CN106140105A - A kind of preparation method of waste water mercury-removing adsorbent - Google Patents

Abstract

The invention discloses the preparation method of a kind of waste water mercury-removing adsorbent, it is that Pericarpium Musae is pulverized, add sodium hydroxide solution to soak, it is washed with water and washs Fructus Musae corium farinosum to neutral, in Pericarpium Musae cellulose, add ethyl acrylate, add water, mix homogeneously, at temperature is 60 80 DEG C, it is dried 2 3h, obtains modified Fructus Musae corium farinosum；Take Entermorpha powder and thiourea adds ultrasonic stirrer, add suitable quantity of water and carry out ultrasonic reaction, reacted pastel is placed in heat drying 1 2h in the baking oven of 70 80 DEG C, obtains modified Entermorpha powder；Again modification Fructus Musae corium farinosum, modified Entermorpha powder are added agitator, add cerous sulfate solution and sodium alginate, add water furnishing pasty state, pastel is put into microwave heating equipment heat drying, be cooled to room temperature, grind, obtain waste water mercury-removing adsorbent.The adsorbent of the present invention has the advantages such as raw material sources are extensive, with low cost, specific surface area is big, adsorption capacity is big, adsorption efficiency is high, preparation technology is simple, and waste water mercury ion is had good absorption property.

Description

A kind of preparation method of waste water mercury removal adsorbent

technical field

The invention relates to the technical field of adsorption materials, in particular to a preparation method of an adsorbent for removing mercury from wastewater.

Background technique

In recent years, with the development of the heavy metal industry and the arbitrary discharge of heavy metal wastewater without treatment, the content of heavy metal ions in natural water bodies has increased, and water pollution incidents have occurred frequently. Heavy metals are one of the important causes of environmental pollution. When heavy metals enter the environment, they cannot be biodegraded into harmless substances. At the same time, suspended particles in the water absorb and precipitate heavy metal ions, making the water polluted by heavy metals for a long time. And so it came about. What's more, the heavy metals that exist in living organisms are accumulated and enriched, and they also participate in the cycle of the biosphere, endangering human health, and are a type of pollutant that is extremely harmful to the ecological environment. Heavy metal pollution in water has become a worldwide environmental problem of concern to the whole society.

Mercury-containing wastewater mainly comes from non-ferrous metal smelters, instrument factories and some chemical plants. Mercury is a very toxic metal. Organic mercury is more toxic than metallic mercury and inorganic mercury compounds, so poisoning is more likely to occur. Both organic mercury and methylmercury can enter the human body through the respiratory tract, digestive tract, and skin. Inorganic mercury accumulates mainly in the kidneys, followed by the liver and spleen; methylmercury not only accumulates in the liver, kidneys and other organs, but also accumulates in the brain tissue through the blood-brain barrier. Mercury poisoning can damage the central nervous system. In mild cases, it manifests as stomatitis, tremor, impatience, irritability and emotional instability. In severe cases, it causes mental disorders, reduced behavioral control ability, quadriplegia, deafness and blindness, and even becomes an idiot. Therefore, how to treat mercury-containing wastewater economically and effectively has become one of the important research directions in our country.

There are many treatment methods for mercury-containing wastewater. The sulfide precipitation method, ferrite method, flotation method, and xanthate are suitable for treating a small amount of mercury-containing wastewater, and the treatment of a large amount of mercury-containing wastewater. The treatment methods for mercury-containing industrial wastewater include Chemical precipitation, coagulation precipitation, ion exchange, adsorption, etc. Because the adsorption method has the advantages of simple process flow, good treatment effect and strong operability, it has been widely used in the treatment of mercury ions in wastewater. Among them, activated carbon, as an effective adsorbent for wastewater treatment, can be used to remove most heavy metals and organic molecules and has strong adsorption capacity. However, the resource of activated carbon is limited, and the cost of treating wastewater in large quantities is high, the life is short, and the regeneration operation cost is high. It is widely used in underdeveloped areas. Existing polymer adsorbents, adsorbents prepared from waste, and composite adsorbents also have problems such as high cost, low adsorption efficiency, and easy to produce secondary pollution. Therefore, how to improve the adsorption efficiency of the adsorbent and reduce the secondary pollution caused by the use of the adsorbent is a research hotspot today.

Contents of the invention

Aiming at the problems existing in the existing adsorbents, the present invention provides an adsorbent for removing mercury from waste water with large specific surface area, large adsorption capacity, high adsorption efficiency, low cost, simple preparation process, safety and environmental protection.

In order to achieve the above object, the present invention is achieved through the following technical solutions:

A preparation method of mercury-removing adsorbent for wastewater, comprising banana peel, ethyl acrylate, enteromorpha powder, sulfur Urea, cerium sulfate and sodium alginate are used as raw materials, and the adsorbent is made by microwave heating method. The specific operation steps are as follows:

(1) Crush 100 parts of banana peel, add sodium hydroxide solution to soak for 3-5 hours, then wash the banana peel powder with water until neutral to obtain banana peel cellulose; add 10-15 parts of ethyl acrylate to the banana peel cellulose , then add 100-120 parts of water, mix evenly, and dry at a temperature of 60-80°C for 2-3 hours to obtain modified banana peel powder;

(2) Take 50-70 parts of Enteromorpha powder and 6-10 parts of thiourea and add them to an ultrasonic stirrer, then add an appropriate amount of water for ultrasonic reaction, and place the reacted paste in an oven at 70-80°C to heat and dry for 1- 2h, get modified enteromorpha powder;

(3) Add the above-mentioned modified banana peel powder and modified enteromorpha powder into the mixer, add 4-6 parts of cerium sulfate solution and 10-15 parts of sodium alginate, then add water to make a paste, put the paste Put it into a microwave heating equipment, microwave at a temperature of 120-140°C for 30-60min, cool to room temperature, and grind to obtain a mercury-removing adsorbent for wastewater.

Preferably, the water content of the above-mentioned banana peel is 12%.

Preferably, the above step (1) is to crush the banana peel to 40-60 mesh.

Preferably, the concentration of the above-mentioned sodium hydroxide is 3-5 mol/L.

Preferably, the above-mentioned Hutai powder is washed fresh Hutai powder, dried to a water content of 10%, and then crushed to 80 mesh to obtain Hutai powder.

Preferably, the ultrasonic reaction in the above step (2) is performed at an ultrasonic frequency of 60-80 kHz for 20-30 minutes.

Preferably, the power of the microwave in the above step (3) is 200-300W.

Preferably, the concentration of the above-mentioned cerium sulfate solution is 5 mol/L.

Preferably, the grinding in the above step (3) is to grind the material to a particle size of 0.5-1.0 mm.

Compared with prior art, advantage and beneficial effect of the present invention are:

1. The adsorbent prepared by the present invention has the advantages of wide source of raw materials, low cost, large specific surface area, large adsorption capacity, high adsorption efficiency, simple preparation process, environmental protection and easy degradation, and has good adsorption performance for mercury ions. Wastewater treatment has broad market prospects.

2. The present invention uses the agricultural waste banana peel as the main raw material, which not only has a wide range of raw material sources and low price, but also realizes the recycling and utilization of waste and increases the application value of the banana peel.

3. This method uses sodium hydroxide and ethyl acrylate to modify the banana peel, which can remove the pigment, lignin and hemicellulose of the banana peel, because the molecular chain of ethyl acrylate has a large number of active groups such as carboxyl groups. , which can activate the adsorption sites and improve the adsorption performance of the adsorbent.

4. The present invention uses Enteromorpha with wide distribution, fast propagation speed and short growth cycle as raw material, which not only provides an effective treatment approach for the disaster of the Formosa, the porous structure of the Formosa can provide effective adsorption sites for heavy metals, and simultaneously Taiwan is rich in various macromolecular substances such as protein, polysaccharide and crude fiber, and contains a large number of functional groups such as hydroxyl, carboxyl and amino groups, which can undergo a relatively complete complexation reaction with mercury ions, thereby achieving better adsorption effects.

5. This method adopts ultrasonic treatment of Enteromorpha powder, which can quickly break the cell wall of the plant, so that more internal functional groups are exposed to combine with metal ions, and the adsorption effect of heavy metal mercury ions in wastewater is significantly improved.

6. The present invention adopts thiourea to modify Enteromorpha powder, which can endow the adsorbent with larger specific surface area and adsorption capacity, and improve the adsorption performance of the adsorbent to mercury ions.

7. In this method, cerium sulfate is added in the preparation process of the adsorbent, which can improve the adsorption capacity and adsorption efficiency of the adsorbent.

8. The present invention uses microwave heating, which has the advantages of fast heating speed, uniform temperature of the heating system, and low energy consumption.

9. The adsorbent prepared by the present invention has good adsorption performance, wherein the specific surface area of the adsorbent is 300-350m ² /g, and the adsorption rate for mercury ions is over 98%.

detailed description

The present invention will be further described below in conjunction with specific examples, but not limited to the protection scope of the present invention.

Example 1

A kind of preparation method of waste water mercury removal adsorbent, concrete operation steps are as follows:

(1) Crush 100kg of banana peels with a water content of 12% to 40 meshes, add 5mol/L sodium hydroxide solution for soaking for 3 hours, then wash the banana peel powder with water until neutral to obtain banana peel cellulose; Add 12kg of ethyl acrylate to the peel cellulose, then add 100kg of water, mix well, and dry at a temperature of 60°C for 3 hours to obtain modified banana peel powder;

(2) Get 50kg of Enteromorpha powder and 6kg of thiourea into an ultrasonic mixer, then add 100kg of water, and conduct an ultrasonic reaction at an ultrasonic frequency of 80kHz for 20min, place the reacted paste in an oven at 70°C for 2h and heat and dry it to obtain Modified enteromorpha powder;

(3) Add the above-mentioned modified banana peel powder and modified enteromorpha powder to the stirrer, add 5 kg of cerium sulfate solution and 10 kg of sodium alginate, then add water to adjust to a paste, put the paste into microwave heating equipment, and The power is 250W, the temperature is 120°C, microwave for 60min, cool to room temperature, and grind the material to a particle size of 0.5mm to obtain the mercury-removing adsorbent for wastewater.

Example 2

A kind of preparation method of waste water mercury removal adsorbent, concrete operation steps are as follows:

(1) Crush 100kg of banana peels with a water content of 12% to 40 meshes, add 5 mol/L sodium hydroxide solution to soak for 3 hours, then wash the banana peel powder with water until neutral to obtain banana peel cellulose; Add 10kg of ethyl acrylate to the cellulose, then add 100kg of water, mix well, and dry at 80°C for 2 hours to obtain modified banana peel powder;

(2) Take 60kg of Enteromorpha powder and 8kg of thiourea and add them to an ultrasonic mixer, then add 120kg of water, and conduct an ultrasonic reaction at an ultrasonic frequency of 60kHz for 30min, place the reacted paste in an oven at 80°C and heat and dry it for 1.5h. Obtain modified enteromorpha powder;

(3) Add the above-mentioned modified banana peel powder and modified enteromorpha powder to the stirrer, add 4 kg of cerium sulfate solution and 12 kg of sodium alginate, then add water to adjust to a paste, put the paste into microwave heating equipment, and The power is 200W, the temperature is 130°C, microwave for 45 minutes, cool to room temperature, and grind the material to a particle size of 0.5mm to obtain the mercury-removing adsorbent for wastewater.

Example 3

A kind of preparation method of waste water mercury removal adsorbent, concrete operation steps are as follows:

(1) Crush 100kg of banana peels with a water content of 12% to 60 mesh, add 3 mol/L sodium hydroxide solution to soak for 5 hours, then wash the banana peel powder with water until neutral to obtain banana peel cellulose; Add 15kg of ethyl acrylate to the cellulose, then add 120kg of water, mix evenly, and dry at 80°C for 2.5h to obtain modified banana peel powder;

(2) Get 70kg of Enteromorpha powder and 10kg of thiourea and add it to an ultrasonic mixer, then add 150kg of water, and conduct an ultrasonic reaction at an ultrasonic frequency of 70kHz for 30min, place the reacted paste in an oven at 80°C for 2h and heat and dry it to obtain Modified enteromorpha powder;

(3) Add the above-mentioned modified banana peel powder and modified enteromorpha powder to the stirrer, add 6 kg of cerium sulfate solution and 12 kg of sodium alginate, then add water to adjust to a paste, put the paste into microwave heating equipment, and The power is 300W, the temperature is 140°C, microwave for 30min, cool to room temperature, and grind the material to a particle size of 1.0mm to obtain the mercury-removing adsorbent for wastewater.

Example 4

A kind of preparation method of waste water mercury removal adsorbent, concrete operation steps are as follows:

(1) Crush 100 kg of banana peels with a water content of 12% to 60 mesh, add 5 mol/L sodium hydroxide solution to soak for 5 hours, and then wash the banana peel powder with water until neutral to obtain banana peel cellulose; Add 12kg of ethyl acrylate to the cellulose, then add 100kg of water, mix evenly, and dry at 80°C for 2 hours to obtain modified banana peel powder;

(2) Get 60 kg of Enteromorpha powder and 10 kg of thiourea and add them to an ultrasonic mixer, then add 120 kg of water, and conduct an ultrasonic reaction at an ultrasonic frequency of 60 kHz for 60 min, place the reacted paste in an oven at 80° C. for heating and drying for 1 h to obtain Modified enteromorpha powder;

(3) Add the above-mentioned modified banana peel powder and modified enteromorpha powder to the agitator, add 5 kg of cerium sulfate solution and 15 kg of sodium alginate, then add water to adjust to a paste, put the paste into microwave heating equipment, and The power is 250W, the temperature is 120°C, microwave for 60min, cool to room temperature, and grind the material to a particle size of 1.0mm to obtain the mercury-removing adsorbent for wastewater.

The method of using the adsorbent is: at room temperature, put 3g of the adsorbent into 1L of waste water containing mercury ions, control the pH to 6, stir at a speed of 300r/min for 60min, separate the adsorbent, and the waste water can be adsorbed mercury ions in.

The adsorption properties of the adsorbents prepared in Examples 1-4 were measured as follows. The specific surface area of the adsorbent is measured by the specific surface area. The concentration of mercury ions was measured by atomic absorption spectrophotometry, and then the adsorption rate was calculated according to the following formula. The measurement results are shown in the table below.

ŋ=(C ₀ -C _i )×100%/C ₀

Among them, C ₀ and C _i are the content (mg/L) of mercury ions in wastewater before and after adsorption, and ŋ is the adsorption rate.

It can be seen from the measurement results that the adsorbent prepared by the present invention has a large specific surface area, and the adsorption rate of mercury ions reaches more than 98%, and has broad application prospects in industrial wastewater treatment.

The above content cannot be deemed that the specific implementation of the present invention is limited to these descriptions. For those of ordinary skill in the technical field of the present invention, without departing from the concept of the present invention, some simple deduction or replacement can also be made, which should be regarded as Belonging to the scope of patent protection of the present invention determined by the submitted claims.

Claims (9)

1. the preparation method of a waste water mercury-removing adsorbent, it is characterised in that: it is with mass ratio as 100:10-15:50-70:6- The Pericarpium Musae of 10:4-6:10-15, ethyl acrylate, Entermorpha powder, thiourea, cerous sulfate and sodium alginate, as raw material, pass through microwave Heating makes adsorbent, and concrete operation step is as follows:

(1) 100 parts of Pericarpium Musae are pulverized, add sodium hydroxide solution and soak 3-5h, be washed with water and wash Fructus Musae corium farinosum extremely neutrality, Pericarpium Musae cellulose；Adding 10-15 part ethyl acrylate in Pericarpium Musae cellulose, add 100-120 part water, mixing is all Even, at temperature is 60-80 DEG C, it is dried 2-3h, obtains modified Fructus Musae corium farinosum；

(2) take Entermorpha powder 50-70 part and thiourea 6-10 part add ultrasonic stirrer, add suitable quantity of water and carry out ultrasonic reaction, Reacted pastel is placed in heat drying 1-2h in the baking oven of 70-80 DEG C, obtains modified Entermorpha powder；

(3) above-mentioned modified Fructus Musae corium farinosum, modified Entermorpha powder are added agitator, add cerous sulfate solution 4-6 part and sodium alginate 10-15 part, adds water furnishing pasty state, pastel is put into microwave heating equipment, microwave 30-at temperature is 120-140 DEG C 60min, is cooled to room temperature, grinds, obtains waste water mercury-removing adsorbent.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: the water content of described Pericarpium Musae It is 12%.

The preparation method of waste water mercury-removing adsorbent the most according to claim 2, it is characterised in that: step (1) is by Pericarpium Musae It is crushed to 40-60 mesh.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: the concentration of described sodium hydroxide For 3-5mol/L.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: described waterside platform powder is by fresh Waterside platform powder cleaning, drying are 10% to water content, then are crushed to 80 mesh, obtain waterside platform powder.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: ultrasonic described in step (2) Reaction is ultrasonic reaction 20-30min under supersonic frequency is 60-80kHz.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: step (3) described microwave Power is 200-300W.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: described cerous sulfate solution dense Degree is 5mol/L.

The preparation method of waste water mercury-removing adsorbent the most according to claim 1, it is characterised in that: step (3) described grinding is Grinding the material to particle diameter is 0.5-1.0mm.