CN103127917B - Preparation method of drinking water treatment agent - Google Patents

Abstract

A drinking water treatment agent, which is prepared by adding tourmaline and magnetic chitosan microsphere mixed powder into sodium alginate and polyvinyl alcohol, dissolving, mixing, and then solidifying into balls; magnetic chitosan microsphere is made of super Paramagnetic iron tetroxide, 1-10wt% chitosan acetic acid solution, liquid paraffin, Span-80, and glutaraldehyde solution are used as reaction materials, and are prepared by emulsification and cross-linking method. Superparamagnetic ferric iron tetroxide and chitosan The mass ratio of acetic acid solution is 1:1-10, the volume ratio of liquid paraffin and Span-80 is 10-100:1, and the volume ratio of chitosan acetic acid solution of superparamagnetic iron tetroxide and paraffin-Span-80 mixture is 1 :1～10, the mixed solution of chitosan acetic acid solution of superparamagnetic ferroferric oxide, paraffin, Span-80, and glutaraldehyde solution in a volume ratio of 5～50:1. The water treatment agent of the present invention has a removal rate of 80% to 90% for volatile phenols in water, and a removal rate of 93% for chromium in water. At the same time, it has large adsorption capacity, high purification efficiency, low cost, renewability, non-toxicity, and The environment has no pollution and other advantages.

Description

A kind of preparation method of tourmaline/magnetic chitosan microsphere treatment agent

The present invention is a divisional application with an application date of September 23, 2011 and an application number of 201110284933.4.

technical field

The invention relates to a water treatment preparation, in particular to a water treatment agent with good effect on removing volatile phenol in water and a preparation method thereof, belonging to the field of water treatment.

Background technique

In recent years, the unique properties and structure of magnetic chitosan microspheres have attracted widespread attention, especially in the application research of water treatment, which has achieved good results. Magnetic chitosan can be used to remove Cu ²⁺ , Cr ²⁺ , Hg ²⁺ , Zn ²⁺ , Pb ²⁺ , Ca ²⁺ , Ag ⁺ and other metal ions in water, and can also be used to treat organic wastewater, and can be quickly Achieve balance. Wong and G.Mckay et al ^{. [22-23]} have done a detailed study on the treatment of printing and dyeing wastewater with chitosan, and the results show that chitosan has a high affinity for many types of dyes, including disperse, direct, active, Acid, sulfur and Nafto dyes, only have a low affinity for basic dyes. Hong Aizhen et al ^[24] used magnetic microspheres made of chitosan-coated iron to treat acidic azo dye wastewater. The results showed that for a certain concentration of methyl orange solution, more than 95% could be removed in just 1 hour; while activated carbon required 8h to remove 88%. Han Deyan et al ^[25] have also done related experiments, and the removal rate of chroma in printing and dyeing wastewater is over 98% after 1 hour of reaction. There is also literature ^[27] reporting that protein, starch, etc. in food processing wastewater can be recovered by using chitosan as a flocculant. Scholars at home and abroad have discussed the application value of magnetic chitosan from different angles through a large number of studies. There have been many literature reports on the use of magnetic chitosan for metal ions, papermaking wastewater, printing and dyeing wastewater, etc. The purification research of phenol, especially the exploration of new substances produced by re-crosslinking it with other substances is very rare.

Known for its pyroelectricity and piezoelectricity, tourmaline has been fully used in the industrial field from the 18th century to the middle of the 20th century, but its electrical properties and environmental protection functions have not been paid attention to. In 1989, Kubo proposed for the first time that there is an electrostatic field on the surface of tourmaline particles, and predicted the application prospect of tourmaline in the field of environment. Japanese scholars have also found that the river water containing tourmaline in the formation is difficult to be polluted, which has opened up the application of tourmaline in the field of environmental protection. Relevant studies have shown that tourmaline has good polarity, strong surface static electricity, and strong adsorption to harmful ions in water (such as Cu, As(Ⅲ), F-, etc.), and can be used to purify water bodies. Polluted good environment mineral material. Up to now, there has not been any related report about utilizing chitosan and tourmaline to jointly prepare water purifying agent to purify water.

Contents of the invention

The object of the present invention is to provide a water treatment agent with high removal rate of phenol in water.

Another object of the present invention is to provide a preparation method of the above-mentioned water treatment agent.

The purpose of the present invention is achieved through the following technical solutions:

A water treatment agent is characterized in that: it is made by adding the mixed powder of tourmaline and magnetic chitosan microspheres to sodium alginate and polyvinyl alcohol, dissolving, mixing, and then solidifying into balls; the magnetic shell Polycan microspheres are made of superparamagnetic ferric oxide powder, 1-10wt% (preferably 2wt%) chitosan acetic acid solution, liquid paraffin, Span-80, and glutaraldehyde solution as reaction materials, and are cross-linked by emulsification. Prepared by method, wherein the mass ratio of superparamagnetic iron tetroxide and said chitosan acetic acid solution is 1:1～10 (preferred mass ratio is 2:5); the volume ratio of liquid paraffin and Span-80 is 10～100 : 1 (the preferred volume ratio is 40:1); the volume ratio of the chitosan acetic acid solution of superparamagnetic ferroferric oxide and the paraffin-Span-80 mixed solution is 1:1～10, preferably 1:2; the above The volume ratio of the chitosan acetic acid solution of superparamagnetic iron tetroxide, paraffin, and Span-80 to glutaraldehyde solution (preferably of analytical grade) is 5-50:1, preferably 25:1.

In the preparation of tourmaline and magnetic chitosan microspheres, if there are too few balls, they are easy to loosen during use, and if there are too many balls, too thick will affect the function of the active ingredients, which will affect the processing efficiency. In order to further improve the uniformity and effectiveness of balling, thereby improving the removal rate of the water treatment agent of the present invention to phenol, in the mixed powder of the above-mentioned tourmaline and magnetic chitosan microspheres, the quality of tourmaline and magnetic chitosan microspheres The ratio is 1-10:1, preferably 5:2, and the mass ratio of the mixed powder of sodium alginate, polyvinyl alcohol, tourmaline and magnetic chitosan microspheres is 1:1-10:1-12, preferably The ratio is 1:6:7.

Preferably, the superparamagnetic ferric oxide powder of the present invention is prepared as follows:

Weigh 5.56g FeSO ₄ ·7H ₂ O, 6.5g FeCl ₃ and 1.7mL concentrated hydrochloric acid and dissolve them in 50mL distilled water degassed with N ₂ beforehand, then add the above dropwise to 250mL 1.0mol/L NaOH solution. Stir slowly (100r/min) in a water bath at 80°C for 5min, then stir mechanically at a high speed (2000r/min), until a black precipitate appears in the solution, and continue stirring for 30min. After the reaction was finished, it was left to cool down to room temperature, and the black precipitate was separated by applying an external magnetic field, washed three times with deionized water and absolute ethanol, and dried in a vacuum oven at 60°C for 12 hours before use.

Chitosan acetic acid solution of the present invention is prepared by dissolving chitosan in acetic acid solution (preferably using analytically pure); said chitosan is preferably chitosan with a deacetylation degree of 90%, purchased from Shanghai Hufeng Biochemical Reagent Co., Ltd. is a commercially available product.

Preferably, the tourmaline of the present invention is produced in Chifeng, Inner Mongolia, and is a commercially available product.

The preparation method of above-mentioned water treatment agent, prepares as follows:

a. Pretreatment of tourmaline

The tourmaline is crushed through a 100-400 mesh sieve (preferably 200 mesh), washed 5 to 7 times with a NaOH solution (preferably 5%) with a mass concentration of 2-10% to remove the attached anions and cations on the surface, and then used After washing with ion water for the same number of times, put it in the oven to dry and set aside;

b. Preparation of superparamagnetic Fe3O4 powder

Weigh 5.56g FeSO ₄ ·7H ₂ O, 6.5g FeCl ₃ and 1.7mL concentrated hydrochloric acid and dissolve in 50mL pre-degassed distilled water with N ₂ , then add the above dropwise to 250mL 1.0mol/L NaOH solution; Stir at a slow speed of 100r/min in a water bath at 80°C for 5min, and then stir mechanically at a speed of 2000r/min until a black precipitate appears in the solution, and continue to stir for 30min; Separate the black precipitated product, wash it with deionized water and absolute ethanol three times, and dry it in a vacuum oven at 60°C for 12 hours before use;

c. Preparation of Magnetic Chitosan Microspheres

Take superparamagnetic ferric oxide powder and join in the chitosan acetic acid solution that mass concentration is 1～10% (preferably 2%), wherein the mass ratio of superparamagnetic ferric oxide and chitosan acetic acid solution 1:1 to 1:10 (preferably 2:5), stir and mix evenly, then transfer to the liquid paraffin and Span-80 mixture, wherein the volume ratio of liquid paraffin to Span-80 is 10:1 to 100:1 (preferred volume ratio is 40:1), adjust pH value to 3.0～12.0 (preferably 9.0), 100～500r/min (preferably 200r/min) stir 30min, the chitosan of described superparamagnetic iron tetroxide The volume ratio of acetic acid solution to paraffin-Span-80 mixed solution is 1:1～1:10 (preferably 1:2); dropwise add glutaraldehyde solution, chitosan acetic acid solution of superparamagnetic iron tetraoxide and The mixed solution of paraffin, Span-80, and glutaraldehyde solution (preferably using analytical grade) have a volume ratio of 5:1 to 50:1 (preferably 25:1), and continue to stir at 20 to 80°C (preferably 40°C) After 60 minutes, let it fully react, then filter under reduced pressure, extract with petroleum ether and absolute ethanol for 1-10 times (preferably 3 times), and vacuum dry at 20-100°C (preferably 50°C) to obtain the product;

d. Preparation of tourmaline/magnetic chitosan microspheres (MCD)

Grind the above-mentioned magnetic chitosan microspheres into 100-400 mesh (preferably 140 mesh) powder, and then mix it with tourmaline powder in a mass ratio of 1:1-10:1 (preferably 5:2) Mix well to prepare mixed powder; prepare microspheres by mixing sodium alginate, polyvinyl alcohol and mixed powder according to the ratio of 1:1:1 to 1:10:12 (preferably mass ratio 1:6:7); prepare microspheres When heating and dissolving sodium alginate and polyvinyl alcohol for 15 minutes, then add the mixed powder and stir evenly, cool for 5 to 60 minutes (preferably 20 minutes), and then use a constant flow pump to continuously drop the suspension to a concentration of 1 to 10 wt at a constant flow rate. %CaCl ₂ (preferably 2wt%) in a saturated boric acid solution for solidification. After curing for 5-40 hours (preferably 20 hours), the pellets are filtered out, rinsed with water, and then dried for later use. The present invention has following beneficial effect:

The water treatment agent of the present invention can reach 80%-90% removal rate of volatile phenols in drinking water sources (such as groundwater, reservoir water, etc.), and 93% removal rate of chromium, and the treatment effect is remarkable, see the specific embodiment part, At the same time, the treatment agent of the present invention has the advantages of large adsorption capacity, high purification efficiency, low cost, renewability, non-toxicity, and no pollution to the environment. The preparation method of the water treatment agent of the invention is simple and convenient, has strong repeatability and low cost, and is suitable for industrial scale production.

Detailed ways

The present invention is specifically described below through the examples, it is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, those skilled in the art can according to the above-mentioned present invention Contents Some non-essential improvements and adjustments are made to the present invention.

Example 1

A water treatment agent is prepared in the following steps:

a. Pretreatment of tourmaline

Crush tourmaline through a 200-mesh sieve, wash 5-7 times with NaOH solution with a mass concentration of 5% to remove the anions and cations attached to the surface, and then wash with deionized water for the same number of times, then put it in an oven to dry, and wait for use;

b. Preparation of superparamagnetic Fe3O4 powder

Weigh 5.56g FeSO ₄ ·7H ₂ O, 6.5g FeCl ₃ and 1.7mL concentrated hydrochloric acid and dissolve in 50mL pre-degassed distilled water with N ₂ , then add the above dropwise to 250mL 1.0mol/L NaOH solution; Stir at a slow speed (100r/min) in a water bath at 80°C for 5min, and then stir rapidly (2000r/min) mechanically, until a black precipitate appears in the solution, and continue to stir for 30min; The black precipitate was separated by applying an external magnetic field, washed three times with deionized water and absolute ethanol, and dried in a vacuum oven at 60°C for 12 hours before use.

c. Preparation of Magnetic Chitosan Microspheres

The superparamagnetic ferric iron tetroxide powder that takes particle diameter about 20nm joins in the chitosan acetic acid solution that mass concentration is 2%, and the mass ratio of described superparamagnetic ferric ferric oxide and chitosan acetic acid solution is 2 :5; after stirring and mixing evenly, transfer to the mixed solution of liquid paraffin (analytical pure) and Span-80 (edible), wherein the volume ratio of liquid paraffin and Span-80 is 40:1, adjust the pH value to 9.0, 200r /min stirred for 30min, wherein the volume ratio of chitosan acetic acid solution of superparamagnetic ferric oxide to paraffin-Span-80 mixed solution was 1:2; glutaraldehyde solution was added dropwise, superparamagnetic ferric oxide The mixture of chitosan acetic acid solution, paraffin, and Span-80, with a volume ratio of glutaraldehyde solution (analytical pure) of 25:1, was stirred at 40°C for 60 minutes to fully react, and then filtered under reduced pressure. Sequentially extract three times with petroleum ether and absolute ethanol, and vacuum-dry at 50°C to obtain it;

d. Preparation of tourmaline/magnetic chitosan microspheres (MCD)

Grind the above-mentioned magnetic chitosan microspheres into 140-mesh powder, and then fully mix with the above-mentioned tourmaline powder according to the ratio of 5:2 to obtain a mixed powder; mix sodium alginate, polyvinyl alcohol and the mixed powder according to the mass ratio Prepare microspheres at a ratio of 1:6:7; when preparing microspheres, first heat and dissolve sodium alginate and polyvinyl alcohol for 15 minutes, then add the mixed powder and stir evenly, and after cooling for 20 minutes, use a constant flow pump to continuously pump the suspension at a constant flow rate. Drop it into a saturated boric acid solution containing 2% CaCl ₂ for solidification, filter out the pellets after solidification for 20 hours, rinse them with water and dry them for later use.

Embodiment 2～7: carry out by following each material and step, all the other are with embodiment 1.

The removal rate of the tourmaline/magnetic chitosan microspheres prepared above is 78% to 90% for the volatile phenol in the source water.

Application Example 1

Tourmaline/Magnetic Chitosan Microspheres (MCD) Microspheres Purify Water Samples

1. Experiment on the removal of volatile phenol in water

Get the water sample of 50ml source water (containing volatile phenol 0.0043-0.0049mg/L) in the 250ml Erlenmeyer flask, add the MCD microsphere that embodiment 1 makes, adjust experimental condition, leave standstill after oscillating for a certain period of time in the constant temperature oscillation box , Filtration, use to measure the phenol content in the filtrate, and the removal rate of MCD to volatile phenol can be obtained by calculation. The experimental design is shown in Table 1 and Table 2. Each experiment was repeated three times, and the average value was taken.

(1), single factor experiment

Table 1 Single factor experimental design

(2), secondary regression combination of political and religious rotation

On the basis of the above, the quadratic regression orthogonal rotation combination 3 (1/2) design is used to design the factors of MCD pellets on volatile phenol in water, and the dosage of MCD (x ₁ ) and the pH value of the solution (x ₂ ) are taken. and reaction time (x ₃ ) are used as three factors to be investigated, and five levels are selected for each factor, as shown in Table 2.

Table 2 Orthogonal test factor level coding table

2. Experiment on the removal of Cr in water

Get 50ml source water (containing Cr0.045-0.056mg/L) in the 250ml Erlenmeyer flask, add the MCD microspheres that embodiment 1 makes, adjust experimental condition, leave standstill, filter after vibrating in constant temperature shaking box for a certain hour, The volatile phenol in the filtrate was measured by gas chromatography, the Cr(VI) in the filtrate was measured by atomic absorption spectrophotometry, and the removal rate of Cr(VI) by the microspheres could be obtained by calculation. The experimental design is shown in Table 1 and Table 2. Each experiment was repeated three times, and the average value was taken.

Table 1 Single factor experimental design

Table 2 Orthogonal test factor level coding table

(3) Conclusion:

1. Experiment on the removal of volatile phenol in water

(1) Single factor experiments show that MCD pellets can be used to remove volatile phenols in water. When the time is 1.5h and the dosage of MCD is 2.5g, the potential removal rate of volatile phenol in water reaches 84.17%.

(2) On the basis of the single factor experiment, using the theory and method of regression design, the optimal experimental conditions were determined through the DPS data processing system: the dosage of MCD was 2.16g, the processing time was 1.12h, and the pH value was 10.55. Under this condition, the removal rate of volatile phenol in water reaches 90.72%.

2. Chromium removal experiment in water

(1) The single factor experiment shows that when MCD is used to remove chromium in source water, the removal rate of chromium in source water reaches the best when the dosage is 3g, the pH is 6, and the reaction time is 90min.

(2) Based on the single factor experiment, using the theory and method of regression design, the optimal experimental conditions determined by the DPS data processing system: the dosage of microspheres is 2.444g, the pH value of the solution is 4.6, and the reaction time is 80.4min. Under these conditions, the removal rate of chromium in source water can reach 93.13%.

(3) Based on the single factor experiment, using the theory and method of regression design, the optimal experimental conditions were determined through the DPS data processing system: the reaction time was 80.4min, the pH value was 4.6, and the dosage of microspheres was 2.444g. Under these conditions, according to the mathematical model, the removal rate of Cr(VI) in source water can reach 93.93%.

Claims (1)

1. A preparation method of drinking water treatment agent, prepared according to the following steps: a. Pretreatment of tourmaline Crush the tourmaline through a 200-mesh sieve, wash it with 5% NaOH solution for 5 to 7 times to remove the anions and cations attached to the surface, and then wash it with deionized water for the same number of times, then put it in the oven and dry it. use; b. Preparation of superparamagnetic Fe3O4 powder Weigh 5.56 g FeSO ₄ 7H ₂ O, 6.5 g FeCl ₃ and 1.7 mL of concentrated hydrochloric acid and dissolve them in 50 mL of distilled water degassed with N ₂ beforehand, then add the above dropwise to 250 mL of 1.0mol/L NaOH solution ; Stir slowly at 100r/min in a water bath at 80°C for 5min, then stir mechanically at a speed of 2000r/min until a black precipitate appears in the solution, and continue stirring for 30min; Separate the black precipitated product, wash it with deionized water and absolute ethanol three times, and dry it in a vacuum oven at 60°C for 12 hours before use; c. Preparation of Magnetic Chitosan Microspheres The superparamagnetic ferric iron tetroxide powder that takes particle diameter about 20nm joins in the chitosan acetic acid solution that mass concentration is 2%, and the mass ratio of described superparamagnetic ferric ferric oxide and chitosan acetic acid solution is 2 :5; after stirring and mixing evenly, transfer to the mixed solution of liquid paraffin and Span-80, wherein the volume ratio of liquid paraffin and Span-80 is 40:1, adjust the pH value to 9.0, stir 30min at 200 r/min, wherein super The volume ratio of chitosan acetic acid solution of paramagnetic iron ferric oxide and liquid paraffin-Span-80 mixture is 1:2; dropwise add glutaraldehyde solution, chitosan acetic acid solution of superparamagnetic iron ferric oxide Mixed solution with liquid paraffin and Span-80, the volume ratio of glutaraldehyde solution is 25:1, continue to stir at 40°C for 60 minutes to make it fully react, then filter under reduced pressure, and extract with petroleum ether and absolute ethanol in sequence Extracted three times, dried under vacuum at 50°C to obtain; d. Preparation of drinking water treatment agent Grind the above-mentioned magnetic chitosan microspheres into 140-mesh powder, and then fully mix them with the above-mentioned tourmaline powder according to the ratio of 5:2 by mass to obtain a mixed powder; mix sodium alginate, polyvinyl alcohol and the mixed powder Prepare microspheres according to the mass ratio of 1:6:7; when preparing microspheres, first heat and dissolve sodium alginate and polyvinyl alcohol for 15 minutes, then add the mixed powder and stir evenly, after cooling for 20 minutes, use a constant flow pump to continuously Slowly drop the suspension into a saturated boric acid solution containing 2wt% CaCl ₂ for solidification, filter out the pellets after solidification for 20 h, rinse them with water and dry them for later use.