CN106630183A - Preparation of biological purification carrier for wastewater purification - Google Patents

Preparation of biological purification carrier for wastewater purification Download PDF

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Publication number
CN106630183A
CN106630183A CN201611029779.5A CN201611029779A CN106630183A CN 106630183 A CN106630183 A CN 106630183A CN 201611029779 A CN201611029779 A CN 201611029779A CN 106630183 A CN106630183 A CN 106630183A
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attapulgite
solution
minutes
wastewater treatment
biological
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CN201611029779.5A
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Chinese (zh)
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CN106630183B (en
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邵素英
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邵素英
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12Naturally occurring clays or bleaching earth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • Y02W10/45

Abstract

The invention provides a biological purification carrier for wastewater treatment. The biological purification carrier can be prepared by the following method: mixing attapulgite to be treated and MBAA in saline water, and performing stirring for 1 to 3h at 50 to 70 DEG C; mixing a biological macromolecular solution and the mixed solution, heating the solution to 40 to 60 DEG C, adding activated sludge in an amount which is 2 to 5 percent on the basis of the mass of the attapulgite and a nanometer iron-manganese composite oxide in an amount which is 1 to 3 percent on the basis of the mass of the attapulgite, adding carbon nanotubes in an amount which is 2 to 5 percent on the basis of the mass of the attapulgite, performing stirring treatment for 1 to 3h at the stirring speed of 5 to 10 revolutions per minute, then adding a cyclodextrin composite solution into the mixed solution, performing stirring for 20 to 40 minutes at 20 to 30 DEG C, performing standing for 30 minutes at 10 DEG C, regulating the temperature to -5 to 7 DEG C, preserving heat for 40 to 60 minutes, performing slow stirring for curing and crosslinking, wrapping the mixture with a gauze, performing extruding for water removal, and performing flushing for twice to three times with a 10 to 20 percent tannic acid solution; treating the mixture for 8 to 10h in a 50 to 70 DEG C drying oven. According to the biological purification carrier, pollutants in wastewater can be efficiently adsorbed and removed, the biological purification carrier is strong, stable and high in abrasion resistance, and has good elastic effects, and a production process is simple and easy to operate and master.

Description

It is prepared by a kind of biological cleaning carrier of purification of waste water

The present invention be directed to Application No. 2015104632804, a kind of entitled biology for wastewater purification is only Change the divisional application of carrier patent application;

Technical field

The invention belongs to field of waste water treatment.

Background technology

With developing rapidly for modern industry and urbanization, water pollution is on the rise.Method of wastewater treatment mainly has chemistry The precipitation method, electrolysis, ion-exchange, membrane processing method etc., but there is complex process when processing in these methods, it is cumbersome, Operating cost is high, produces the defects such as secondary pollution.Develop and the use of new efficient, low toxicity, inexpensive water technology is solution Certainly one of key of water pollution problems.

Attapulgite (also known as palygorskite) is a kind of natural non-metallic mineral material, is a kind of with chain layer structure The clay mineral of magnesium silicate containing Shuifu County, typical chemical formula is Si8Mg6O20(OH)2(OH2)4·4H2O, structure belongs to 2:1 type clay pit Thing, each 2:In 1 unit structure layer, at a certain distance direction overturns on tetrahedron chip angle top, forming layer chain.In tetrahedron Bar interband forms the passage parallel with chain, and zeolite water and the crystallization water are filled in passage.Attapulgite fibre structure generally comprises three Individual level:1. basic structural unit is micro- bar-shaped or fibrous monocrystal, and abbreviation rod is brilliant.2. by the list of monocrystalline aggregate parallel Brilliant beam.3. the aggregation mutually piled up by brilliant beam (brilliant including rod).The special construction of attapulgite makes it have very big Specific surface area, physical absorption is very capable.On the other hand, attapulgite carries aspect negative electrical charge, and having in Inter layer adsorption can So that charge balance, such attapulgite is just provided with stronger ionic adsorption exchange capacity for the cation of exchangeability.

Attapulgite has good suspension in water, although therefore attapulgite has good adsorption capacity, for For water treatment field, the attapulgite of powder cannot be direct plungeed into used in water, need to take at certain method Reason.At present, preferable processing method is to adopt certain immobilized attapulgite of carrier, then is put into used in water.There is inventor to exist A kind of preparation method of absorbent-type macromolecule composite aquogel and products thereof is disclosed in invention【201020595998.1】, utilize Macromolecule hydrogel makees carrier, immobilized attapulgite, so as to play the suction-operated of attapulgite well.But, this is concavo-convex The efficiency of rod soil composite aquogel Adsorption of Heavy Metal Ions is low, adsorbance is little, cleans difficult after gel adsorption heavy metal ion, and Gel does not have sensitiveness to the pH value of solution, it is impossible to by the absorption for controlling the pH value of solution to control heavy metal ion Amount.

A kind of method of a large amount of production gamma-polyglutamic acids, application number:201110216717.6.A kind of γ of disclosure of the invention- The production method of polyglutamic acid, more particularly to a kind of method of the gamma-polyglutamic acid of a large amount of production high concentrations.The skill of the present invention Art plan explanation is as follows:1. the activation of bacterial classification;2. the preparation of seed liquor;3. ferment tank;It is characterized in that by fermentation During add the fed-batch medium being made up of glucose, ammonium nitrate, CaCl26H2O and FeCl36H2O, make fermentation production rate 1.18g/lh is reached, so as to reach the purpose for efficiently preparing big weight gamma-polyglutamic acid.

The patent of invention of the arsenic removal material of entitled a kind of nanometer of ferro manganese composite oxides and preparation method thereof, the invention is related to And the arsenic removal material of a kind of nanometer of ferro manganese composite oxides, it is a nanometer ferro manganese composite oxides, the atom of institute's iron content, manganese and oxygen Than for 4:3:(8~10), wherein manganese are+4 valencys, and iron is+trivalent, and the BET specific surface area of the arsenic removal material is 225~282m2/ G, average grain diameter is 10~20nm.The patent No.:CN201210237752.0.

Chen great Jun, Dong Aijuan, Jiang Zequan etc. a kind of device of magnetic attapulgite wastewater treatment:China, 201120143921.5 [P] .2011-12-14. this patent provides a kind of device of magnetic attapulgite wastewater treatment, realizes Dynamic Adsorption of the magnetic attapulgite in water process, and used with pulverulence, eliminate the trouble of granulation.And overcome Attapulgite difficult detached difficult problem in water phase, without adding the heavy agent of wadding magnetic attapulgite can be made to isolate from water phase Come, eliminate the secondary pollution for being possible to bring because adding the heavy agent of wadding.It is concavo-convex that the i.e. controllable magnetic of wastewater flow is adjusted simultaneously Rod soil and the action time of waste water, optimal adsorption effect is reached, can be recessed to change magnetic according to the concentration of useless impurities in water The addition of convex rod soil, it is optimum with the utilization ratio for realizing magnetic attapulgite.

Li Yanhua. it is a kind of for the attapulgite modified and preparation method thereof of sewage disposal:China, 201410383602.X [P] .2014-12-10. this patented invention is a kind of for the attapulgite modified of sewage disposal, by attapulgite Addition acrylamide, increased the flocculation reaction to water pollutant;By adding ammonium molybdate, ammonium chloride, cetyl front three Base ammonium bromide, increased adsorptivity.The attapulgite activation degree is high, and be modified uniform, excellent performance, it is adaptable to waste water control, Excellent adsorption, does not produce secondary pollution.The filler of coating, rubber is can also be used to simultaneously, and not only suspension is good, and thixotropy is good, But also with rustless property.

The method that surfactant-modified attapulgite removes heavy metal in percolate:The patent No. 201410744321.2, this patent disclose a kind of surfactant-modified attapulgite and remove heavy metal in percolate Method, heavy metal in percolate is purified using the attapulgite after surfactant-modified.The method energy Effectively the heavy metal in percolate is adsorbed, its percolate removal efficiency of heavy metals is than only using original recessed The efficiency of convex rod soil improves 30%, and better than traditional adsorption method.

A kind of threonine modified attapulgite earth adsorbing and its .201410453968.X is applied, this patent disclose one The preparation method of threonine modified attapulgite earth adsorbing is planted, using conventional chemical agent threonine to from uniqueness point The attapulgite of the good colloidal nature such as scattered, high temperature resistant, salt resistance alkali and higher adsorption bleaching ability is modified, and obtains right Printing dye and heavy metal wastewater thereby have the attapulgite modified absorption of excellent adsorption capacity.The adsorbent of preparation to dyeing waste water and Heavy metal wastewater thereby has excellent adsorption capacity, wherein may be up to 650 and 1380mg/ to methylene blue and acid fuchsin saturated extent of adsorption G, is 143mg/g and 81mg/g to the saturated extent of adsorption of copper and chromium heavy metal wastewater thereby.

The application study [J] in the treatment of waste water of bodied ferric sulfate composite flocculation agent. Information, 2012 (6):77-79. This document proposes a kind of preparation technology of attapulgite-bodied ferric sulfate composite flocculation agent, as a result shows bodied ferric sulfate There is good flocculation and treatment effect to waste water with the attapulgite modified composite flocculation agent prepared for raw material.By to it CODcr clearances and turbidity removal rate in sanitary wastewater is compared, and obtains the optimum preparation technology bar of composite flocculation agent Part:Attapulgite heat treatment temperature is 400 DEG C, recombination reaction temperature 50 C, attapulgite dosage 2.0g/L, compound reaction time Between be 4h.

The preparation of the attapulgite clay/carbon composite of Xu Lingshu and its water pollution are processed applies Primary Study, is published in Yangzhou University, 2013. this document are prepared concave convex rod and are glued with attapulgite clay and sucrose by hydrothermal synthesis reaction as raw material Soil/carbon composite so as to can efficient absorption and go in eliminating water dissolubility micro quantity organic pollutant and toxic heavy metal from Son.As a result show that carbon is coated on concave convex rod plane of crystal with the form of amorphous carbon, hydrophilic organofunctional is occurred in that in material Group so that its organophilic can have significant improvement.In hydro-thermal reaction, reaction time, temperature, pH and concave convex rod glue Soil has a significant impact with the ratio of carbon source quality to the absorption property of attapulgite clay/carbon composite.

Chen Hui, Qiang Yinghuai, Yin Hui. the synthesis of attapulgite/polyacrylamide hybrid flocculant and its flocculating properties are studied [J]. nonmetallic ore, 2011,34 (2):36-39. this document adopts the scattered method of ultrasonic wave, N- methacryl-N '- Pyrimidine piperazine (MPMP) and potassium peroxydisulfate (K2S2O8) composition redox system under, acrylamide triggered monomer (AM) is in acid There is graft polymerization reaction in attapulgite modified (ATP) surface, generate attapulgite grafted polyacrylamide hybrid flocculant (ATP/PAM).It is dirty by the real life that sewage and solid content 5.2% are simulated to 2.5wt% kaolin, 5wt% bloodstone Water process finds that ATP/PAM flocculates, and the alumen ustum sinking speed to be formed is fast, and flocculation time is short, and the sludge quantity of generation is few, very big It is better than common PAM in the range of addition, the efficiency and ability of sewage disposal can be effectively improved.

The content of the invention

It is an object of the invention to provide a kind of biological cleaning carrier for wastewater treatment, can prepare by the following method:

The attapulgite of pretreatment mixes with MBAA in salt solution, and at 50-70 DEG C 1-3h is stirred;Boiomacromolecule is molten Liquid mixes with above-mentioned mixed solution, and above-mentioned solution is heated into 40-60 DEG C, adds the activated sludge of attapulgite quality 2-5% With the nanometer ferro manganese composite oxides of 1-3%, the CNT stir process 1-3 hour of attapulgite quality 2-5% is added, stirred Mix speed and turn/min for 5-10.Mixed liquor being stated then up and adding cyclodextrin composite solution, at 20-30 DEG C 20-40 minutes are stirred, After placing 30 minutes at 10 DEG C, adjustment temperature is -5-7 DEG C and is kept for 40-60 minutes carry out being slowly stirred solidification crosslinking, will be above-mentioned mixed Water is removed in extrusion after compound gauze wrapped.Rinsed 2-3 time with 10-20% tannic acid solutions;Said mixture places 50-70 DEG C of baking Case is processed after 8-10 hours.

Preferably in the oven stage:Mixture to be placed and be warmed up to 85 DEG C of guarantors after 50-70 DEG C of oven 8-10 hour Hold 2-5 minutes cool to 50-70 DEG C keep 1 hour.

The attapulgite of pretreatment and the ratio of MBAA are 10:4-8.

The salt solution is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 2-5%, and polyvinyl alcohol mass concentration is 3-8%.

The preparation method of CNT is:Add methanol aqueous solution weight in volume ratio is for the methanol aqueous solution of 10-25% Sediment is collected in the CNT of amount 20-30%, immersion treatment 30-50 minute, subsequently centrifugation.

The addition of the biological macromolecular solution is 2-8 times of attapulgite quality.

The preparation method of biological macromolecular solution is as follows:

The polyglutamic acid zymotic fluid that fermented and cultured is obtained is with Ganoderma Lucidum fermented and cultured liquid according to 1:6-8 mixes, subsequently Heating is concentrated to the 10-40% of mixed volume.

The polyglutamic acid zymotic fluid is conventionally cultivated with Ganoderma Lucidum fermentation culture.

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

Containing the boric acid of the cyclodextrin and 35-45% that weight ratio is 8-15% in cyclodextrin composite solution.

The pretreatment of attapulgite.The attapulgite of mesh~1000 mesh of particle diameter 300, be by attapulgite addition volumetric concentration The methanol solution of 15-35%, control temperature is in 45-50 DEG C of Electric Pulse Treatment;Subsequently supernatant liquor is taken after precipitation 1-2 hours, on Continue 500rpm centrifugation 1min in layer clear liquid plus after a small amount of distilled water is well mixed, then take its supernatant liquor, so wash repeatedly After washing supernatant liquor 3~5 times, finally it is centrifuged with 2000-3000, takes its precipitation, at 90 DEG C 24h is vacuum dried, is ground Sieve by mesh~400 mesh sieve of particle diameter 200 after mill, collect attapulgite stand-by.

Electric Pulse Treatment condition is as follows:High-voltage pulse processes 5-10 minutes;High-pressure pulse electric (PEF) processing parameter is preferable Ground is:Electric-field intensity 20-40KV/cm, burst length 400-600 μ S, pulse frequency 200-300Hz.

Beneficial effect:

Compared with prior art, its remarkable advantage is the present invention:(1) the inventive method gained adsorbent energy efficient absorption is clear Except the pollutant in waste water, such as heavy metal ion, dyestuff and petrochemical industry pollutant.(2) crosslinking adsorbent be with intensity and Stability, will not cause secondary pollution to water body, and adsorbent elastic effect is good, and abrasion strength resistance is high;(3) raw material sources are rich Richness, simple production process, raw material easy processing, technique is easy to grasp.

Embodiment 1

It is an object of the invention to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:

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

The attapulgite of pretreatment mixes with MBAA in salt solution, and at 60 DEG C 2h is stirred;By biological macromolecular solution with Above-mentioned mixed solution mixing, by above-mentioned solution 50 DEG C are heated to, and add the activated sludge of attapulgite quality 4% and 2% receive Rice ferro manganese composite oxides, add the CNT stir process of attapulgite quality 4% 2 hours, and mixing speed is 8 turns/ min.Mixed liquor is stated then up and adds cyclodextrin composite solution, stirred 30 minutes at 25 DEG C, after placing 30 minutes at 10 DEG C, adjust Whole temperature is that -7 DEG C of holdings carry out being slowly stirred solidification crosslinking for 50 minutes, and extrusion after said mixture gauze wrapped is gone into water. Rinsed 3 times with 15% tannic acid solution;Said mixture placed 60 DEG C of ovens after 10 hours.

The attapulgite of pretreatment and the ratio of MBAA are:10:6.

The salt solution is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 4%, and polyvinyl alcohol mass concentration is 5%.

The preparation method of CNT is:Add methanol aqueous solution weight in the methanol aqueous solution that volume ratio is 15% Deposit is collected in 25% CNT, immersion treatment 30-50 minute, subsequently centrifugation.

The addition of the biological macromolecular solution is 6 times of attapulgite quality.

The preparation method of biological macromolecular solution is as follows:

The polyglutamic acid zymotic fluid that fermented and cultured is obtained is with Ganoderma Lucidum fermented and cultured liquid according to 1:7 mixing, subsequently adopt The 30% of mixed volume is concentrated to concentrator.

The polyglutamic acid zymotic fluid is conventionally cultivated with Ganoderma Lucidum fermentation culture.

The concentration of activated sludge is 4000mg/L;

Boric acid containing 14% cyclodextrin and 42% in cyclodextrin composite solution.

The pretreatment of attapulgite.The attapulgite of mesh~1000 mesh of particle diameter 300, be by attapulgite addition volumetric concentration 25% methanol solution, control temperature is in 45-50 DEG C of Electric Pulse Treatment;Subsequently precipitation takes supernatant liquor, supernatant liquor after 1 hour In plus a small amount of distilled water be well mixed after continue 500rpm centrifugation 1min, then take its supernatant liquor, such cyclic washing upper strata After clear liquid 3~5 times, finally it is centrifuged with 2200, takes its precipitation, 24h is vacuum dried at 90 DEG C, particle diameter is pressed after grinding 200 mesh~300 mesh sieve are sieved, and collect attapulgite stand-by.

Electric Pulse Treatment condition is as follows:High-voltage pulse is processed 6 minutes;High-pressure pulse electric (PEF) processing parameter is preferably For:Electric-field intensity 30KV/cm, the μ S of burst length 500, pulse frequency 200Hz.

Embodiment 2

It is an object of the invention to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:

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

The attapulgite of pretreatment mixes with MBAA in salt solution, and at 50 DEG C 3h is stirred;By biological macromolecular solution with Above-mentioned mixed solution mixing, by above-mentioned solution 40 DEG C are heated to, and add the activated sludge of attapulgite quality 5% and 1% receive Rice ferro manganese composite oxides, add the CNT stir process of attapulgite quality 5% 1 hour, and mixing speed is 5 turns/ min.Mixed liquor is stated then up and adds cyclodextrin composite solution, stirred 40 minutes at 20 DEG C, after placing 30 minutes at 10 DEG C, adjust Whole temperature is that -5 DEG C of holdings carry out being slowly stirred solidification crosslinking for 60 minutes, and extrusion after said mixture gauze wrapped is gone into water. Rinsed 2 times with 10% tannic acid solution;Said mixture placed 55 DEG C of ovens after 10 hours.

The attapulgite of pretreatment and the ratio of MBAA are:10:4.

The salt solution is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 2%, and polyvinyl alcohol mass concentration is 3%.

The preparation method of CNT is:Add methanol aqueous solution weight in the methanol aqueous solution that volume ratio is 10% Deposit is collected in 30% CNT, immersion treatment 30 minutes, subsequently centrifugation.

The addition of the biological macromolecular solution is 8 times of attapulgite quality.

The preparation method of biological macromolecular solution is as follows:

The polyglutamic acid zymotic fluid that fermented and cultured is obtained is with Ganoderma Lucidum fermented and cultured liquid according to 1:8 mixing, subsequently adopt The 10% of mixed volume is concentrated to concentrator.

The polyglutamic acid zymotic fluid is conventionally cultivated with Ganoderma Lucidum fermentation culture.

The concentration of activated sludge is 5000mg/L;

Boric acid containing 15% cyclodextrin and 45% in cyclodextrin composite solution.

The pretreatment of attapulgite.The attapulgite of mesh~1000 mesh of particle diameter 300, be by attapulgite addition volumetric concentration 35% methanol solution, control temperature is in 45-50 DEG C of Electric Pulse Treatment;Subsequently precipitation takes supernatant liquor, supernatant liquor after 1 hour In plus a small amount of distilled water be well mixed after continue 500rpm centrifugation 1min, then take its supernatant liquor, such cyclic washing upper strata After clear liquid 3~5 times, finally it is centrifuged with 2000, takes its precipitation, 24h is vacuum dried at 90 DEG C, particle diameter is pressed after grinding 200 mesh~400 mesh sieve are sieved, and collect attapulgite stand-by.

Electric Pulse Treatment condition is as follows:High-voltage pulse is processed 10 minutes;High-pressure pulse electric (PEF) processing parameter is preferably For:Electric-field intensity 40KV/cm, the μ S of burst length 400, pulse frequency 300Hz.

Embodiment 3

It is an object of the invention to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:

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

The attapulgite of pretreatment mixes with MBAA in salt solution, and at 50 DEG C 1h is stirred;By biological macromolecular solution with Above-mentioned mixed solution mixing, by above-mentioned solution 40 DEG C are heated to, and add the activated sludge of attapulgite quality 2% and 1% receive Rice ferro manganese composite oxides, add the CNT stir process 1 hour of attapulgite quality 2-5%, and mixing speed is 5 turns/ min.Mixed liquor is stated then up and adds cyclodextrin composite solution, stirred 20 minutes at 20 DEG C, after placing 30 minutes at 10 DEG C, adjust Whole temperature is that -7 DEG C of holdings carry out being slowly stirred solidification crosslinking for 60 minutes, and extrusion after said mixture gauze wrapped is gone into water. Rinsed 2 times with 10% tannic acid solution;Mixture places 70 DEG C of ovens and 85 DEG C of holdings cooling in 5 minutes is warmed up to after 8 hours Kept for 1 hour to 70 DEG C.

The attapulgite of pretreatment and the ratio of MBAA are:10:4.

The salt solution is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 2%, and polyvinyl alcohol mass concentration is 3%.

The preparation method of CNT is:Add methanol aqueous solution weight in the methanol aqueous solution that volume ratio is 10% Deposit is collected in 20% CNT, immersion treatment 50 minutes, subsequently centrifugation.

The addition of the biological macromolecular solution is 4 times of attapulgite quality.

The preparation method of biological macromolecular solution is as follows:

The polyglutamic acid zymotic fluid that fermented and cultured is obtained is with Ganoderma Lucidum fermented and cultured liquid according to 1:7 mixing, subsequently adopt The 10% of mixed volume is concentrated to concentrator.

The polyglutamic acid zymotic fluid is conventionally cultivated with Ganoderma Lucidum fermentation culture.

The concentration of activated sludge is 3000mg/L;

Boric acid containing 8% cyclodextrin and 35% in cyclodextrin composite solution.

The pretreatment of attapulgite.The attapulgite of mesh~500 mesh of particle diameter 300, be by attapulgite addition volumetric concentration 25% methanol solution, control temperature is in 45-50 DEG C of Electric Pulse Treatment;Subsequently supernatant liquor is taken after precipitation 1-2 hours, upper strata is clear Continue 500rpm centrifugation 1min in liquid plus after a small amount of distilled water is well mixed, its supernatant liquor is then taken, on such cyclic washing After layer clear liquid 3~5 times, finally it is centrifuged with 2000-3000, takes its precipitation, 24h is vacuum dried at 90 DEG C, after grinding Sieve by mesh~400 mesh sieve of particle diameter 200, collect attapulgite stand-by.

Electric Pulse Treatment condition is as follows:High-voltage pulse is processed 5 minutes;High-pressure pulse electric (PEF) processing parameter is preferably For:Electric-field intensity 20KV/cm, the μ S of burst length 400, pulse frequency 300Hz.

The preparation method of polyglutamic acid zymotic fluid may also be employed following method:

Using bacillus licheniformis (Bacillus licheniformis).

The fermentation process is:30L fermentation tanks liquid amount is 15L, using above-mentioned fermentation medium, the inoculum concentration of seed liquor For 1.0%~15.0%, 30~40 DEG C of fermentation temperature, fermentation time 24~72 hours, 0.5~2.0vvm of ventilation, dissolved oxygen 1~ 50%, 200~400rpm of rotating speed.

Fermentation medium is consisted of (g/L):Glucose 80, sodium glutamate 80, ammonium nitrate 18, NaCl 10, MgSO4·6H2O 0.5, CaCl2·6H2O 1.0, FeSO4·6H2O 0.01, arginine 0.44, histidine 0.26. threonines 0.5, methionine 0.4, choline 0.1, glutamine 0.5, pyridoxol 0.001.

Using effect is tested:

Test 1

5L is added to this adsorbent 20g contain Pb:150mg/L and Zn:260mg/L,Ni2+:In 90mg/L waste water, 45 points The ion concentration of Zhong Houyong inductance coupled plasma optical emission spectrographic determination heavy metal in waste water is Pb:13.3mg/L and Zn: 12.6mg/L.Ni2+:6.5mg/L

Test 2

50L is added to this adsorbent 50g contain Ni2+:850mg/L and Cu2+:100mg/L it is useless in, use after 30 minutes It is Ni that inductively coupled plasma emission spectrography determines the ion concentration of heavy metal in waste water2+:5.8mg/L and Cu2+: 3.3mg/L。

Test 3

150L is added to this adsorbent 100g contain composite waste that 125mg/L is containing peacock green and crystal violet concentration In, vibration absorption 30 minutes measures percent of decolourization for 95% and 97%.

Test 4

It is added in the wastewater containing phenol that 100L contains 60mg/L with this adsorbent 60g, AAS is used after 0.6h It is 1.5mg/L to determine phenol in wastewater concentration.

Claims (9)

1. a kind of biological cleaning support preparation method of wastewater treatment, as follows:
The attapulgite of pretreatment mixes with MBAA in salt solution, and at 60 DEG C 2h is stirred;By biological macromolecular solution with it is above-mentioned Mixed solution mixes, and above-mentioned solution is heated into 50 DEG C, adds the activated sludge and 2% Nanoscale Iron of attapulgite quality 4% Manganese composite oxide, adds the CNT stir process of attapulgite quality 4% 2 hours, and mixing speed is 8 turns/min.So Backward above-mentioned mixed liquor adds cyclodextrin composite solution, stirs 30 minutes at 25 DEG C, after placing 30 minutes at 10 DEG C, adjusts temperature Keep carrying out within 50 minutes being slowly stirred solidification crosslinking for -7 DEG C, water is removed into extrusion after said mixture gauze wrapped.With 15% Tannic acid solution is rinsed 3 times;Said mixture placed 60 DEG C of ovens after 10 hours.
2. the biological cleaning support preparation method of wastewater treatment according to claim 1, the attapulgite of the pretreatment It is with the ratio of MBAA:10:6.
3. the biological cleaning support preparation method of wastewater treatment according to claim 1, the salt solution is KCL and poly- Ethene mixed alkoxide solution, KCL mass concentrations are 4%, and polyvinyl alcohol mass concentration is 5%.
4. the biological cleaning support preparation method of wastewater treatment according to claim 1, the preparation side of the CNT Method is:Add the CNT of methanol aqueous solution weight 25%, immersion treatment 30- in the methanol aqueous solution that volume ratio is 15% 50 minutes, deposit was collected in subsequently centrifugation.
5. the biological cleaning support preparation method of wastewater treatment according to claim 1, the boiomacromolecule is molten The addition of liquid is 6 times of attapulgite quality.
6. the biological cleaning support preparation method of wastewater treatment according to claim 1, the biological macromolecular solution Preparation method is as follows:The polyglutamic acid zymotic fluid that fermented and cultured is obtained is with Ganoderma Lucidum fermented and cultured liquid according to 1:7 mixing, with It is concentrated to the 30% of mixed volume using concentrator afterwards.
7. the biological cleaning support preparation method of wastewater treatment according to claim 1, the concentration of the activated sludge is 4000mg/L。
8. the biological cleaning support preparation method of wastewater treatment according to claim 1, in the cyclodextrin composite solution Boric acid containing 14% cyclodextrin and 42%.
9. the biological cleaning support preparation method of wastewater treatment according to claim 1, the pretreatment of the attapulgite: The attapulgite of mesh~1000 mesh of particle diameter 300, adds the methanol solution that volumetric concentration is 25%, control temperature to exist attapulgite 45-50 DEG C of Electric Pulse Treatment;Subsequently precipitation takes supernatant liquor after 1 hour, after adding a small amount of distilled water to be well mixed in supernatant liquor Continue 500rpm centrifugation 1min, then take its supernatant liquor, after such cyclic washing supernatant liquor 3~5 times, finally entered with 2200 Row centrifugation, takes its precipitation, and 24h is vacuum dried at 90 DEG C, sieves by mesh~300 mesh sieve of particle diameter 200 after grinding, collects recessed Convex rod soil is stand-by:Electric Pulse Treatment condition is as follows:High-voltage pulse is processed 6 minutes;High-pressure pulse electric (PEF) processing parameter is preferable Ground is:Electric-field intensity 30KV/cm, the μ S of burst length 500, pulse frequency 200Hz.
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