CN107876002B - Preparation method of adsorption material for landscape water, obtained product and application - Google Patents
Preparation method of adsorption material for landscape water, obtained product and application Download PDFInfo
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- CN107876002B CN107876002B CN201711098783.1A CN201711098783A CN107876002B CN 107876002 B CN107876002 B CN 107876002B CN 201711098783 A CN201711098783 A CN 201711098783A CN 107876002 B CN107876002 B CN 107876002B
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
Abstract
The invention discloses a preparation method of an adsorption material for landscape water, an obtained product and application thereof2Soaking the material in the solution, standing and drying to obtain the landscape water adsorption material. The invention uses the hydroxy alumina as the adsorption material, and adopts a special method to load the hydroxy alumina on the nontoxic and tasteless porous SiO2On the material substrate, the high-adsorbability landscape water adsorption material is obtained. The adsorption material for landscape water is simple to prepare, low in cost, simple and easy to implement, strong in operability and clear and thorough in algae for treating landscape water, is suitable for landscape water with various shapes and scales, is particularly suitable for the requirements of landscape water treatment at present, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of an adsorption material for landscape water, an obtained product and application, and belongs to the technical field of landscape water adsorption treatment.
Background
The landscape water is a water body used for visual appreciation, such as water in various community landscapes, which is different from the running water in rivers and lakes, is easily polluted, particularly, is easily eutrophicated due to the effects of the discharge of rainwater on the ground, the irradiation of sunlight and the like, so that various algae are generated, and the algae not only affect the appearance, but also deteriorate the water body and influence the living environment. At present, the algae is treated by adopting a manual cleaning method and an ecological system purification method, the former method is simple but has high labor intensity and can not be completely treated, the latter method has high requirements on water bodies, the installation and operation of the ecological system need high maintenance cost and long period, and vicious circle can be caused if the management is not good, so people desire a convenient, quick and low-cost algae treatment method.
Disclosure of Invention
Aiming at the current situation that algae in the existing landscape water is difficult to treat, the invention provides a preparation method of an adsorption material for landscape water and an obtained product. The method has the advantages that the hydroxy alumina is used as the adsorption material, the hydroxy alumina is firmly loaded on the nontoxic and tasteless porous silica matrix through special operation, the adsorption material for the landscape water is obtained, the method is simple to operate and low in cost, and the obtained adsorption material for the landscape water can be used for removing algae in the landscape water.
Aiming at the requirements of low cost, sustainability, easy operation and the like of landscape algae pollution treatment, the invention also provides a landscape water treatment method, and the method utilizes the landscape water adsorption material to treat algae in landscape water. The adsorbing material for landscape water can be placed in a cage-shaped bag to be directly put into water, is convenient to use and simple to operate, algae can be adsorbed and gathered together after entering a water body, and then the algae can be manually removed.
The specific technical scheme of the invention is as follows:
a preparation method of an adsorption material for landscape water comprises the following steps:
(1) dispersing the aluminum hydroxide into a thioglycollic acid solution, and uniformly stirring to obtain an aluminum hydroxide solution;
(2) porous SiO2Soaking the material in the above hydroxy alumina solution, standing to fix hydroxy alumina to porous SiO2And standing the materials, and drying to obtain the landscape water adsorption material.
In the preparation method, the mass ratio of the aluminum oxyhydroxide to the thioglycolic acid to the water is 1: 0.01: 70-90. According to the invention, under the action of thioglycollic acid, the aluminum oxyhydroxide can firmly grow on the porous silicon dioxide material, so that the aluminum oxyhydroxide can still be firmly loaded on the porous silicon dioxide material after entering water.
In the above preparation method, porous SiO2The material is kept stand and soaked in the hydroxy alumina solution for 2 to 2.5 days.
In the above preparation method, the aluminum oxyhydroxide is fibrous, and those skilled in the art can prepare the aluminum oxyhydroxide by using a preparation method satisfying the requirement in the prior art, for example, the aluminum oxyhydroxide can be prepared by a method reported in the literature (Rsc. adv. 2015,5,33155-33162).
In the above preparation method, the porous silica is SiO containing through macropores prepared by the special method of the present invention2Material, use of the materialThe material may promote the growth of aluminum oxyhydroxide on the silica. In addition, the product can be prepared by other methods in the prior art by the skilled person, but the effect is not as good as the invention. The invention has simple operation and large specific surface area of porous SiO2The preparation method of the material comprises the following steps:
dissolving PVP into a mixed solution of ethanol and water, stirring uniformly, then adding orthosilicate ester and ammonia water, stirring fully to hydrolyze the orthosilicate ester, and then standing to obtain SiO2a/PVP mixed gel block; mixing SiO2Drying and calcining the/PVP mixed gel block to obtain porous SiO2A material.
Further, porous SiO is prepared2When the concentration of ammonia water is 25wt%, the mass ratio of PVP, orthosilicate ester, ammonia water, water and ethanol is 1: 1: 0.1: 10-20: 20-30. The purpose of the orthosilicate is to provide a silicon source, and the orthosilicate can be tetraethoxysilane, tetrabutyl orthosilicate and the like, and tetraethoxysilane is commonly used.
Further, porous SiO is prepared2Adding orthosilicate ester and ammonia water, stirring for 5-6h, and standing for 2-2.5 days.
Further, porous SiO is prepared2In the case of materials, SiO2the/PVP mixed gel block was dried at 110 ℃. After drying, SiO2the/PVP mixed gel block is calcined in the air, the calcining temperature is 700 ℃, and the calcining time is 2 h.
In the preparation method of the invention, the finally obtained landscape water adsorption material is made of porous SiO2The material consists of aluminum oxyhydroxide. Through component analysis, the hydroxy aluminum oxide and the porous SiO2The mass ratio of the materials is 1-5: 100. the aluminum oxyhydroxide grows on the surface and in the pores of the porous silicon dioxide material through chemical bonds.
The adsorbing material for landscape water, which is disclosed by the invention, is low in cost, non-toxic and pollution-free, can efficiently adsorb various algae in landscape water, is placed in a cage-shaped bag and directly thrown into a water body, is convenient to operate, low in technical difficulty, suitable for complex diversity of landscape water algae, and wide in application prospect. Therefore, the adsorption material for landscape water obtained by the invention is also within the protection range.
The invention also provides a landscape water treatment method, which comprises the following steps: the algae in the landscape water are attracted and gathered together by the landscape water attracting material, and then the algae are directly removed from the landscape water together with the landscape water attracting material. The adsorption material for landscape water adsorbs the algae together through chemical adsorption, and is convenient for fishing and removing.
In the landscape water treatment method, the landscape water adsorption material can be filled into the cage-shaped bag for use, and then the cage-shaped bag is directly put into the landscape water. The cage-shaped bag can be tied on the floating ball and put into water to ensure that the cage-shaped bag is positioned in the water.
In the landscape water treatment method, the amount of the adsorption material for landscape water is 50-200g/m3The water and the landscape water adsorbing material after adsorbing the algae can be repeatedly used after being calcined for the second time, and can be recycled for 10 times.
The invention uses the hydroxy alumina as the adsorption material, and adopts a special method to load the hydroxy alumina on the nontoxic and tasteless porous SiO2On the material substrate, the high-adsorbability landscape water adsorption material is obtained. The adsorption material for landscape water is simple to prepare, low in cost, simple and easy to implement, strong in operability and clear and thorough in algae for treating landscape water, is suitable for landscape water with various shapes and scales, is particularly suitable for the requirements of landscape water treatment at present, and has wide application prospect.
Detailed Description
The present invention is further illustrated by the following examples, which should be understood as being merely illustrative and not limiting. In the following examples, the concentration of ammonia water used was 25% by weight. The aluminum oxyhydroxide used is prepared according to the method of the document Rsc. adv. 2015,5,33155-33162, and the final aluminum oxyhydroxide obtained is fibrous.
Example 1
1.1 dissolving 5g of PVP in a solution of 100g of ethanol and 50g of water, stirring, adding 5g of tetraethoxysilane and 0.5g of ammonia water, stirring for 5 hours, and standing for 2 days to obtain SiO2PVP mixed gel block；
1.2 drying the sample obtained in step 1.1 at 110 deg.C, then calcining at 700 deg.C under oxidizing conditions (i.e. air atmosphere, the same applies below) for 2 hours to obtain porous SiO2Material with a specific surface area of about 500m2/g；
1.3 dispersing 10g of aluminum oxyhydroxide into 700mL of thioglycolic acid aqueous solution (containing 0.1g of thioglycolic acid), and uniformly stirring to obtain an aluminum oxyhydroxide solution; then the porous SiO2And soaking the material in a hydroxy alumina solution, standing for 2 days, and drying to obtain the landscape water adsorption material. Through component analysis, in the adsorption material for landscape water, aluminum hydroxide and porous SiO2The mass ratio of the materials is 5: 100.
example 2
2.1 dissolving 5g of PVP in a solution of 150g of ethanol and 100g of water, stirring, adding 5g of methyl orthosilicate and 0.5g of ammonia water, stirring for 5 hours, and standing for 2 days to obtain SiO2a/PVP mixed gel block;
2.2 drying the sample obtained in step 2.1 at 110 ℃ and then calcining it for 2 hours under the oxidation condition of 700 ℃ to obtain porous SiO2A material;
2.3 dispersing 10g of aluminum oxyhydroxide into 900mL of thioglycolic acid aqueous solution (containing 0.1g of thioglycolic acid), and uniformly stirring to obtain an aluminum oxyhydroxide solution; then the porous SiO2And soaking the material in a hydroxy alumina solution, standing for 2 days, and drying to obtain the landscape water adsorption material. Through component analysis, in the adsorption material for landscape water, aluminum hydroxide and porous SiO2The mass ratio of the materials is 3: 100.
example 3
3.1 dissolving 5g of PVP in a solution of 120g of ethanol and 80g of water, stirring, adding 5g of propyl orthosilicate and 0.5g of ammonia water, stirring for 5 hours, and standing for 2 days to obtain SiO2a/PVP mixed gel block;
3.2 drying the sample obtained in step 3.1 at 110 ℃ and then calcining the dried sample for 2 hours under the oxidation condition of 700 ℃ to obtain porous SiO2A material;
3.3 dispersing 10g of aluminum oxyhydroxide into 800mL of an aqueous thioglycolic acid solution (containing 0.1g of thioglycolic acid)) Uniformly stirring to obtain a hydroxy aluminum oxide solution; then the porous SiO2And soaking the material in a hydroxy alumina solution, standing for 2 days, and drying to obtain the landscape water adsorption material. Through component analysis, in the adsorption material for landscape water, aluminum hydroxide and porous SiO2The mass ratio of the materials is 1: 100.
Comparative example 1
Porous SiO was prepared as in example 12A material. 10g of aluminum oxyhydroxide was dispersed in 700mL of water, after which porous SiO was added2And soaking the material in a hydroxy alumina solution, standing for 2 days, and drying to obtain the landscape water adsorption material. The hydroxyl aluminum oxide does not grow to porous SiO by the observation of an electron microscope2Above all, it cannot be used in water.
Comparative example 2
An adsorption material for landscape water was prepared according to the method of example 1, except that: the thioglycolic acid was replaced by mercaptopropionic acid. Through component analysis, only a small amount of aluminum oxyhydroxide in the finally obtained adsorption material for landscape water is adsorbed to the porous SiO2The composition analysis showed that the aluminum oxyhydroxide and the porous SiO2The mass ratio of the materials is less than 0.05: 100.
Comparative example 3
An adsorption material for landscape water was prepared according to the method of example 1, except that: porous SiO2The material was immersed in a solution of aluminum oxyhydroxide and allowed to stand for 1 day. The observation of an electron microscope shows that the hydroxyl aluminum oxide is on SiO2The distribution is more uniform, but the amount is less, and the composition analysis shows that the hydroxy aluminum oxide and the porous SiO2The mass ratio of the materials is 0.05: 100.
comparative example 4
An adsorption material for landscape water was prepared according to the method of example 1, except that: porous SiO2The material is replaced by common sol-gel SiO2I.e. preparation of SiO2PVP is not added. Electron microscope observation shows that the aluminum oxyhydroxide is adsorbed on SiO2Surface, compositional analysis showed aluminum oxyhydroxide and SiO2The mass ratio of the materials is 0.01: 100.
application example
The inventionThe prepared adsorption material for landscape water can be used for landscape water treatment, and comprises the following steps: the adsorption material for landscape water is filled into a cage-shaped bag, and the cage-shaped bag is provided with air holes and can permeate water. Putting the cage-shaped bags on the floating ball into water to ensure that the cage-shaped bags are positioned in the water, adding 100g of landscape water adsorption material into each cage-shaped bag, and adding every m of landscape water adsorption material32 cage-shaped bags are added into the water body, and are uniformly distributed in the water body when being thrown. After the cage-shaped bag is thrown into the water body for 10 days, the algae in the water body are adsorbed and gathered on the cage-shaped bag, and the gathered algae are removed manually. The adsorbing material recovered from the cage-type bag can be recycled after calcination treatment.
In order to verify the adsorption and aggregation effects of the landscape water adsorption material on algae, the following simulation experiment was performed, the experimental subject was the landscape water adsorption material of example 3 and comparative example 3, and the landscape water used was a rockery landscape in a certain community. The adsorbing materials for landscape water of example 3 and comparative example 3 were packed in respective cage-type bags, each 100 g. According to the method, the water is thrown in two different areas in landscape water every m32 cage-shaped bags are respectively added into the water body. The results after 10 days showed that the algae in the area adjacent to the product of example 3 were completely adsorbed, whereas only about 20% of the algae in the other area to which the product of comparative example 3 was added were adsorbed and removed, and the adsorption effect was poor.
Claims (8)
1. A preparation method of an adsorption material for landscape water is characterized by comprising the following steps:
(1) dispersing the aluminum oxyhydroxide into a water solution of thioglycollic acid, and uniformly stirring to obtain an aluminum oxyhydroxide solution;
(2) porous SiO2Soaking the material in the above hydroxy alumina solution, standing to fix hydroxy alumina to porous SiO2Standing the materials, and drying to obtain the landscape water adsorption material;
the mass ratio of the aluminum oxyhydroxide to the thioglycolic acid to the water is 1: 0.01: 70-90;
porous SiO in the obtained adsorption material for landscape water2The mass ratio of the material to the aluminum oxyhydroxide is100：1-5。
2. The method of claim 1, wherein: porous SiO2The material is kept stand and soaked in the hydroxy alumina solution for 2 to 2.5 days.
3. The method according to claim 1 or 2, characterized in that: porous SiO2The preparation method of the material comprises the following steps: dissolving PVP into a mixed solution of ethanol and water, stirring uniformly, then adding orthosilicate ester and ammonia water, stirring fully to hydrolyze the orthosilicate ester, and then standing to obtain SiO2a/PVP mixed gel block; mixing SiO2Drying and calcining the/PVP mixed gel block to obtain porous SiO2A material.
4. The method of claim 3, wherein: preparation of porous SiO2When the concentration of ammonia water is 25wt%, the mass ratio of PVP, orthosilicate ester, ammonia water, water and ethanol is 1: 1: 0.1: 10-20: 20-30 parts of; the orthosilicate is tetraethoxysilane.
5. The method of claim 3, wherein: preparation of porous SiO2Adding orthosilicate ester and ammonia water, stirring for 5-6h, and standing for 2-2.5 days; SiO 22the/PVP mixed gel block is calcined in the air, the calcining temperature is 700 ℃, and the calcining time is 2 h.
6. The adsorption material for landscape water prepared by the method for preparing an adsorption material for landscape water according to any one of claims 1 to 5.
7. A landscape water treatment method is characterized in that: the landscape water adsorbent material of claim 6 is used to adsorb algae in landscape water together, and then the algae and landscape water adsorbent material are removed together directly from the landscape water.
8. The landscape water treatment method according to claim 7, wherein: and (3) filling the landscape water adsorption material into a cage-shaped bag, and then directly putting the cage-shaped bag into the landscape water.
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| WO2002083297A1 (en) * | 2001-04-16 | 2002-10-24 | Ims Llc | Adsorbent materials for treating biodegradable waste and process for their preparation |
| CN103111254A (en) * | 2013-03-16 | 2013-05-22 | 青岛科技大学 | Preparation method of hollow microspheres with hierarchical structure |
| CN103301815A (en) * | 2012-03-09 | 2013-09-18 | 中原工学院 | Preparation method for bacterial cellulose water ultrafiltration adsorption material |
| CN106115837A (en) * | 2016-07-30 | 2016-11-16 | 铜仁市万山区龙门山泉饮用水有限公司 | A kind of drinkable water is with filtering granule |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2002083297A1 (en) * | 2001-04-16 | 2002-10-24 | Ims Llc | Adsorbent materials for treating biodegradable waste and process for their preparation |
| CN103301815A (en) * | 2012-03-09 | 2013-09-18 | 中原工学院 | Preparation method for bacterial cellulose water ultrafiltration adsorption material |
| CN103111254A (en) * | 2013-03-16 | 2013-05-22 | 青岛科技大学 | Preparation method of hollow microspheres with hierarchical structure |
| CN106115837A (en) * | 2016-07-30 | 2016-11-16 | 铜仁市万山区龙门山泉饮用水有限公司 | A kind of drinkable water is with filtering granule |
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