CN106630183B - Preparation of a biological purification carrier for wastewater purification - Google Patents

Abstract

The invention provides a biological purification carrier for wastewater treatment, which can be prepared by the following method: mix pretreated attapulgite and MBAA in brine, and stir at 50-70°C for 1-3h; mix the biopolymer solution with the above-mentioned mixed solution Mix, heat the above solution to 40-60°C, add 2-5% of attapulgite mass activated sludge and 1-3% nanometer iron-manganese composite oxide, add attapulgite mass 2-5% carbon nano Stir the tube for 1-3 hours, the stirring speed is 5-10 rpm, then add the cyclodextrin complex solution to the above mixture, stir at 20-30°C for 20-40 minutes, place it at 10°C for 30 minutes, adjust The temperature is -5-7°C and kept for 40-60 minutes for slow stirring, curing and cross-linking. The above mixture is wrapped with gauze and squeezed to remove water, rinsed with 10-20% tannic acid solution for 2-3 times; the above mixture is placed for 50 ‑70°C oven treatment for 8‑10 hours. The invention can efficiently absorb and remove pollutants in waste water. It has strength and stability, good elastic effect, and high wear resistance. The production process is simple, easy to process, and easy to master. .

Description

Preparation of a biological purification carrier for wastewater purification

The present invention is a divisional application for a patent application with the application number 2015104632804 and the title of a biological purification carrier for wastewater purification treatment;

technical field

The invention belongs to the field of wastewater treatment.

Background technique

With the rapid development of modern industry and urbanization, water pollution is becoming more and more serious. Wastewater treatment methods mainly include chemical precipitation method, electrolysis method, ion exchange method, membrane treatment method, etc., but these methods have defects such as complex process, cumbersome operation, high operating cost, and secondary pollution. One of the keys to solving water pollution problems is to develop and use new high-efficiency, low-toxicity, and cheap water treatment technologies.

Attapulgite (also known as palygorskite) is a natural non-metallic mineral material. It is a hydrous magnesium-rich silicate clay mineral with a chain layer structure. The typical chemical formula is Si ₈ Mg ₆ O ₂₀ (OH) ₂ (OH ₂ ) ₄ ·4H ₂ O, the structure is a 2:1 type clay mineral, in each 2:1 unit structure layer, the corners of the tetrahedral wafers are reversed at a certain distance, forming a layer chain. Channels parallel to the chains are formed between the tetrahedral strips, and the channels are filled with zeolite water and crystallization water. The attapulgite fiber structure generally includes three levels: ① The basic structural unit is a micro-rod or fiber-like single crystal, referred to as a rod crystal. ② A single crystal bundle formed by parallel aggregation of single crystals. ③ Aggregates formed by stacking crystal bundles (including rod crystals) on each other. The special structure of attapulgite makes it have a large specific surface area and strong physical adsorption capacity. On the other hand, attapulgite has a negative charge on the layer, and exchangeable cations are adsorbed between the layers to balance the charge, so attapulgite has a strong ion adsorption and exchange capacity.

Attapulgite has good suspension in water, so although attapulgite has good adsorption capacity, for the field of water treatment, powdered attapulgite cannot be directly put into water for use, and certain methods need to be adopted. deal with. At present, a better treatment method is to use a certain carrier to immobilize attapulgite, and then put it into water for use. An inventor disclosed a preparation method of an adsorption-type polymer composite hydrogel and its product [ 201020595998.1 ], using polymer hydrogel as a carrier to immobilize attapulgite, so as to play a good role in attapulgite Soil adsorption. However, the attapulgite composite hydrogel has low efficiency and small adsorption capacity for heavy metal ions, and it is difficult to clean the gel after absorbing heavy metal ions, and the gel is not sensitive to the pH value of the solution, so it is impossible to control the pH value of the solution. to control the adsorption of heavy metal ions.

A method for mass production of γ-polyglutamic acid, application number: 201110216717.6. The invention discloses a production method of gamma-polyglutamic acid, in particular relates to a method for mass production of high-concentration gamma-polyglutamic acid. The technical scheme of the present invention is summarized as follows: 1. the activation of bacterial classification; 2. the preparation of seed liquid; 3. fermentor fermentation; it is characterized in that by adding glucose, ammonium nitrate, CaCl2. The fed-batch medium composed of 6H2O made the fermentation yield reach 1.18g/l·h, so as to achieve the purpose of efficiently producing a large amount of γ-polyglutamic acid.

The invention patent titled a nano-iron-manganese composite oxide arsenic-removing material and its preparation method relates to a nano-iron-manganese composite oxide arsenic-removing material, which is a nano-iron-manganese composite oxide containing iron , the atomic ratio of manganese and oxygen is 4:3:(8～10), wherein manganese is +4 valence, iron is +3 valence, the BET specific surface area of described arsenic removal material is 225～282m2/g, average particle diameter 10-20nm. Patent number: CN201210237752.0.

Chen Dajun, Dong Aijuan, Jiang Zequan, etc. A magnetic attapulgite wastewater treatment device: China, 201120143921.5 [P]. 2011-12-14. This patent provides a magnetic attapulgite wastewater treatment device, which realizes magnetic attapulgite Dynamic adsorption of soil in water treatment, and use in powder state, eliminating the trouble of granulation. And it overcomes the problem that attapulgite is difficult to separate in the water phase, and the magnetic attapulgite can be separated from the water phase without adding a flocculation agent, eliminating the possibility of secondary contamination caused by the addition of a flocculation agent. Pollution. At the same time, adjusting the wastewater flow rate can control the interaction time of magnetic attapulgite and wastewater to achieve the best adsorption effect. It can also change the amount of magnetic attapulgite according to the concentration of impurities in wastewater to achieve the utilization efficiency of magnetic attapulgite. best.

Li Yanhua. A modified attapulgite for sewage treatment and its preparation method: China, 201410383602.X[P].2014-12-10. This patent invented a modified attapulgite for sewage treatment Soil, by adding acrylamide to attapulgite, the flocculation of pollutants in water is increased; by adding ammonium molybdate, ammonium chloride, and cetyltrimethylammonium bromide, the adsorption capacity is increased. The attapulgite has high activation degree, uniform modification and excellent performance, is suitable for sewage treatment, has good adsorption, and does not produce secondary pollution. At the same time, it can also be used as a filler for coatings and rubber. It not only has good suspension and thixotropy, but also has antirust performance.

Surfactant-modified attapulgite method for removing heavy metals in landfill leachate: Patent No. 201410744321.2, this patent discloses a method for surfactant-modified attapulgite to remove heavy metals in landfill leachate. The deactivated attapulgite can purify heavy metals in landfill leachate. The method can effectively adsorb heavy metals in landfill leachate, and the removal efficiency of heavy metals in landfill leachate is 30% higher than that of using only original attapulgite, and is superior to traditional adsorption methods.

A threonine-modified attapulgite adsorbent and its application. 201410453968.X, this patent discloses a preparation method of a threonine-modified attapulgite adsorbent, using commonly used chemical agent threonine to select Modified attapulgite with excellent colloidal properties such as unique dispersion, high temperature resistance, and salt-alkali resistance and high adsorption and decolorization ability is modified to obtain modified attapulgite adsorption with excellent adsorption capacity for printing and dyeing dyes and heavy metal wastewater. The prepared adsorbent has excellent adsorption capacity for printing and dyeing wastewater and heavy metal wastewater, among which the saturated adsorption capacity for methylene blue and acid fuchsin can be as high as 650 and 1380 mg/g, and the saturated adsorption capacity for copper and chromium heavy metal wastewater is 143 mg/g and 81 mg/g g.

Application research of polymeric ferric sulfate composite flocculant in wastewater treatment [J]. Science and Technology Information, 2012 (6): 77-79. This document proposes a preparation process of attapulgite-polymeric ferric sulfate composite flocculant, The results show that the composite flocculant prepared from polyferric sulfate and modified attapulgite has good flocculation and treatment effect on wastewater. By comparing its CODcr removal rate and turbidity removal rate in domestic wastewater, the optimal preparation process conditions of the composite flocculant are obtained: the heat treatment temperature of attapulgite is 400°C, the composite reaction temperature is 50°C, and the attapulgite is added The amount is 2.0g/L, and the composite reaction time is 4h.

Xu Lingshu’s preliminary research on the preparation of attapulgite clay/carbon composites and its application in water pollution treatment, published in Yangzhou University, 2013. This paper prepared attapulgite clay/carbon by using attapulgite clay and sucrose as raw materials through hydrothermal synthesis reaction The composite material enables it to efficiently adsorb and remove dissolved trace organic pollutants and toxic heavy metal ions in water. The results show that carbon is coated on the surface of attapulgite crystals in the form of amorphous carbon, and hydrophilic organic functional groups appear in the material, which greatly improves its organophilic performance. In the hydrothermal reaction, the reaction time, temperature, pH and the mass ratio of attapulgite clay to carbon source all have a great influence on the adsorption performance of attapulgite clay/carbon composites.

Chen Hui, Qiang Yinghuai, Yin Hui. Synthesis of attapulgite/polyacrylamide hybrid flocculant and its flocculation characteristics[J]. Nonmetallic Minerals, 2011,34(2):36-39. This document Using ultrasonic dispersion method, in the redox system composed of N-methacryloyl-N'-pyrimidine piperazine (MPMP) and potassium persulfate (K ₂ S ₂ O ₈ ), the acrylamide monomer (AM) Grafting polymerization occurred on the surface of acid-modified attapulgite (ATP) to generate attapulgite-grafted polyacrylamide hybrid flocculant (ATP/PAM). Through the treatment of simulated sewage with 2.5wt% kaolin, 5wt% hematite and actual domestic sewage with a solid content of 5.2%, it was found that the alum flowers formed by ATP/PAM flocculation settling speed is fast, the flocculation time is short, and the amount of sludge produced is small. It is superior to ordinary PAM in a large range of addition amount, and can effectively improve the efficiency and capacity of sewage treatment.

Contents of the invention

The purpose of this invention is to provide a kind of biological purification carrier for wastewater treatment, which can be prepared by the following method:

Mix the pretreated attapulgite and MBAA in brine, stir at 50-70°C for 1-3h; mix the biopolymer solution with the above mixed solution, heat the above solution to 40-60°C, add the mass of attapulgite 2-5% activated sludge and 1-3% nano-iron-manganese composite oxide, add attapulgite mass 2-5% carbon nanotubes and stir for 1-3 hours, the stirring speed is 5-10 rpm . Then add the cyclodextrin complex solution to the above mixture, stir at 20-30°C for 20-40 minutes, place it at 10°C for 30 minutes, adjust the temperature to -5-7°C and keep it for 40-60 minutes for slow stirring, curing and crosslinking , Wrap the above mixture with gauze and squeeze to remove water. Rinse with 10-20% tannic acid solution for 2-3 times; place the above mixture in an oven at 50-70°C for 8-10 hours.

Preferably in the oven treatment stage: the mixture is placed in an oven at 50-70°C for 8-10 hours, then heated to 85°C and kept for 2-5 minutes, then cooled to 50-70°C and kept for 1 hour.

The ratio of pretreated attapulgite to MBAA is 10:4-8.

The brine is a mixed solution of KCL and polyvinyl alcohol, the mass concentration of KCL is 2-5%, and the mass concentration of polyvinyl alcohol is 3-8%.

The preparation method of the carbon nanotube is as follows: adding 20-30% of the weight of the methanol aqueous solution to the methanol aqueous solution with a volume ratio of 10-25%, soaking the carbon nanotube for 30-50 minutes, and then centrifuging to collect the precipitate.

The added amount of the biopolymer solution is 2-8 times of the mass of the attapulgite.

The preparation method of biopolymer solution is as follows:

The polyglutamic acid fermentation liquid obtained by fermentation culture is mixed with the ganoderma lucidum fermentation culture liquid at a ratio of 1:6-8, and then heated and concentrated to 10-40% of the mixed volume.

The polyglutamic acid fermentation liquid and the Ganoderma lucidum fermentation liquid can be cultured according to conventional methods.

The concentration of activated sludge is 3000-5000mg/L;

The cyclodextrin complex solution contains 8-15% cyclodextrin and 35-45% boric acid in weight ratio.

Pretreatment of attapulgite. Attapulgite with a particle size of 300 mesh to 1000 mesh, add attapulgite to a methanol solution with a volume concentration of 15-35%, and control the temperature at 45-50°C for electric pulse treatment; then precipitate for 1-2 hours and take the supernatant, Add a small amount of distilled water to the supernatant and mix it evenly, then continue to centrifuge at 500rpm for 1min, then take the supernatant, wash the supernatant repeatedly in this way for 3 to 5 times, and finally use 2000-3000 for centrifugation, take the precipitate, and store it at 90°C Vacuum dry for 24 hours, after grinding, sieve through a sieve with a particle size of 200 mesh to 400 mesh, and collect attapulgite for later use.

The electric pulse treatment conditions are as follows: high-voltage pulse treatment for 5-10 minutes; high-voltage pulse electric field (PEF) treatment parameters are preferably: electric field strength 20-40KV/cm, pulse time 400-600μS, pulse frequency 200-300Hz.

Beneficial effect:

Compared with the prior art, the present invention has the following remarkable advantages: (1) The adsorbent obtained by the method of the present invention can efficiently adsorb and remove pollutants in waste water, such as heavy metal ions, dyes and petrochemical pollutants. (2) The cross-linked adsorbent has strength and stability, will not cause secondary pollution to the water body, and the adsorbent has good elasticity and high wear resistance; (3) The source of raw materials is abundant, the production process is simple, and the raw materials are easy to process , the craft is easy to master.

Example 1

The object of the present invention is to provide a biological purification carrier for wastewater treatment. The technical scheme is as follows:

The preparation method of the biological purification carrier for wastewater treatment is as follows:

Mix the pretreated attapulgite and MBAA in brine, and stir at 60°C for 2 hours; mix the biopolymer solution with the above mixed solution, heat the above solution to 50°C, and add activated sludge with 4% mass of attapulgite and 2% nano-iron-manganese composite oxide, adding attapulgite mass 4% carbon nanotubes and stirring for 2 hours, the stirring speed is 8 revolutions/min. Then add the cyclodextrin complex solution to the above mixed solution, stir at 25°C for 30 minutes, then place it at 10°C for 30 minutes, adjust the temperature to -7°C and keep it for 50 minutes for slow stirring, solidification and crosslinking, and wrap the above mixture with gauze Squeeze to remove water. Rinse 3 times with 15% tannic acid solution; place the above mixture in an oven at 60°C for 10 hours.

The ratio of pretreated attapulgite to MBAA is 10:6.

The brine is a mixed solution of KCL and polyvinyl alcohol, the mass concentration of KCL is 4%, and the mass concentration of polyvinyl alcohol is 5%.

The preparation method of the carbon nanotube is as follows: adding 25% of the weight of the methanol aqueous solution to the methanol aqueous solution with a volume ratio of 15% of the carbon nanotube, soaking for 30-50 minutes, and then centrifuging to collect the precipitated matter.

The added amount of the biopolymer solution is 6 times of the mass of attapulgite.

The preparation method of biopolymer solution is as follows:

The polyglutamic acid fermentation liquid obtained from the fermentation culture is mixed with the ganoderma lucidum fermentation culture liquid at a ratio of 1:7, and then concentrated to 30% of the mixed volume by using a concentration device.

The polyglutamic acid fermentation liquid and the Ganoderma lucidum fermentation liquid can be cultured according to conventional methods.

The concentration of activated sludge is 4000mg/L;

The cyclodextrin complex solution contains 14% cyclodextrin and 42% boric acid.

Pretreatment of attapulgite. Attapulgite with a particle size of 300 mesh to 1000 mesh, add attapulgite to a methanol solution with a volume concentration of 25%, and control the temperature at 45-50°C for electric pulse treatment; after precipitation for 1 hour, take the supernatant, put Add a small amount of distilled water and mix well, continue to centrifuge at 500rpm for 1min, then take the supernatant, wash the supernatant repeatedly in this way for 3 to 5 times, and finally use 2200 for centrifugation, take the precipitate, vacuum dry at 90°C for 24h, after grinding Sieve through a sieve with a particle size of 200 mesh to 300 mesh, and collect the attapulgite for later use.

The electric pulse treatment conditions are as follows: high-voltage pulse treatment for 6 minutes; high-voltage pulse electric field (PEF) treatment parameters are preferably: electric field intensity 30KV/cm, pulse time 500μS, pulse frequency 200Hz.

Example 2

The object of the present invention is to provide a biological purification carrier for wastewater treatment. The technical scheme is as follows:

The preparation method of the biological purification carrier for wastewater treatment is as follows:

Mix the pretreated attapulgite and MBAA in brine, and stir at 50°C for 3 hours; mix the biopolymer solution with the above mixed solution, heat the above solution to 40°C, and add activated sludge with 5% mass of attapulgite and 1% nano-iron-manganese composite oxide, adding 5% carbon nanotubes of attapulgite mass and stirring for 1 hour, the stirring speed is 5 rpm. Then add the cyclodextrin complex solution to the above mixed solution, stir at 20°C for 40 minutes, place it at 10°C for 30 minutes, adjust the temperature to -5°C and keep it for 60 minutes for slow stirring, curing and crosslinking, and wrap the above mixture with gauze Squeeze to remove water. Rinse twice with 10% tannic acid solution; place the above mixture in an oven at 55°C for 10 hours.

The ratio of pretreated attapulgite to MBAA is 10:4.

The brine is a mixed solution of KCL and polyvinyl alcohol, the mass concentration of KCL is 2%, and the mass concentration of polyvinyl alcohol is 3%.

The preparation method of the carbon nanotube is as follows: adding 30% of the weight of the methanol aqueous solution to the methanol aqueous solution with a volume ratio of 10% of the carbon nanotube, soaking for 30 minutes, and then centrifuging to collect the precipitated matter.

The added amount of the biopolymer solution is 8 times of the mass of attapulgite.

The preparation method of biopolymer solution is as follows:

The polyglutamic acid fermentation broth obtained from the fermentation culture is mixed with the ganoderma fermentation culture fluid at a ratio of 1:8, and then concentrated to 10% of the mixed volume by using a concentration device.

The polyglutamic acid fermentation liquid and the Ganoderma lucidum fermentation liquid can be cultured according to conventional methods.

The concentration of activated sludge is 5000mg/L;

The cyclodextrin complex solution contains 15% cyclodextrin and 45% boric acid.

Pretreatment of attapulgite. Attapulgite with a particle size of 300 mesh to 1000 mesh, add attapulgite to a methanol solution with a volume concentration of 35%, and control the temperature at 45-50°C for electric pulse treatment; after precipitation for 1 hour, take the supernatant, put Add a small amount of distilled water and mix well, continue to centrifuge at 500rpm for 1min, then take the supernatant, wash the supernatant repeatedly for 3 to 5 times, and finally use 2000 for centrifugation, take the precipitate, vacuum dry at 90°C for 24h, after grinding Sieve through a sieve with a particle size of 200 mesh to 400 mesh, and collect the attapulgite for later use.

The electric pulse treatment conditions are as follows: high-voltage pulse treatment for 10 minutes; high-voltage pulse electric field (PEF) treatment parameters are preferably: electric field intensity 40KV/cm, pulse time 400μS, pulse frequency 300Hz.

Example 3

The object of the present invention is to provide a biological purification carrier for wastewater treatment. The technical scheme is as follows:

The preparation method of the biological purification carrier for wastewater treatment is as follows:

Mix the pretreated attapulgite and MBAA in brine, and stir at 50°C for 1 hour; mix the biopolymer solution with the above mixed solution, heat the above solution to 40°C, and add activated sludge with 2% mass of attapulgite and 1% nano-iron-manganese composite oxide, adding attapulgite mass 2-5% carbon nanotubes and stirring for 1 hour, the stirring speed is 5 revolutions/min. Then add the cyclodextrin complex solution to the above mixture, stir at 20°C for 20 minutes, place it at 10°C for 30 minutes, adjust the temperature to -7°C and keep it for 60 minutes for slow stirring, curing and crosslinking, wrap the above mixture with gauze Squeeze to remove water. Rinse twice with 10% tannic acid solution; place the mixture in an oven at 70°C for 8 hours, then raise the temperature to 85°C and keep it for 5 minutes, then cool down to 70°C and keep it for 1 hour.

The ratio of pretreated attapulgite to MBAA is 10:4.

The brine is a mixed solution of KCL and polyvinyl alcohol, the mass concentration of KCL is 2%, and the mass concentration of polyvinyl alcohol is 3%.

The preparation method of the carbon nanotube is as follows: adding 20% of the weight of the methanol aqueous solution to the methanol aqueous solution with a volume ratio of 10% of the carbon nanotube, soaking for 50 minutes, and then centrifuging to collect the precipitated matter.

The added amount of the biopolymer solution is 4 times of the mass of attapulgite.

The preparation method of biopolymer solution is as follows:

The polyglutamic acid fermentation liquid obtained from the fermentation culture is mixed with the ganoderma lucidum fermentation culture liquid at a ratio of 1:7, and then concentrated to 10% of the mixed volume by using a concentration device.

The polyglutamic acid fermentation liquid and the Ganoderma lucidum fermentation liquid can be cultured according to conventional methods.

The concentration of activated sludge is 3000mg/L;

The cyclodextrin complex solution contains 8% cyclodextrin and 35% boric acid.

Pretreatment of attapulgite. For attapulgite with a particle size of 300 mesh to 500 mesh, add attapulgite to a methanol solution with a volume concentration of 25%, and control the temperature at 45-50°C for electric pulse treatment; Add a small amount of distilled water to the solution and mix it evenly, then continue to centrifuge at 500rpm for 1min, then take the supernatant, wash the supernatant repeatedly in this way for 3 to 5 times, and finally use 2000-3000 for centrifugation, take the precipitate, and vacuum dry at 90°C After 24 hours, after grinding, sieve through a sieve with a particle size of 200 mesh to 400 mesh, and collect attapulgite for later use.

The electric pulse treatment conditions are as follows: high voltage pulse treatment for 5 minutes; high voltage pulse electric field (PEF) treatment parameters are preferably: electric field intensity 20KV/cm, pulse time 400μS, pulse frequency 300Hz.

The preparation method of polyglutamic acid fermented liquid also can adopt following method:

Bacillus licheniformis was used.

The fermentation method is as follows: a 30L fermentation tank has a liquid volume of 15L, using the above-mentioned fermentation medium, the inoculation amount of the seed liquid is 1.0% to 15.0%, the fermentation temperature is 30 to 40°C, the fermentation time is 24 to 72 hours, and the ventilation rate is 0.5 ～2.0vvm, dissolved oxygen 1～50%, rotating speed 200～400rpm.

The composition of the fermentation medium is (g/L): glucose 80, sodium glutamate 80, ammonium nitrate 18, NaCl 10, MgSO ₄ 6H ₂ O 0.5, CaCl ₂ 6H ₂ O 1.0, FeSO ₄ 6H ₂ O 0.01, arginine 0.44, histidine 0.26, threonine 0.5, methionine 0.4, choline 0.1, glutamine 0.5, pyridoxine 0.001.

Use effect experiment:

test 1

Add 20g of this adsorbent to 5L of waste water containing Pb: 150mg/L and Zn: 260mg/L, Ni ²⁺ : 90mg/L, and use inductively coupled plasma emission spectrometry to measure the ion concentration of heavy metals in the waste water after 45 minutes Pb: 13.3mg/L and Zn: 12.6mg/L.Ni ²⁺ : 6.5mg/L

test 2

Add 50 g of this adsorbent to 50 L of waste containing Ni ²⁺ : 850 mg/L and Cu ²⁺ : 100 mg/L. After 30 minutes, use inductively coupled plasma emission spectrometry to measure the ion concentration of heavy metals in the waste water as Ni ^{2 +} : 5.8mg/L and Cu ²⁺ : 3.3mg/L.

Test 3

Add 100 g of this adsorbent to 150 L of mixed wastewater containing malachite green and crystal violet at a concentration of 125 mg/L, shake and adsorb for 30 minutes, and the decolorization rates are 95% and 97%.

Test 4

Add 60g of this adsorbent into 100L of phenol-containing wastewater containing 60mg/L, and measure the concentration of phenol in the wastewater by spectrophotometry after 0.6h of use to be 1.5mg/L.

Claims (9)

1. A biological purification carrier preparation method for waste water treatment, as follows: Mix the pretreated attapulgite and MBAA in brine, and stir at 60°C for 2 hours; mix the biopolymer solution with the above mixed solution, heat the above solution to 50°C, and add activated sludge with 4% mass of attapulgite and 2% nano-iron-manganese composite oxide, adding attapulgite quality 4% carbon nanotubes and stirring for 2 hours, the stirring speed is 8 revolutions/min; Stir for 30 minutes, place at 10°C for 30 minutes, adjust the temperature to -7°C and keep for 50 minutes for slow stirring, curing and crosslinking, wrap the above mixture with gauze and squeeze to remove water; rinse with 15% tannic acid solution for 3 times ; The above mixture can be placed in an oven at 60°C for 10 hours. 2. The biological purification carrier preparation method for wastewater treatment according to claim 1, the mass ratio of the pretreated attapulgite and MBAA is: 10:6. 3. The biological purification carrier preparation method for wastewater treatment according to claim 1, wherein the brine is a mixed solution of KCl and polyvinyl alcohol, the mass concentration of KCl is 4%, and the mass concentration of polyvinyl alcohol is 5%. 4. the biological purification carrier preparation method of waste water treatment according to claim 1, the preparation method of described carbon nanotube is: in the methanol aqueous solution that volume ratio is 15%, add the carbon nanotube of methanol aqueous solution weight 25%, soak Treat for 30-50 minutes, then centrifuge to collect the precipitated material. 5. The method for preparing a biological purification carrier for wastewater treatment according to claim 1, wherein the added amount of the biopolymer solution is 6 times the mass of attapulgite. 6. the biological purification carrier preparation method of waste water treatment according to claim 1, the preparation method of described biopolymer solution is as follows: the polyglutamic acid fermented liquid that fermentation culture obtains and ganoderma fermentation culture liquid are according to 1:7 Mixed and then concentrated to 30% of the mixed volume using thickening equipment. 7. The method for preparing a biological purification carrier for wastewater treatment according to claim 1, wherein the concentration of the activated sludge is 4000mg/L. 8. The method for preparing a biological purification carrier for wastewater treatment according to claim 1, wherein the cyclodextrin composite solution contains 14% cyclodextrin and 42% boric acid by weight. 9. The preparation method of the biological purification carrier for wastewater treatment according to claim 1, the pretreatment of the attapulgite: the attapulgite with a particle size of 300 mesh to 1000 mesh, adding the attapulgite to methanol with a volume concentration of 25% Solution, control the temperature at 45-50°C for electric pulse treatment; then take the supernatant after precipitation for 1 hour, add a small amount of distilled water to the supernatant and mix evenly, continue to centrifuge at 500rpm for 1min, then take the supernatant, and wash the supernatant repeatedly in this way After 3 to 5 times, centrifuge at 2200rpm, take the precipitate, and vacuum dry at 90°C for 24 hours. After grinding, sieve through a sieve with a particle size of 200 to 300 mesh, and collect attapulgite for use: electric pulse treatment conditions As follows: high-voltage pulse treatment for 6 minutes; high-voltage pulsed electric field (PEF) treatment parameters are preferably: electric field intensity 30KV/cm, pulse time 500μS, pulse frequency 200Hz.