CN102274727B - A kind of drinking water purification agent and preparation method thereof - Google Patents

Abstract

The invention discloses a drinking water purifying agent and a preparation method thereof. The method prepares composite microspheres by using titanium dioxide as a catalyst and limonite as a carrier, wherein the limonite is first embedded in polyvinyl alcohol and sodium alginate to form limonite microspheres and the limonite microspheres are coated with a nano titanium dioxide layer. When the purifying agent disclosed by the invention is used, the chromium and phenol in drinking water are reduced effectively, the rate of remove of Cr(VI) from water source water reaches 77.76 to 95.83 percent, and the rate of the removal of phenol from the water source water reaches 87.77 to 97.73 percent; and the purifying agent can supply trace element to the water source water, and the water source water is purified effectively, and the quality of the drinking water source is improved greatly.

Description

A kind of drinking water purification agent and preparation method thereof

technical field

The invention relates to the field of water treatment, in particular to the field of drinking water treatment, in particular to a drinking water purifying agent and a preparation and use method thereof.

Background technique

Since the end of the 1970s, there have been a large number of research reports on the treatment of various types of sewage by photocatalysts at home and abroad. The degradation objects involve many important organic compounds such as phenols and dyes and some inorganic compounds. Commonly used photocatalysts include: TiO ₂ , CdS, ZnO, ZnS, AgI and other semiconductor materials. Due to the relatively stable chemical and optical properties of TiO ₂ , high photocatalytic activity and harmlessness, it has been widely studied. However, the suspension phase TiO ₂ catalyst has disadvantages such as easy condensation and deactivation of the catalyst and difficult recovery during use, which limits its application in water treatment; the supported TiO ₂ catalyst has the advantages of easy separation, easy recovery, and reusability. , is one of the current research hotspots in the field of semiconductor photocatalytic materials. Currently commonly used carriers include: SiO ₂ , activated carbon, glass fiber, clay (or other natural minerals), polysaccharides, zeolites and metals, etc. Compared with a single titanium dioxide system, the liquid-solid separation of the supported TiO ₂ - system is easier , can be recycled and reused, so the supported _TiO2 photocatalyst has become a research hotspot.

However, the treatment effect of supported TiO ₂ photocatalysts for water treatment is not ideal enough, and the use of Muyu stone-loaded nano-TiO ₂ to treat drinking water has never been involved.

Contents of the invention

The object of the present invention is to provide a drinking water purifier with good treatment effect, and the drinking water purifier has good treatment effect.

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

Another object of the present invention is to provide a method for using the above-mentioned drinking water purifying agent.

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

A drinking water purifier, characterized in that: it is a composite microsphere made of titanium dioxide as a catalyst and a wooden fish stone as a carrier; the wooden fish stone must first be embedded with polyvinyl alcohol and sodium alginate to make a wooden fish stone The microspheres are then coated with a nano-titanium dioxide layer. Both polyvinyl alcohol and sodium alginate are commercially available products.

In order to improve the adsorption activity of the prepared Muyushi microspheres, the mass ratio of the sodium alginate, polyvinyl alcohol and Muyushi is 1:1-10:1-12, more preferably 1:6:8.

In order to further improve the adsorption activity and stability of the Muyushi microspheres, the Muyushi microspheres prepared above are also solidified, and then coated with a nano-titanium dioxide layer; Saturated boric acid solution containing 1-10% (preferably 2%) CaCl ₂ , calculated by mass percentage. (The saturated boric acid solution containing _CaCl2 is configured as follows: For example, the saturated boric acid solution containing 2% _CaCl2 is to weigh 2 parts of _CaCl2 and add it to 98 parts of saturated boric acid solution)

In order to improve the ability of the drinking water purifying agent of the present invention to degrade organic matter in water and precipitate unstable metal ions, preferably, the nano-titanium dioxide must first be pretreated, specifically, the mass ratio of nano-titanium dioxide and absolute ethanol is 1:2-10 ( The preferred mass ratio is 1:4) to dissolve into a suspension, and at the same time of alcoholysis, add acetylacetone with a volume percentage concentration of 5-20% (preferably 10%), and use a volume percentage concentration of 2-10% (preferably 5%) HNO ₃ to adjust the pH value to 2-3, put it into a shaking box, and alcoholize 1 ~9 h (preferably 5 h), take out, age for 3~5 days, and set aside.

A preparation method of a drinking water purifier, characterized in that: firstly, pretreating Muyu stone and nano-titanium dioxide;

The pretreatment of the Muyu stone is to crush it through a 100-400 mesh sieve (preferably 200 mesh), and wash it with a NaOH solution with a mass concentration of 2-10% (preferably 5%) for 5 to 7 times to remove the attached surface. Anions and cations, and then wash the same number of times with deionized water, put it in the oven to dry, and set aside;

The pretreatment of nano-titanium dioxide is to dissolve nano-titanium dioxide and absolute ethanol at a mass ratio of 1:2-10 (preferably 1:4) into a suspension, and alcoholyze at 1mL/min-10mL Add acetylacetone with a volume percent concentration of 5-20% (preferably 10%) at a rate of 5mL/min (preferred speed is 5mL/min), and adjust with _HNO3 with a volume percent concentration of 2-10% (preferably 5%) The pH value is 2-3, put it into a shaking box, and alcoholize for 1-9 h (preferably 5 h) at a temperature of 20-80°C (preferably 50°C), a rotation speed of 100-200 r/min (preferably 160 r/min), Take out and age for 3 to 5 days to obtain a nano-titanium dioxide solution for use;

Then prepare Muyushi/nano _{TiO2composite} microspheres as follows:

Mix polyvinyl alcohol and sodium alginate, heat to dissolve for 10-25 minutes, preferably 15 minutes, then add Muyu stone and stir evenly, the mass ratio of sodium alginate: polyvinyl alcohol: Muyu stone is 1:1-10: 1-12 , preferably 1:6:8, after cooling for 10 to 60 minutes, preferably 30 minutes, use a constant flow pump to continuously drop the suspension to a concentration of 1-10% (preferably 2%, in terms of mass percentage) CaCl ₂ in a saturated boric acid solution, the curing time is 5-40 h, preferably 15-25 h, more preferably 20 h, and then filtered out to obtain Muyushi microspheres, rinsed with water and dried for subsequent use;

Add the above-prepared Muyushi microspheres into the above-mentioned alcoholized titanium dioxide solution, soak them, take them out, drain them, dry them naturally, and then put them in a muffle furnace for 60-180 minutes at 50-300°C (preferably 100°C) (preferably 90 min), repeat 1-10 times (preferably 3 times), and prepare Muyushi/nano-TiO ₂ supported active microsphere catalyst.

The present invention has following beneficial effect:

The carrier Muyushi (Limonite, LNT) used in the present invention is called "China's first sacred stone", also known as Yuyuliang, Yuliangshi, and Taiyiyuliang, and is a mineral traditional Chinese medicine rich in iron (Fe). "Shen Nong's Materia Medica" is listed as the top grade, and it is believed that "long-term use can prolong life". Modern pharmacological research shows that Muyu stone has antibacterial, improving body immunity, anti-aging, anti-tumor effects, and has certain analgesic and hematopoietic effects; Muyu stone teabag soaking liquid and digestive juice contain iron, copper, Zinc, strontium and other essential trace elements for the human body and a large amount of macro elements such as potassium, sodium, calcium and magnesium, and no recognized elements harmful to the human body such as lead _and chromium; The active microsphere purifier purifies drinking water, which can increase the essential trace elements and some macro elements in the drinking water, and has a good health care effect on the human body.

Utilize purifying agent of the present invention to effectively reduce chromium and phenol in drinking water, can make the removal rate of Cr(VI) in water source water reach 77.76%～95.83%, the removal rate of phenol reaches 87.77%～97.73%; Supplementing the trace elements in the source water effectively purifies the source water and greatly improves the quality of the drinking water source.

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

One, a kind of drinking water purification agent, make according to the following steps:

1. Pretreatment of Muyu stone

The Muyu stone tested in this experiment was produced on the west side of the Taishan Mountains in Shandong Province; the drinking water for the test was taken from a drinking water source in Yongchuan, Chongqing City (at a water depth of 1m to 1.5m). Muyu stone is crushed through a 200-mesh sieve, washed with 5% NaOH solution for 5 to 7 times to remove the anions and cations attached to the surface, and then washed with deionized water for the same number of times, then dried in an oven for use ;

2. Pretreatment of nano-titanium dioxide

Weigh nanometer TiO ₂ (manufactured by Degussa, Germany, P25 type), dissolve it with absolute ethanol at a mass ratio of 1:4 to form a suspension, and slowly add it at a rate of 5 mL/min at a volume percentage concentration of 10% during alcoholysis. The acetylacetone is adjusted to a pH value of 2-3 with 5% HNO ₃ by volume, placed in a shaking box, alcoholized for 5 h at a temperature of 50°C and a rotational speed of 160 r/min, taken out, and aged for 3-5 God, to be used;

3. Preparation of Muyushi/nano-TiO ₂ composite microspheres

In this experiment, polyvinyl alcohol and sodium alginate were mixed, heated and dissolved for 15 minutes, then a certain amount of wood fish stone was added and stirred evenly, the mass ratio of polyvinyl alcohol: sodium alginate: wood fish stone was 6:1:8, and after cooling for 30 minutes, use The flow pump continuously drips the suspension into a saturated boric acid solution containing 2% (by mass percentage) CaCl ₂ for solidification at a constant flow rate. After solidification for 20 h, filter out the Muyushi microspheres, rinse them with water, and dry them for later use. ;

The Muyushi microspheres prepared above were soaked in the above alcoholized titanium dioxide solution, then taken out, drained, dried naturally and then placed in a muffle furnace for 90 min at 100°C, repeated 3 times to prepare TiO ₂ / Muyushi supported active microsphere catalyst.

2. Purify and treat drinking water sources with the Muyushi/nano- _TiO2 composite microspheres prepared above

Take 100mL of drinking water source water in a 250mL Erlenmeyer flask, add Muyushi/TiO ₂ composite microspheres, treat the water sample with a fluorescent lamp as the experimental light source, measure the chromium content in the water after the reaction, and calculate the Muyushi load. The removal rate of phenol and chromium in water by nano-titanium dioxide photocatalyst; the specific steps are as follows:

1. Removal of phenol

The dosage of Muyushi/nano-TiO ₂ composite microspheres is 1.56g, the pH value of the solution is 4.5, the reaction time is 102.12min, and the light intensity is 1710.8 (x10 lux). The removal rate of phenol in the source water after purification treatment is 97.73%.

2. Removal of chromium

The dosage of Muyushi/TiO ₂ is 1.0g, the pH of the solution is 3.5, the reaction time is 99.22min, and the light intensity is 1600 (x10 lux). The removal rate of Cr(VI) in source water after purification treatment was 95.83%.

Example 2

One, a kind of drinking water purifying agent, make according to the following steps:

1. Pretreatment of Muyu stone

Muyu stone is crushed through a 100-mesh sieve, washed with 10% NaOH solution for 5 to 7 times to remove the anions and cations attached to the surface, and then washed with deionized water for the same number of times, then dried in an oven for use ;

2. Pretreatment of nano-titanium dioxide

Weigh nano TiO ₂ (manufactured by Degussa, Germany, type P25), and dissolve it with absolute ethanol at a mass ratio of 1:2 to form a suspension. The acetylacetone is adjusted to a pH value of 2-3 with 2% HNO ₃ by volume, placed in a shaking box, alcoholized for 6 h at a temperature of 25°C and a rotational speed of 100 r/min, taken out, and aged for 3-5 God, to be used;

3. Preparation of Muyushi/nano-TiO ₂ composite microspheres

In this experiment, polyvinyl alcohol and sodium alginate were mixed, heated and dissolved for 25 minutes, and then Muyu stone was added and stirred evenly. The mass ratio of polyvinyl alcohol: sodium alginate: Muyu stone was 10:1:1, and a constant flow pump was used after cooling for 10 minutes. Continuously drip the suspension into a saturated boric acid solution containing 1% (by mass percentage) CaCl ₂ to solidify at a constant flow rate, filter out the Muyushi microspheres after solidification for 40 h, rinse them with water, and dry them for later use;

The Muyushi microspheres prepared above were soaked in the above alcoholized titanium dioxide solution, then taken out, drained, dried naturally and then placed in a muffle furnace for 60 min at 300°C, repeated twice to prepare TiO ₂ / Muyushi supported active microsphere catalyst.

2. Purify and treat drinking water sources with the Muyushi/nano- _TiO2 composite microspheres prepared above

Take 100mL of drinking water source water in a 250mL Erlenmeyer flask, add Muyushi/TiO ₂ composite microspheres, treat the water sample with a fluorescent lamp as the experimental light source, measure the chromium content in the water after the reaction, and calculate the Muyushi load. The removal rate of phenol and chromium in water by nano-titanium dioxide photocatalyst; the specific steps are as follows:

Removal of phenol and chromium

The dosage of Muyushi/nano TiO ₂ composite microspheres is 1.2g, the pH value of the solution is 4, the reaction time is 100min, and the light intensity is 1700 (x10 lux). The removal rate of phenol in the water source water after purification treatment is 90%. The removal rate of Cr(VI) in water is up to 87%.

Example 3

One, a kind of drinking water purifying agent, make according to the following steps:

1. Pretreatment of Muyu stone

Muyu stone is crushed through a 400-mesh sieve, washed with 10% NaOH solution for 5 to 7 times to remove the anions and cations attached to the surface, and then washed with deionized water for the same number of times, then dried in an oven for use ;

2. Pretreatment of nano-titanium dioxide

Weigh nanometer TiO ₂ (produced by Degussa, Germany, P25 type), dissolve it with absolute ethanol at a mass ratio of 1:10 to form a suspension, and at the same time of alcoholysis, slowly add it at a rate of 1.5mL/min with a concentration of 19% by volume. % acetylacetone, adjust the pH value to 2-3 with 8% _HNO3 by volume, put it into the shaking box, and alcoholize it for 2 hours at a temperature of 77°C and a speed of 190r/min, take it out, and age it for 3-5 God, to be used;

3. Preparation of Muyushi/nano-TiO ₂ composite microspheres

In this experiment, polyvinyl alcohol and sodium alginate were mixed, heated and dissolved for 12 minutes, and then Muyu stone was added and stirred evenly. The mass ratio of polyvinyl alcohol: sodium alginate: Muyu stone was 1:1:1, and a constant flow pump was used after cooling for 55 minutes. Continuously drop the suspension into a saturated boric acid solution containing 8% (by mass percentage) CaCl ₂ for solidification at a constant flow rate, filter out the Muyushi microspheres after solidification for 6 h, rinse with water and dry for later use;

The Muyushi microspheres prepared above were soaked in the alcoholized titanium dioxide solution, then taken out, drained, dried naturally, and then placed in a muffle furnace for 170 minutes at 60°C. Repeated 6 times to prepare TiO ₂ / Muyushi supported active microsphere catalyst.

2. Purify and treat drinking water sources with the Muyushi/nano- _TiO2 composite microspheres prepared above

Take 100mL of drinking water source water in a 250mL Erlenmeyer flask, add Muyushi/TiO ₂ composite microspheres, treat the water sample with a fluorescent lamp as the experimental light source, measure the chromium content in the water after the reaction, and calculate the Muyushi load. The removal rate of phenol and chromium in water by nano-titanium dioxide photocatalyst; the specific steps are as follows:

Removal of phenol and chromium

The dosage of Muyushi/nano TiO ₂ composite microspheres is 1.2g, the pH value of the solution is 4, the reaction time is 100min, and the light intensity is 1700 (x10 lux). The removal rate of phenol in the water source water after purification treatment is 88%. The removal rate of Cr(VI) in water is up to 80%.

Example 4

One, a kind of drinking water purifying agent, make according to the following steps:

1. Pretreatment of Muyu stone

Muyu stone is crushed through a 300-mesh sieve, washed with 7% NaOH solution for 5 to 7 times to remove the anions and cations attached to the surface, and then washed with deionized water for the same number of times, then dried in an oven for use ;

2. Pretreatment of nano-titanium dioxide

Weigh nano-TiO ₂ (manufactured by Degussa, Germany, P25 type), dissolve it with absolute ethanol at a mass ratio of 1:10 to form a suspension, and alcoholize it for use;

3. Preparation of Muyushi/nano-TiO ₂ composite microspheres

In this experiment, polyvinyl alcohol and sodium alginate were mixed, heated and dissolved, and then Muyu stone was added and stirred evenly. The mass ratio of polyvinyl alcohol: sodium alginate: Muyu stone was 8:1:12, and Muyu stone microspheres were obtained;

Add the above-prepared Muyushi microspheres into the above-mentioned alcoholized titanium dioxide solution, soak them, take them out, drain them, dry them naturally, and then burn them in a muffle furnace to prepare a TiO ₂ /Muyushi supported active microsphere catalyst .

2. Purify and treat drinking water sources with the Muyushi/nano- _TiO2 composite microspheres prepared above

Take 100mL of drinking water source water in a 250mL Erlenmeyer flask, add Muyushi/TiO ₂ composite microspheres, treat the water sample with a fluorescent lamp as the experimental light source, measure the chromium content in the water after the reaction, and calculate the Muyushi load. The removal rate of phenol and chromium in water by nano-titanium dioxide photocatalyst; the specific steps are as follows:

The dosage of Muyushi/nano TiO ₂ composite microspheres is 1.2g, the pH value of the solution is 4, the reaction time is 100min, and the light intensity is 1700 (x10 lux). The removal rate of Cr(VI) in the post-source water reaches 78-93%.

Claims (5)

1. A drinking water purifying agent, characterized in that: it is a composite microsphere made of titanium dioxide as a catalyst and a wooden fish stone as a carrier; said wooden fish stone will first be embedded and made by polyvinyl alcohol and sodium alginate Muyushi microspheres are solidified by using a saturated boric acid solution containing 1 to 10% CaCl ₂ in terms of mass percentage, and then coated with a nano-titanium dioxide layer; the sodium alginate, polyvinyl alcohol and Muyu The mass ratio of stone is 1:1-10: 1-12; the nano-titanium dioxide must first be pretreated, specifically, the nano-titanium dioxide and absolute ethanol are dissolved into a suspension with a mass ratio of 1:2-10, alcoholysis At the same time, add acetylacetone with a concentration of 5 to 20% by volume, adjust the pH value to 2 to 3 with _HNO3 with a concentration of 2 to 10% by volume, and put it into a shaking box at a temperature of 20 to 80°C. Rotate at 100-200 r/min, alcoholize for 1-9 hours, take it out, age for 3-5 days, and set aside. 2. The drinking water purifying agent according to claim 1, characterized in that: the mass ratio of sodium alginate, polyvinyl alcohol and Muyu stone is 1:6:8. 3. The drinking water purifying agent according to claim 1 or 2, characterized in that: in the pretreatment of nano-titanium dioxide, the mass ratio of nano-titanium dioxide and absolute ethanol is 1:4, and the alcoholysis is added simultaneously The volume percentage concentration of acetylacetone is 10%, and the volume percentage concentration of HNO ₃ to adjust the pH value is 5%; it is placed in a shaking box at a temperature of 50°C and a rotation speed of 160r/min, and alcoholized for 5 h. 4. a preparation method of drinking water purifying agent as claimed in claim 1, is characterized in that: first wooden fish stone and nanometer titanium dioxide are carried out pretreatment; The pretreatment of the Muyu stone is to crush it through a 100-400 mesh sieve, wash it with a NaOH solution with a mass concentration of 2-10% for 5 to 7 times to remove the anions and cations attached to the surface, and then wash it with deionized water. After the number of times, put it in the oven to dry and set aside; The pretreatment of nano-titanium dioxide is to dissolve nano-titanium dioxide and absolute ethanol in a mass ratio of 1:2-10 into a suspension, and at the same time of alcoholysis, add volume percentage concentration at a rate of 1mL/min-10mL/min 5-20% acetylacetone, adjust the pH value to 2-3 with _HNO3 with a concentration of 2-10% by volume, put it in a shaking box, at a temperature of 20-80°C, and a speed of 100-200 r/min , alcoholized for 1 to 9 h, taken out and aged for 3 to 5 days to obtain a nano-titanium dioxide solution for use; Then prepare Muyushi/nano _{TiO2composite} microspheres as follows: Mix polyvinyl alcohol and sodium alginate, heat to dissolve for 10-25 minutes, then add Muyu stone and stir evenly, the mass ratio of sodium alginate: polyvinyl alcohol: Muyu stone is 1:1-10: 1-12, cool for 10- After 60 minutes, use a constant flow pump to continuously drop the suspension into a saturated boric acid solution containing 1-10% CaCl ₂ in terms of mass percentage to solidify. The solidification time is 5-40 h, and then filter out to obtain Muyushi microspheres, rinsed with water and dried for later use; Add the above-prepared Muyushi microspheres into the above-mentioned alcoholized titanium dioxide solution and soak them, then take them out, drain them, dry them naturally, and then place them in a muffle furnace for 60-180 minutes at 50-300°C, repeating 1-10 minutes. Second, Muyushi/nano-TiO ₂ supported active microsphere catalysts were prepared. 5. the preparation method of drinking water purifying agent as claimed in claim 4 is characterized in that: first wooden fish stone and nanometer titanium dioxide are carried out pretreatment; The pretreatment of the Muyu stone is to crush it through a 200-mesh sieve, wash it with a NaOH solution with a mass concentration of 5% 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. Put it in the oven to dry and set aside; The pretreatment of nano-titanium dioxide is to dissolve nano-titanium dioxide and absolute ethanol into a suspension in a mass ratio of 1:4, and at the same time of alcoholysis, add acetylacetone with a volume percentage concentration of 10% at a rate of 5mL/min , adjust the pH value to 2-3 with 5% HNO ₃ by volume, put it in a shaking box, age at 50°C, 160 r/min, alcoholize for 5 h, take it out, and age for 3-5 days to get Nano titanium dioxide solution, stand-by; Then prepare Muyushi/nano _{TiO2composite} microspheres as follows: Mix polyvinyl alcohol and sodium alginate, heat to dissolve for 15 minutes, then add Muyu stone and stir evenly. The mass ratio of sodium alginate: polyvinyl alcohol: Muyu stone is 1:6:8. After cooling for 30 minutes, use a constant flow pump to Continuously drip the suspension into a saturated boric acid solution containing 2% CaCl ₂ in terms of mass percentage for solidification. The solidification time is 20 h, and then filter out to obtain Muyushi microspheres. Rinse them with water and dry them for later use. ; The Muyushi microspheres prepared above were soaked in the above alcoholized titanium dioxide solution, then taken out, drained, dried naturally and then placed in a muffle furnace for 90 min at 100°C, repeated 3 times to prepare Muyushi / Nano TiO ₂ supported active microsphere catalyst.