CN111389380A

CN111389380A - Treatment material for heavy metals in sewage and preparation method thereof

Info

Publication number: CN111389380A
Application number: CN202010268098.4A
Authority: CN
Inventors: 不公告发明人
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-04-08
Filing date: 2020-04-08
Publication date: 2020-07-10

Abstract

The invention discloses a treatment material for heavy metal in sewage and a preparation method thereof, wherein the treatment material for heavy metal comprises the following raw materials in parts by weight: 25-30 parts of sepiolite, 50-70 parts of deionized water, 300 parts of hydrochloric acid solution 250-containing sand, 1-3 parts of aluminum oxide, 1-3 parts of manganese sand, 1-3 parts of montmorillonite, 1-3 parts of apatite, 1-3 parts of bentonite, 5-8 parts of calcium hydroxide, 0.5-2 parts of N, N-methylene bisacrylamide, 5.5-8 parts of humic acid, 15-18 parts of polyvinyl alcohol and 8-15 parts of modified cellulose; the modified cellulose is prepared in the preparation process, ether bonds are contained in the modified cellulose to form cellulose ether, a single cellulose ether molecule also contains two carbonyl groups, and the modified cellulose contains a large number of hydroxyoxime groups, so that the modified cellulose can easily form stable chelate with heavy metal ions to be adsorbed on the surface of the cellulose, and the N-acetyl imidazole is grafted on the surface of the cellulose, so that the heavy metal ion adsorption capacity of the modified cellulose is further enhanced.

Description

Treatment material for heavy metals in sewage and preparation method thereof

Technical Field

The invention belongs to the field of sewage treatment, and particularly relates to a treatment material for heavy metals in sewage and a preparation method thereof.

Background

With the rapid development of global economy, heavy metals enter water in the form of artificial pollution such as mining, metal smelting and processing, discharge of chemical wastewater, abuse of pesticides and fertilizers, disposal of household garbage and other natural sources such as geological erosion, weathering and the like, and heavy metal pollution has the characteristics of easy biological enrichment, biological amplification effect generation and high toxicity, so that the heavy metal pollution in the water pollutes the water environment and seriously harms the survival of human beings and various organisms, and the research on treatment materials for the heavy metals in the sewage is increasingly valued by people;

chinese invention patent CN105692771A discloses a heavy metal sewage treatment material, which comprises the following raw materials by mass: 10-20 parts of hydrochloric acid modified sepiolite, 15-25 parts of pyridine quaternary ammonium salt type cationic polyacrylamide, 5-8 parts of zeolite powder, 2-8 parts of modified attapulgite, 10-25 parts of crosslinked carboxylic acid methyl starch, 5-10 parts of hydroxypropyl cellulose graft copolymer, 2-8 parts of ferric sulfate, 1-5 parts of lime powder and 3-8 parts of activated carbon powder; the raw materials of the heavy metal sewage treatment material prepared by the method are easy to regenerate, no energy consumption is generated in the sewage treatment process, but the heavy metal treatment effect is general, the preparation method of the heavy metal sewage treatment material is complex, the preparation efficiency is low, and the market popularization is not facilitated.

Disclosure of Invention

The invention aims to provide a treatment material for heavy metals in sewage and a preparation method thereof, aiming at improving the defects of the common treatment material for heavy metals in sewage in the current market, the invention prepares a modified cellulose when preparing the treatment material for heavy metals, the modified cellulose contains cellulose ether bond, a single cellulose ether molecule also contains two carbonyl groups, the carbonyl groups can form coordinate bond with heavy metal ions to complex and adsorb metal ions, the modified fiber contains a large amount of hydroxyoxime groups, the hydroxyoxime groups have the characteristics of amide and oxime groups, two atoms with arc electron pairs of nitrogen and oxygen exist in the hydroxyoxime groups, the positions of the hydroxyoxime groups are close to each other, the special structure ensures that the hydroxyoxime groups are easy to form stable chelate compounds with heavy metal ions to be adsorbed on the surface of the cellulose, and further, the cellulose is chemically grafted to graft N-acetyl imidazole on the surface of the cellulose, the surface of the cellulose contains a large number of imidazolyl, so that the heavy metal ion adsorption capacity of the modified cellulose is further enhanced.

The technical problems to be solved by the invention are as follows:

1. the treatment material for heavy metal commonly used in the market at present needs to consume a large amount of materials in the material preparation process, the preparation cost is high, the prepared treatment material for heavy metal generates solid precipitate after adsorbing heavy metal, but the solid precipitate has low stability and is easy to decompose again, so that a part of heavy metal ions still remain in the treated water, and the sewage treatment effect is general;

2. the traditional preparation method of the heavy metal treatment material is complex, the time consumed by the crushing and mixing process in the preparation process is long, the crushing effect is poor, and the required powder particle size can be achieved through multiple times of crushing, so that the preparation efficiency of the metal treatment material is low.

The purpose of the invention can be realized by the following technical scheme:

a treatment material for heavy metal in sewage and a preparation method thereof are disclosed, wherein the treatment material for heavy metal is composed of the following raw materials by weight: 25-30 parts of sepiolite, 50-70 parts of deionized water, 300 parts of hydrochloric acid solution 250-containing sand, 1-3 parts of aluminum oxide, 1-3 parts of manganese sand, 1-3 parts of montmorillonite, 1-3 parts of apatite, 1-3 parts of bentonite, 5-8 parts of calcium hydroxide, 0.5-2 parts of N, N-methylene bisacrylamide, 5.5-8 parts of humic acid, 15-18 parts of polyvinyl alcohol and 8-15 parts of modified cellulose;

the preparation method of the heavy metal treatment material comprises the following steps:

step S1: adding sepiolite and deionized water into a reaction kettle, stirring for 5-10min at the rotation speed of 1000-1500r/min and the temperature of 25-30 ℃, filtering, adding the filtered sepiolite into an oven, and drying for 30-45min at the temperature of 100-110 ℃ to obtain the cleaned sepiolite;

step S2: adding the dried and cleaned sepiolite obtained in the step S1 and a hydrochloric acid solution into a reaction kettle, stirring for 18-20h at the rotation speed of 100-300r/min and the temperature of 65-70 ℃, filtering to remove filtrate, and drying for 3-5h at the temperature of 110-120 ℃ to obtain the processed sepiolite;

step S3: selecting a 1250-mesh oscillating sieve plate, opening a first oscillator, a crushing screw rod, a second oscillator and a motor to enable a crushing and mixing device to normally work, adding alumina, manganese sand, montmorillonite, apatite and bentonite into a crushing bin from a crushing feed inlet, crushing the blocky materials into powder by the crushing screw rod, enabling the materials to fall onto the oscillating sieve plate, enabling the powder reaching 1250 meshes to fall into a crushing storage bin under the action of the first oscillator, remaining the powder not reaching 1250 meshes in the crushing bin to continue crushing until reaching 1250 meshes, enabling the powder to enter the mixing bin through an anti-blocking device to be primarily stirred under the action of a first stirring rod, enabling the stirred powder to enter a discharge outlet and a second stirring rod to be secondarily stirred, and collecting the crushed and mixed powder through a material collecting tank to obtain mixed powder;

step S4: adding deionized water, calcium hydroxide, N-methylene bisacrylamide and humic acid into a stirring kettle, and carrying out ultrasonic stirring for 30-40min at the rotation speed of 1000-1500r/min and the temperature of 80-90 ℃ to prepare suspension;

step S5: adding the sepiolite obtained in the step S2, the mixed powder obtained in the step S3, the suspension obtained in the step S4, polyvinyl alcohol and modified cellulose into a reaction kettle, carrying out ultrasonic stirring for 1-2h under the condition of the rotation speed of 800-.

Further, the concentration of the hydrochloric acid solution is 1.2-1.5 mol/L, and the ratio of the amount of the deionized water in the step S1 to the amount of the deionized water in the step S4 is 8: 1.

Further, the modified fiber comprises the following raw materials in parts by weight: 25-30 parts of cotton, 10-15 parts of sodium hydroxide solution, 10-15 parts of chloroacetic acid solution, 25-30 parts of 2-iodoxybenzoic acid, 10-15 parts of dimethyl sulfoxide, 40-50 parts of acetic acid solution, 0.5-1 part of concentrated sulfuric acid, 25-30 parts of acetic anhydride, 15-20 parts of deionized water, 12.5-15 parts of hydroxylamine hydrochloride, 10-15 parts of hydrochloric acid solution, 20-30 parts of ethanol, 20-30 parts of N-acetylimidazole, 0.65-0.75 part of potassium peroxydisulfate, 7.5-10 parts of N, N-methylene bisacrylamide and 20-30 parts of methanol;

the modified cellulose is prepared by the following method:

a1: adding cotton into an opening crusher for crushing to obtain powdery refined cotton with certain fineness and bulk density, adding half amount of the powdery refined cotton and sodium hydroxide solution into a reaction kettle, heating for 50-60min under the conditions of the rotation speed of 100-300r/min and the temperature of 35-40 ℃, adding chloroacetic acid solution into the reaction kettle, and reacting under the conditions of the rotation speed of 100-300r/min and the temperature of 74-78 ℃ to obtain an intermediate A;

a2: adding the intermediate A prepared in the step A1, 2-iodoxybenzoic acid and dimethyl sulfoxide into a reaction kettle, reacting for 2-3h at the rotation speed of 500-;

a3: adding the other half of powdery refined cotton and acetic acid solution into a reaction kettle, reacting for 25-30min at 65-75 ℃, adding concentrated sulfuric acid and acetic anhydride, reacting at the rotation speed of 500r/min and the temperature of 80-100 ℃ to obtain an intermediate C, adding deionized water, hydroxylamine hydrochloride and sodium hydroxide solution into the reaction kettle, stirring at the rotation speed of 1000r/min and the temperature of 25-30 ℃ for 5-10min, adding the intermediate C into the reaction kettle, reacting for 1.5-2h at the rotation speed of 500r/min and the temperature of 50-55 ℃, adding hydrochloric acid solution until the pH value is 6, standing for 15-20min, and filtering to remove filtrate to obtain an intermediate D;

a4: adding the intermediate B prepared in the step A2, the intermediate D prepared in the step A3, deionized water and ethanol into a reaction kettle, introducing nitrogen, stirring at the rotation speed of 500-800r/min and the temperature of 45-50 ℃ for 1-1.2h, cooling to room temperature, adding N-acetylimidazole, potassium peroxodisulfate and N, N-methylene bisacrylamide into the reaction kettle, reacting at the temperature of 55-75 ℃ for 3-4h, filtering to remove filtrate to obtain solid powder, washing the solid powder for 3-5 times by using methanol, putting the washed solid powder into a drying box, and drying at the temperature of 65-70 ℃ for 20-30min to obtain modified cellulose;

further, the mass fraction of the sodium hydroxide solution is 17-22%, the mass fraction of the chloroacetic acid solution is 10-15%, the mass fraction of the concentrated sulfuric acid is 70-82%, the mass fraction of the acetic acid solution is 80-85%, the mass fraction of the hydrochloric acid solution is 15-20%, and the ratio of the amount of the deionized water in the step A3 to the amount of the deionized water in the step A4 is 1: 3.

Further, the crushing and mixing device in the step S3 comprises a base, a crushing bin, an anti-blocking device and a mixing bin, wherein the base is placed on a horizontal plane, one end of the base is provided with a fixing column, the fixing column is perpendicular to the base, one side of the upper end of the fixing column is provided with a fixing block, the upper end surface of the base is provided with a supporting column, and the upper end surface of the base is provided with a material receiving groove;

the crushing bin comprises a crushing storage bin, one side of the crushing bin is fixedly connected with a fixed block, a crushing feed inlet is formed in the top end of the crushing bin, a plurality of crushing screws are arranged inside the crushing bin, a first oscillator is arranged on one side outside the crushing bin, a crushing bin annular layer is arranged at the bottom end outside the crushing bin, a plurality of screw holes are formed in the crushing bin annular layer, a storage bin annular layer is arranged at the top end outside the crushing storage bin, a plurality of screw holes are formed in the storage bin annular layer, the crushing bin annular layer and the storage bin annular layer are fixedly connected through bolts, the crushing bin and the crushing storage bin are communicated internally, an oscillating sieve plate is arranged at the top end inside the crushing bin, the oscillating sieve plate is matched with the first oscillator, a crushing discharge port is formed in the lower end of the crushing bin, and the lower end;

mix the outside bottom and the support column fixed connection in storehouse, open on the top in mixed storehouse has the feed inlet, the upper end and the lower extreme of anti-clogging device of feed inlet are connected, mix the storehouse, anti-clogging device, smash the inside intercommunication in storehouse three, the top in mixed storehouse is equipped with the motor, the first puddler of fixedly connected with is stretched to the output shaft of motor, first puddler is located the inside in mixing the storehouse, be equipped with a plurality of first stirring vane on the first puddler, the bottom fixedly connected with second puddler of first puddler, be equipped with second stirring vane on the second puddler, open the bottom in mixed storehouse has the discharge gate, the second puddler is located the inside of discharge gate.

Furthermore, the number of the support columns is four, the support columns are uniformly distributed at the bottom of the outer part of the mixing bin, the crushing screw rods are arranged in three rows in a staggered mode, the bottom of the crushing storage bin is conical, and the bottom of the mixing bin is conical.

Further, anti-clogging device include fixed pipe, go up fixed pipe's inside upper end and be equipped with the screw thread, go up fixed pipe's inside lower extreme fixedly connected with rubber tube, go up rubber tube's lower extreme fixedly connected with oscillation tube, outside one side of oscillation tube is equipped with the second oscillator, rubber tube under the lower extreme fixedly connected with of oscillation tube, fixed pipe under the lower extreme fixedly connected with of lower rubber tube, the inside lower extreme of fixed pipe is equipped with the screw thread down, the outside lower extreme of smashing the discharge gate is equipped with the screw thread, the outside upper end of feed inlet is equipped with the screw thread, it is fixed with crushing discharge gate spiro union to go up fixed pipe, fixed pipe is fixed with the feed inlet spiro union down.

The invention has the beneficial effects that:

(1) the material for treating heavy metal in sewage, which is prepared by the invention, has the advantages of simple production process, low manufacturing cost, good effect of removing heavy metal ions, capability of effectively adsorbing heavy metal ions to form stable precipitate, capability of removing the precipitate adsorbing heavy metal by simple filtration, and simple and effective treatment process, and the used raw materials are common materials;

(2) the invention prepares a modified cellulose in the process of preparing a treatment material for heavy metal in sewage, firstly, half of cellulose and sodium hydroxide are subjected to alkalization reaction, the cellulose molecular chain contains 3 hydroxyls which are respectively positioned at 2, 3 and 6 positions of carbon, the hydroxyl on the 2 position of the carbon has larger acidity, the modified cellulose reacts with the sodium hydroxide to ensure that hydrogen on the hydroxyl is replaced by sodium, the modified cellulose further reacts with chloroacetic acid to generate cellulose ether, then 2-iodoxybenzoic acid and dimethyl sulfoxide are added into the cellulose ether, the dimethyl sulfoxide is used as a solvent, the 2-iodoxybenzoic acid is used as an oxidant to oxidize the hydroxyls on the 3 and 6 positions of the carbon into carbonyl, the other half of cellulose, acetic acid solution, concentrated sulfuric acid and acetic anhydride are mixed for reaction, three hydroxyls on the cellulose react with the acetic acid to form three ester groups, and further react with hydroxylamine hydrochloride under the alkaline condition, after the reaction is finished, adding hydrochloric acid solution for acidification, converting three hydroxyl groups on cellulose into hydroxyoxime groups, heating and stirring the respectively treated cellulose, ethanol and deionized water under the protection of nitrogen to uniformly disperse the cellulose in the mixed solution, then adding N-acetylimidazole, taking potassium peroxodisulfate as a water-soluble initiator and N, N-methylene bisacrylamide as a cross-linking agent, chemically grafting the cellulose, grafting an N-acetylimidazole monomer on the surface of the cellulose to prepare the modified cellulose, wherein the natural cellulose has certain heavy metal adsorbability but only a single group on the surface, so that the adsorption capacity to heavy metal ions is not high, the modified cellulose has the same capacity as the natural cellulose for adsorbing heavy metal ions, and simultaneously the modified cellulose contains ether bonds to form cellulose ether, and a single cellulose ether molecule also contains two carbonyl groups, the carbonyl group can form a coordination bond with heavy metal ions to complex and adsorb the metal ions, so that the adsorption capacity of the heavy metal ions is improved, the modified fiber contains a large number of hydroxyoxime groups, the hydroxyoxime groups have the characteristics of amide and oxime groups at the same time, and two atoms with arc electron pairs, close to each other, of nitrogen and oxygen exist in the hydroxyoxime groups, the hydroxyoxime groups are of a special structure, so that the hydroxyoxime groups are easy to form stable chelates with the heavy metal ions to be adsorbed on the surface of the cellulose, the cellulose is further chemically grafted to graft N-acetylimidazole on the surface of the cellulose, the property of the N-acetylimidazole is obtained while the property of the N-acetylimidazole is not influenced, the N-acetylimidazole is grafted on the surface of the cellulose in a large amount, and the imidazolyl group has a good heavy metal ion chelating function, so that the adsorption capacity of the heavy metal;

(3) the invention uses a crushing and mixing device in the process of preparing a treatment material for heavy metal in sewage, the device comprises a base, a crushing bin, an anti-clogging device and a mixing bin, the crushing bin comprises a crushing storage bin, and an oscillating sieve plate inside the crushing storage bin, thereby completing the crushing and screening process, an annular layer of the crushing bin is fixedly connected with an annular layer of the storage bin through bolts, the crushing bin is connected with the crushing storage bin, so that the oscillating sieve plate can be quickly and conveniently replaced according to the particle size of required powder, the anti-clogging device communicates the crushing bin with the mixing bin through a screw connection mode, so that the equipment is more conveniently assembled, the anti-clogging device is provided with an upper rubber tube and a lower rubber tube, so that when the oscillating tube works, the work of the crushing bin and the mixing bin cannot be influenced by oscillation, and the action generated by oscillation acts on the upper rubber tube and the lower rubber tube, the service life of the crushing bin and the mixing bin is further prolonged, and the powder is stirred for multiple times, so that the powder is mixed more sufficiently, and the preparation efficiency of the heavy metal treatment material is improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic structural view of a crushing and mixing device in a treatment material for heavy metals in sewage and a preparation method thereof according to the present invention;

FIG. 2 is a schematic structural diagram of a crushing bin in a crushing and mixing device in the treatment material for heavy metals in sewage and the preparation method thereof according to the present invention;

FIG. 3 is a schematic structural view of an anti-clogging device in a crushing and mixing device for treating heavy metals in sewage and a method for preparing the same according to the present invention;

FIG. 4 is a schematic structural diagram of a mixing bin in a crushing and mixing device in the treatment material for heavy metals in sewage and the preparation method thereof.

In the figure: 1. a base; 11. fixing a column; 12. a fixed block; 13. a support pillar; 14. a material receiving groove; 2. a crushing bin; 21. a crushing feed port; 22. a first oscillator; 221. oscillating the sieve plate; 23. a pulverizing screw; 24. a crushing bin annular layer; 25. crushing the storage bin; 251. the annular layer of the storage bin; 26. crushing a discharge hole; 3. an anti-clogging device; 31. an upper fixed tube; 32. feeding a rubber pipe; 33. an oscillating tube; 331. a second oscillator; 34. a lower rubber tube; 35. a lower fixed tube; 4. a mixing bin; 41. an electric motor; 411. a first stirring rod; 4111. a first stirring blade; 412. a second stirring rod; 4121. a second stirring blade; 42. a feed inlet; 43. and (4) a discharge port.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A treatment material for heavy metals in sewage comprises the following raw materials in parts by weight: 25 parts of sepiolite, 50 parts of deionized water, 250 parts of hydrochloric acid solution, 1 part of alumina, 1 part of manganese sand, 1 part of montmorillonite, 1 part of apatite, 1 part of bentonite, 5 parts of calcium hydroxide, 0.5 part of N, N-methylene bisacrylamide, 5.5 parts of humic acid, 15 parts of polyvinyl alcohol and 8 parts of modified cellulose;

step S1: adding sepiolite and deionized water into a reaction kettle, stirring for 5min at the rotation speed of 1000r/min and the temperature of 25 ℃, filtering, adding the filtered sepiolite into an oven, and drying for 30min at the temperature of 100 ℃ to obtain the cleaned sepiolite;

step S2: adding the dried and cleaned sepiolite obtained in the step S1 and a hydrochloric acid solution into a reaction kettle, stirring for 18 hours at the rotation speed of 100r/min and the temperature of 65 ℃, filtering to remove filtrate, and drying for 3 hours at the temperature of 110 ℃ to obtain the processed sepiolite;

step S3: adding alumina, manganese sand, montmorillonite, apatite and bentonite into a crushing and mixing device, and crushing and mixing to obtain mixed powder;

step S4: adding deionized water, calcium hydroxide, N-methylene bisacrylamide and humic acid into a stirring kettle, and carrying out ultrasonic stirring for 30min at the rotating speed of 1000r/min and the temperature of 80 ℃ to prepare a suspension;

step S5: and (3) adding the sepiolite obtained in the step S2, the mixed powder obtained in the step S3, the suspension obtained in the step S4, polyvinyl alcohol and modified cellulose into a reaction kettle, carrying out ultrasonic stirring for 1h at the rotation speed of 800r/min, distilling at the temperature of 100 ℃, and removing distillate to obtain the heavy metal treatment material.

The modified cellulose is prepared by the following method:

a1: adding cotton into an opening crusher for crushing to obtain powdery refined cotton with certain fineness and bulk density, adding half amount of the powdery refined cotton and a sodium hydroxide solution into a reaction kettle, heating for 50min at the rotating speed of 100r/min and the temperature of 35 ℃, adding a chloroacetic acid solution into the reaction kettle, and reacting at the rotating speed of 100r/min and the temperature of 74 ℃ to obtain an intermediate A;

a2: adding the intermediate A prepared in the step A1, 2-iodoxybenzoic acid and dimethyl sulfoxide into a reaction kettle, reacting for 2 hours at 25 ℃ at the rotation speed of 500r/min, and distilling at 190 ℃ to remove distillate to prepare an intermediate B;

a3: adding the other half of the powdery refined cotton and an acetic acid solution into a reaction kettle, reacting for 25min at 65 ℃, adding concentrated sulfuric acid and acetic anhydride, stirring for 5min at the rotation speed of 300r/min and the temperature of 80 ℃, adding deionized water, hydroxylamine hydrochloride and a sodium hydroxide solution into the reaction kettle, reacting for 1.5h at the rotation speed of 300r/min and the temperature of 25 ℃, adding a hydrochloric acid solution until the pH value is 6, standing for 15min, and filtering to remove filtrate to obtain an intermediate D;

a4: adding the intermediate B prepared in the step A2, the intermediate D prepared in the step A3, deionized water and ethanol into a reaction kettle, introducing nitrogen, stirring at the rotation speed of 500r/min and the temperature of 45 ℃ for 1h, cooling to room temperature, adding N-acetylimidazole, potassium peroxodisulfate and N, N-methylene bisacrylamide into the reaction kettle, reacting at the temperature of 55 ℃ for 3h, filtering to remove filtrate to obtain solid powder, washing the solid powder for 3 times by using methanol, putting the washed solid powder into a drying box, and drying at the temperature of 65 ℃ for 20min to obtain the modified cellulose.

Example 2

A treatment material for heavy metals in sewage comprises the following raw materials in parts by weight: 30 parts of sepiolite, 70 parts of deionized water, 300 parts of hydrochloric acid solution, 3 parts of aluminum oxide, 3 parts of manganese sand, 3 parts of montmorillonite, 3 parts of apatite, 3 parts of bentonite, 8 parts of calcium hydroxide, 2 parts of N, N-methylene bisacrylamide, 8 parts of humic acid, 18 parts of polyvinyl alcohol and 15 parts of modified cellulose;

step S1: adding sepiolite and deionized water into a reaction kettle, stirring for 10min at the rotation speed of 1500r/min and the temperature of 30 ℃, filtering, adding the filtered sepiolite into an oven, and drying for 45min at the temperature of 110 ℃ to obtain the cleaned sepiolite;

step S2: adding the dried and cleaned sepiolite obtained in the step S1 and a hydrochloric acid solution into a reaction kettle, stirring for 20 hours at the rotation speed of 300r/min and the temperature of 70 ℃, filtering to remove filtrate, and drying for 5 hours at the temperature of 120 ℃ to obtain the processed sepiolite;

step S4: adding deionized water, calcium hydroxide, N-methylene bisacrylamide and humic acid into a stirring kettle, and carrying out ultrasonic stirring for 40min at the rotation speed of 1500r/min and the temperature of 90 ℃ to prepare suspension;

step S5: and (3) adding the sepiolite obtained in the step S2, the mixed powder obtained in the step S3, the suspension obtained in the step S4, polyvinyl alcohol and modified cellulose into a reaction kettle, carrying out ultrasonic stirring for 2 hours at the rotation speed of 1000r/min, distilling at the temperature of 110 ℃, and removing distillate to obtain the heavy metal treatment material.

Comparative example 1

Compared with the example 1, the comparative example uses cotton to replace modified cellulose, and comprises the following specific steps:

step S5: and (3) adding the sepiolite obtained in the step S2, the mixed powder obtained in the step S3, the suspension obtained in the step S4, polyvinyl alcohol and cotton into a reaction kettle, carrying out ultrasonic stirring for 1h at the rotation speed of 800r/min, distilling at the temperature of 100 ℃, removing distillate and obtaining the heavy metal treatment material.

Comparative example 2

Compared with the embodiment 1, the carbon fiber powder is used for replacing the modified cellulose, and the specific steps are as follows:

step S5: and (3) adding the sepiolite obtained in the step S2, the mixed powder obtained in the step S3, the suspension obtained in the step S4, polyvinyl alcohol and carbon fiber powder into a reaction kettle, carrying out ultrasonic stirring for 1h at the rotation speed of 800r/min, distilling at the temperature of 100 ℃, removing distillate, and obtaining the heavy metal treatment material.

Comparative example 3

The comparative example is a material commonly used in the market for treating heavy metals in sewage.

The heavy metal treatment performance of examples 1-2 and comparative examples 1-3 was tested, the heavy metal treatment materials prepared in examples 1-2 and comparative examples 1-3 were added to one liter of wastewater, stirred for 30min, filtered to remove the precipitate, and the treated water was tested for heavy metal content, the test results are shown in table 1 below (unit mg/L);

TABLE 1

	Arsenic (As)	Copper (Cu)	Lead (II)	Cadmium (Cd)	Mercury	Nickel (II)	Chromium (III)
								Water sample	13.53	103.28	8.84	9.33	12.18	13.95	15.82
Example 1	0.0076	0.128	0.0042	0.0027	0.00031	0.11	0.023
								Example 2	0.0062	0.134	0.0035	0.0035	0.00028	0.12	0.033
Comparative example 1	0.0283	1.352	0.0938	0.0326	0.00935	0.38	0.126
								Comparative example 2	0.1236	0.826	0.0845	0.0172	0.00427	0.21	0.083
Comparative example 3	0.0166	0.752	0.0184	0.0103	0.00275	0.14	0.043

As can be seen from the above table 1, the heavy metal treatment effect of the heavy metal treatment materials prepared in examples 1-2 is much better than that of comparative examples 1-3, the modified cellulose prepared in the present invention contains ether bonds to form cellulose ether, a single cellulose ether molecule also contains two carbonyl groups, the carbonyl groups can form coordinate bonds with heavy metal ions to complex and adsorb the metal ions, so as to increase the adsorption amount of the heavy metal ions, the modified cellulose contains a large amount of hydroxyoxime groups, the hydroxyoxime groups have the characteristics of amide and oxime groups, and two arc electron pair atoms with nitrogen and oxygen exist in the hydroxyoxime groups, which are close to each other, and the special structure makes the hydroxyoxime groups easy to form stable chelates with the heavy metal ions to adsorb on the cellulose surface, and further, the cellulose is chemically grafted to graft N-acetyl imidazole on the cellulose surface, the properties of N-acetyl imidazole can be obtained without influencing the properties of the fiber, a great amount of N-acetyl imidazole is grafted on the surface of the cellulose, so that the fiber contains a great amount of imidazolyl, the imidazolyl has a good heavy metal ion chelating function, and the heavy metal ion adsorption capacity of the modified cellulose is further enhanced.

Referring to fig. 1-4, the crushing and mixing device used in the above embodiment includes a base 1, a crushing bin 2, an anti-blocking device 3, and a mixing bin 4, the base 1 is placed on a horizontal plane, a fixing column 11 is arranged at one end of the base 1, the fixing column 11 is perpendicular to the base 1, a fixing block 12 is arranged at one side of the upper end of the fixing column 11, a support column 13 is arranged on the upper end surface of the base 1, and a material receiving groove 14 is placed on the upper end surface of the base 1;

the crushing bin 2 comprises a crushing storage bin 25, one side of the crushing bin 2 is fixedly connected with a fixed block 12, a crushing feed inlet 21 is formed in the top end of the crushing bin 2, a plurality of crushing screws 23 are arranged inside the crushing bin 2, a first oscillator 22 is arranged on one side of the outside of the crushing bin 2, a crushing bin annular layer 24 is arranged at the bottom end of the outside of the crushing bin 2, a plurality of screw holes are formed in the crushing bin annular layer 24, a storage bin annular layer 251 is arranged at the top end of the outside of the crushing storage bin 25, a plurality of screw holes are formed in the storage bin annular layer 251, the crushing bin annular layer 24 and the storage bin annular layer 251 are fixedly connected through bolts, the crushing bin 2 is communicated with the inside of the crushing storage bin 25, a vibrating sieve plate 221 is arranged at the top end of the inside of the crushing bin 2, the vibrating sieve plate 221 is matched with the first oscillator 22, a crushing discharge outlet 26 is formed at;

mix the outside bottom and the support column 13 fixed connection of storehouse 4, open on the top of mixing storehouse 4 has feed inlet 42, the upper end and the lower extreme of anti-clogging device 3 of feed inlet 42 are connected, mix storehouse 4, anti-clogging device 3, smash the inside intercommunication of 2 three in the storehouse, the top of mixing storehouse 4 is equipped with motor 41, the first puddler 411 of fixedly connected with is stretched to motor 41's output shaft, first puddler 411 is located the inside of mixing storehouse 4, be equipped with a plurality of first stirring vane 4111 on the first puddler 411, the bottom fixedly connected with second puddler 412 of first puddler 411, be equipped with second stirring vane 4121 on the second puddler 412, the bottom of mixing storehouse 4 is opened there is discharge gate 43, second puddler 412 is located the inside of discharge gate 43.

The number of the support columns 13 is four, the support columns 13 are uniformly distributed at the bottom end of the outer part of the mixing bin 4, the crushing screws 23 are arranged in three rows in a staggered mode, the bottom of the crushing storage bin 25 is conical, and the bottom of the mixing bin 4 is conical.

Anti-clogging device 3 include fixed pipe 31, the inside upper end of going up fixed pipe 31 is equipped with the screw thread, go up rubber tube 32 on the inside lower extreme fixedly connected with of fixed pipe 31, the lower extreme fixedly connected with oscillation tube 33 of going up rubber tube 32, outside one side of oscillation tube 33 is equipped with second oscillator 331, rubber tube 34 under the lower extreme fixedly connected with of oscillation tube 33, fixed pipe 35 under the lower extreme fixedly connected with of lower rubber tube 34, the inside lower extreme of fixed pipe 35 is equipped with the screw thread down, the outside lower extreme of smashing discharge gate 26 is equipped with the screw thread, the outside upper end of feed inlet 42 is equipped with the screw thread, it is fixed with smashing discharge gate 26 spiro union to go up fixed pipe 31, lower fixed pipe 35 is fixed with feed inlet 42 spiro union.

The working principle is as follows: selecting 1250-mesh oscillating screen plate 221, wherein the oscillating screen plate 221 can be quickly and conveniently replaced according to the particle size of the required powder due to the fixed connection of the annular layer 24 of the crushing bin and the annular layer 251 of the storage bin through bolts, opening the first oscillator 22, the crushing screw 23, the second oscillator 331 and the motor 41 to ensure that the crushing and mixing device normally works, adding alumina, manganese sand, montmorillonite, apatite and bentonite into the crushing bin 2 from the crushing feed inlet 21, crushing the blocky materials into powder through the crushing screw 23, enabling the materials to fall onto the oscillating screen plate 221, enabling the 1250-mesh powder to fall into the crushing and storage bin 25 under the action of the first oscillator 22, continuously crushing the powder which does not reach 1250-mesh in the crushing bin 2 until reaching 1250-mesh, enabling the powder to smoothly enter the mixing bin 4 due to the rapid falling and easy blockage of the powder, and ensuring that the blocked powder can smoothly enter the mixing bin 4 under the action of the blockage prevention device 3, anti-clogging device 3 will smash storehouse 2 and mixed storehouse 4 UNICOM through the mode of spiro union, it is more convenient to make equipment assemble, be equipped with rubber tube 32 and lower rubber tube 34 on anti-clogging device 3, make at oscillating pipe 33 at the during operation, can not smash the work of storehouse 2 and mixed storehouse 4 because of the oscillation influence, the effort that produces simultaneously will oscillate is used in last rubber tube 32 and rubber tube 34 down, the life who smashes storehouse 2 and mixed storehouse 4 has further been increased, the powder gets into and mixes storehouse 4 and carry out the primary mixing under the effect of first puddler 411, the powder of accomplishing the stirring gets into and carries out the secondary stirring under the effect of discharge gate 42 second puddler 412, make the powder mix more fully, accomplish the powder after smashing and mixing and collect through receiving groove 14.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims

1. A treatment material for heavy metals in sewage is characterized in that: the feed is prepared from the following raw materials in parts by weight: 25-30 parts of sepiolite, 50-70 parts of deionized water, 300 parts of hydrochloric acid solution 250-containing sand, 1-3 parts of aluminum oxide, 1-3 parts of manganese sand, 1-3 parts of montmorillonite, 1-3 parts of apatite, 1-3 parts of bentonite, 5-8 parts of calcium hydroxide, 0.5-2 parts of N, N-methylene bisacrylamide, 5.5-8 parts of humic acid and 15-18 parts of polyvinyl alcohol;

2. The material as claimed in claim 1, wherein the hydrochloric acid solution has a concentration of 1.2-1.5 mol/L, and the ratio of the amount of deionized water used in step S1 to the amount of deionized water used in step S4 is 8: 1.

3. The material for treating heavy metals in sewage according to claim 1, wherein: the modified fiber comprises the following raw materials in parts by weight: 25-30 parts of cotton, 10-15 parts of sodium hydroxide solution, 10-15 parts of chloroacetic acid solution, 25-30 parts of 2-iodoxybenzoic acid, 10-15 parts of dimethyl sulfoxide, 40-50 parts of acetic acid solution, 0.5-1 part of concentrated sulfuric acid, 25-30 parts of acetic anhydride, 15-20 parts of deionized water, 12.5-15 parts of hydroxylamine hydrochloride, 10-15 parts of hydrochloric acid solution, 20-30 parts of ethanol, 20-30 parts of N-acetylimidazole, 0.65-0.75 part of potassium peroxydisulfate, 7.5-10 parts of N, N-methylene bisacrylamide and 20-30 parts of methanol;

the modified cellulose is prepared by the following method:

a4: adding the intermediate B prepared in the step A2, the intermediate D prepared in the step A3, deionized water and ethanol into a reaction kettle, introducing nitrogen, stirring at the rotation speed of 500-800r/min and the temperature of 45-50 ℃ for 1-1.2h, cooling to room temperature, adding N-acetylimidazole, potassium peroxodisulfate and N, N-methylene bisacrylamide into the reaction kettle, reacting at the temperature of 55-75 ℃ for 3-4h, filtering to remove filtrate to obtain solid powder, washing the solid powder for 3-5 times by using methanol, putting the washed solid powder into a drying box, and drying at the temperature of 65-70 ℃ for 20-30min to obtain the modified cellulose.

4. The material for treating heavy metals in sewage according to claim 3, wherein: the mass fraction of the sodium hydroxide solution is 17-22%, the mass fraction of the chloroacetic acid solution is 10-15%, the mass fraction of the concentrated sulfuric acid is 70-82%, the mass fraction of the acetic acid solution is 80-85%, the mass fraction of the hydrochloric acid solution is 15-20%, and the ratio of the amount of the deionized water in the step A3 to the amount of the deionized water in the step A4 is 1: 3.

5. The material for treating heavy metals in sewage according to claim 1, wherein: the smashing and mixing device in the step S3 comprises a base (1), a smashing bin (2), an anti-blocking device (3) and a mixing bin (4), wherein the base (1) is placed on a horizontal plane, one end of the base (1) is provided with a fixing column (11), the fixing column (11) is perpendicular to the base (1), one side of the upper end of the fixing column (11) is provided with a fixing block (12), the upper end face of the base (1) is provided with a supporting column (13), and the upper end face of the base (1) is provided with a material receiving groove (14);

the crushing bin (2) comprises a crushing storage bin (25), one side of the crushing bin (2) is fixedly connected with a fixed block (12), a crushing feed inlet (21) is formed in the top end of the crushing bin (2), a plurality of crushing screw rods (23) are arranged inside the crushing bin (2), a first oscillator (22) is arranged on one side of the outside of the crushing bin (2), a crushing bin annular layer (24) is arranged at the bottom end of the outside of the crushing bin (2), a plurality of screw holes are formed in the crushing bin annular layer (24), a storage bin annular layer (251) is arranged at the top end of the outside of the crushing storage bin (25), a plurality of screw holes are formed in the storage bin annular layer (251), the crushing bin annular layer (24) is fixedly connected with the storage bin annular layer (251) through bolts, the crushing bin (2) is communicated with the inside of the crushing bin (25), a vibration sieve plate (221) is arranged at the top end of the inside of the crushing bin (2), and the vibration sieve plate (, the lower end of the crushing bin (2) is provided with a crushing discharge hole (26), and the lower end of the crushing discharge hole (26) is connected with the upper end of the anti-blocking device (3);

the bottom end of the outer part of the mixing bin (4) is fixedly connected with the supporting column (13), the top end of the mixing bin (4) is provided with a feeding hole (42), the upper end of the feeding hole (42) is connected with the lower end of the anti-blocking device (3), the mixing bin (4) and the anti-blocking device (3), smash the inside intercommunication of storehouse (2) three, the top of mixing storehouse (4) is equipped with motor (41), the output shaft of motor (41) stretches the first puddler of fixedly connected with (411), first puddler (411) are located the inside of mixing storehouse (4), be equipped with a plurality of first stirring vane (4111) on first puddler (411), the bottom fixedly connected with second puddler (412) of first puddler (411), be equipped with second stirring vane (4121) on second puddler (412), the bottom of mixing storehouse (4) is opened there is discharge gate (43), second puddler (412) are located the inside of discharge gate (43).

6. The material for treating heavy metals in sewage according to claim 5, wherein: the number of the support columns (13) is four, the support columns (13) are uniformly distributed at the bottom end of the outer part of the mixing bin (4), the crushing screws (23) are arranged in three rows in a staggered mode, the bottom of the crushing storage bin (25) is conical, and the bottom of the mixing bin (4) is conical.

7. The material for treating heavy metals in sewage according to claim 5, wherein: anti-clogging device (3) including last fixed tube (31), the inside upper end of going up fixed tube (31) is equipped with the screw thread, go up rubber tube (32) on the inside lower extreme fixedly connected with of fixed tube (31), go up lower extreme fixedly connected with oscillation tube (33) of rubber tube (32), outside one side of oscillation tube (33) is equipped with second oscillator (331), rubber tube (34) under the lower extreme fixedly connected with of oscillation tube (33), fixed tube (35) under the lower extreme fixedly connected with of lower rubber tube (34), the inside lower extreme of fixed tube (35) is equipped with the screw thread down, the outside lower extreme of smashing discharge gate (26) is equipped with the screw thread, the outside upper end of feed inlet (42) is equipped with the screw thread, it is fixed with smashing discharge gate (26) spiro union to go up fixed tube (31), fixed tube (35) is fixed with feed inlet (42) spiro union down.

8. A method for preparing a treatment material for heavy metals in sewage, which is suitable for use in the method of claim 1, characterized by: the method comprises the following steps:

step S3: selecting 1250-mesh oscillating sieve plate (221), opening a first oscillator (22), a crushing screw rod (23), a second oscillator (331) and a motor (41) to enable the crushing and mixing device to work normally, adding alumina, manganese sand, montmorillonite, apatite and bentonite into a crushing bin (2) from a crushing feed inlet (21), crushing the massive materials into powder by the crushing screw rod (23), enabling the materials to fall onto the oscillating sieve plate (221), enabling the powder reaching 1250 meshes to fall into a crushing storage bin (25) under the action of the first oscillator (22), enabling the powder not reaching 1250 meshes to be left in the crushing bin (2) for continuous crushing until reaching 1250 meshes, enabling the powder to enter a mixing bin (4) through an anti-blocking device (3) to be primarily stirred under the action of a first stirring rod (411), enabling the stirred powder to enter a discharge port (42) and perform secondary stirring under the action of a second stirring rod (412), collecting the powder after the crushing and mixing is finished through a material collecting groove (14) to obtain mixed powder;