ethanol, acetone, dimethylformamide and isopropanol in the above solvent is preferably 1:1:0.5:0.5:1.

The further beneficial effect of adopting the above is that the present invention uses a mixed solution of water, ethanol, acetone, dimethylformamide and isopropanol as a solvent, and the solvent used in the present invention can be miscible in any proportion, thereby fully dissolving the solute of the present invention , and then expand the contact area between the various substances, and effectively catalyze the internal reflection of the present invention.

The present invention also provides a preparation method for the above-mentioned novel arsenic adsorption material, comprising the following steps:

1) take each raw material according to the weight fraction of the novel arsenic adsorption material described in any one of claims 1-6, and set aside;

(2) After soaking the weighed cinder in water for 10-60min, dry the soaked cinder;

(3) Sieve the dried coal cinder, discard the under-sieve material, and obtain pulverized coal cinder after the remaining material is ultrasonically pulverized;

(4) After stirring and mixing the pulverized coal slag in step (3) with other raw materials, the coal slag turbid liquid is obtained, and the coal slag turbid liquid is heated up to 150°C at a heating rate of 5°C/min, and kept for 2-12h to obtain a loaded Porous structure cinder of alum;

(5) After filtering the cinder with a porous structure loaded with alum in step (4), drying at 200-240° C. for 1-5 hours to obtain a novel arsenic adsorption material.

Further, the drying temperature in the above step (2) is 100-150° C., and the drying time is 20-40 minutes.

Further, the sieved particle size in the above step (3) is 100-250 mesh.

The further beneficial effect of adopting the above is that the ashes in the briquette cinders are screened out, which can effectively prevent the influence of impurities on the adsorption capacity and adsorption force of the adsorption material of the present invention, promote the formation of the structure of the adsorption material of the present invention, and effectively improve the adsorption capacity. .

Further, in the above step (4), the stirring speed is 1500-3000r/min, and the stirring time is 10-30min.

Compared with the prior art, the beneficial effects of the present invention are:

The arsenic adsorption material obtained in the present invention has a large specific surface area and pore volume, and has good stability and environment-friendly characteristics; the main raw material of the product of the present invention is selected from solid waste, all raw materials are cheap and easy to obtain, and the preparation process is simple , without inert gas protection, low preparation cost, and can meet the needs of industrial production and use; the product of the invention has a large adsorption capacity and a fast adsorption rate, and can simultaneously remove trivalent arsenic and pentavalent arsenic in samples.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

New arsenic adsorption materials:

(1) Weigh 30g of honeycomb briquette cinder, 20g of alum, 5g of organic phosphate, 10g of phthalic acid, 2g of water-based polyurethane, and 40g of solvent for subsequent use. The mass ratio of water, ethanol, and acetone in the solvent is 1:1.5:0.5;

(2) Wet the weighed cinders with water, soak them for 10 minutes, and then dry them at 150°C for 20 minutes;

(3) passing the dried coal cinder through a 250-mesh sieve, discarding the material under the sieve, and ultrasonically pulverizing the remaining material to obtain pulverized coal cinder;

(4) After stirring the pulverized coal cinder and other raw materials at a speed of 3000r/min for 10min for a mixed reaction in step (3), the temperature was raised to 150°C at a heating rate of 5°C/min and kept for 12h to obtain alum-loaded Porous structure cinder;

(5) After drying the mixed solution in step (4) at 200° C. for 5 hours, filter to obtain a novel arsenic adsorption material.

Example 2

New arsenic adsorption materials:

(1) Take by weighing 50g of briquette cinder, 5g of alum, 15g of magnesium sulfate, 20g of ethylenediamine, 10g of water-based polyurethane, and 70g of solvent, for subsequent use, the mass ratio of water, ethanol, acetone, dimethylformamide and isopropanol in the solvent 1:0.5:0.1:0.3:1;

(2) Wet the weighed cinders with water, soak them for 60 minutes, and then dry them at 100°C for 40 minutes;

(3) passing the dried coal cinder through a 100-mesh sieve, discarding the material under the sieve, and ultrasonically pulverizing the remaining material to obtain pulverized coal cinder;

(4) After stirring the pulverized cinder and other raw materials at a rate of 1500r/min for 130min for a mixed reaction in step (3), the mixed solution was heated to 150°C at a heating rate of 5°C/min and kept for 2h to obtain Porous structure cinder loaded with alum;

(5) After the mixed solution in step (4) was dried at 240° C. for 1 hour, it was filtered to obtain a novel arsenic adsorption material.

Example 3

New arsenic adsorption materials:

(1) Weigh 42g of briquette cinder, 13g of alum, 8g of sodium stannate, 17g of ethylenediamine, 6g of methacrylate, and 45g of solvent, and set aside, water, ethanol, acetone, dimethylformamide and isopropanol in the solvent The mass ratio is 1:0.8:0.4:0.8:1;

(2) Wet the weighed cinders with water, soak them for 30 minutes, and then dry them at 140°C for 25 minutes;

(3) passing the dried coal cinder through a 200-mesh sieve, discarding the material under the sieve, and ultrasonically pulverizing the remaining material to obtain pulverized coal cinder;

(4) After stirring the pulverized cinder in step (3) and other raw materials for 15 min at a rate of 2500 r/min for a mixed reaction, the mixed solution was heated to 150 °C at a heating rate of 5 °C/min and kept for 6 h to obtain Porous structure cinder loaded with alum;

(5) After the mixed solution in step (4) was dried at 220° C. for 3 hours, it was filtered to obtain a novel arsenic adsorption material.

Example 4

New arsenic adsorption materials:

(1) Weigh 36g of honeycomb coal cinder, 9g of alum, 8g of organic phosphate, 14g of phthalic acid, 4g of water-based polyurethane, 65g of solvent, for subsequent use, the amount of water, ethanol, acetone, dimethylformamide and isopropanol in the solvent The mass ratio is 1:1:0.5:0.5:1;

(2) Wet the weighed cinders with water, soak them for 45 minutes, and then dry them at 120°C for 30 minutes;

(3) passing the dried coal cinder through a 250-mesh sieve, discarding the material under the sieve, and ultrasonically pulverizing the remaining material to obtain pulverized coal cinder;

(4) After stirring the crushed cinder in step (3) and other raw materials for 30 minutes at a rate of 2000 r/min for a mixed reaction, the mixed solution was heated to 150 °C at a heating rate of 5 °C/min and kept for 8 hours to obtain Porous structure cinder loaded with alum;

(5) After the mixed solution in step (4) was dried at 200° C. for 3 hours, it was filtered to obtain a novel arsenic adsorption material.

Example 5

New arsenic adsorption materials:

(1) Weigh 48g of briquette cinder, 16g of alum, 5-15g of copper sulfate, 15g of ethylenediamine, 3g of water-based polyurethane, and 50g of solvent, and set aside, the amount of water, ethanol, acetone, dimethylformamide and isopropanol in the solvent The mass ratio is 1:1.5:0.2:0.8:2;

(2) Wet the weighed cinders with water, soak them for 20 minutes, and then dry them at 150°C for 30 minutes;

(3) passing the dried coal cinder through a 100-mesh sieve, discarding the material under the sieve, and ultrasonically pulverizing the remaining material to obtain pulverized coal cinder;

(4) After stirring the pulverized cinder in step (3) and other raw materials for 15 minutes at a rate of 3000 r/min for a mixed reaction, the mixed solution was heated to 150 °C at a heating rate of 5 °C/min and kept for 10 h to obtain Porous structure cinder loaded with alum;

(5) After the mixed solution in step (4) was dried at 200° C. for 3 hours, it was filtered to obtain a novel arsenic adsorption material.

Test case

Take each 1g of the products of Examples 1-5 of the present invention, and compare them with the adsorption capacity results of 1g of activated alumina, 1g of activated carbon, 1g of natural zeolite and 1g of commercially available MOF materials, and the specific data are as shown in Table 1;

Table 1 The present invention compares with the adsorption capacity of different types of adsorbents

Adsorbent type Adsorption amount of trivalent arsenic (mg/g) Adsorption amount of pentavalent arsenic (mg/g) Example 1 148.4 126.5 Example 2 152.6 134.3 Example 3 138.7 130.6 Example 4 165.3 151.7 Example 5 150.7 143.3 Activated alumina 22.3 66.5 activated carbon 55.3 22.5 natural zeolite 48.6 26.6 Commercially available MOF materials 115.8 104.2

It can be seen from the above data that the adsorption capacity of the novel arsenic adsorption material of the present invention to trivalent As and pentavalent As under the same conditions is much higher than that of the adsorbents in the prior art, which proves that the present invention is a kind of high-efficiency, large adsorption A new type of arsenic adsorption material with high capacity.

Claims (10)

1. a kind of novel arsenic adsorbent material, which is characterized in that be made of the raw material of following parts by weight: 30-50 parts of honeycomb briquette cinder, 5-20 parts of alum, 5-15 parts of stabilizer, 10-20 parts of organic ligand, 2-10 parts of adhesive, 40-70 parts of solvent.

2. a kind of novel arsenic adsorbent material according to claim 1, which is characterized in that the stabilizer is magnesium sulfate, sulfuric acid One or more of copper, sodium stannate, organic phosphate.

3. a kind of novel arsenic adsorbent material according to claim 2, which is characterized in that the organic phosphate is phosphoric acid first Ester, etherophosphoric acid or phenyl phosphate.

4. a kind of novel arsenic adsorbent material according to claim 1, which is characterized in that the organic ligand is ethylenediamine or neighbour Phthalic acid.

5. a kind of novel arsenic adsorbent material according to claim 1, which is characterized in that the adhesive be aqueous polyurethane or Methacrylate.

6. a kind of novel arsenic adsorbent material according to claim 1, which is characterized in that the solvent be water, ethyl alcohol, acetone, The mixing of any one or more of dimethylformamide, isopropanol.

7. a kind of preparation method of novel arsenic adsorbent material, which comprises the following steps:

(1) each raw material is weighed by the weight fraction of any one of the claim 1-6 novel arsenic adsorbent material, it is spare；

(2) cinder weighed up is soaked in water after 10-60min, the cinder after immersion is dried；

(3) cinder after drying is sieved, casts out screenings matter, surplus materials crushed after Ultrasonic Pulverization Cinder；

(4) smashed cinder in step (3) is stirred after mixing with other raw materials, cinder turbid is obtained, by cinder Turbid is warming up to 150 DEG C with the heating rate of 5 DEG C/min, keeps 2-12h, obtains the porous structure cinder of load alum；

(5) by after the porous structure cinder filtration of the load alum in step (4), dry 1-5h, is obtained at 200-240 DEG C Novel arsenic adsorbent material.

8. a kind of preparation method of novel arsenic adsorbent material according to claim 7, which is characterized in that described in step (2) Drying temperature is 100-150 DEG C, drying time 20-40min.

9. a kind of preparation method of novel arsenic adsorbent material according to claim 7, which is characterized in that described in step (3) Passing-screen size is 100-250 mesh.

10. a kind of preparation method of novel arsenic adsorbent material according to claim 7, which is characterized in that described in step (4) Stirring rate is 1500-3000r/min, mixing time 10-30min.