CN108079973A - A kind of preparation method of biological cleaning carrier for wastewater treatment - Google Patents

A kind of preparation method of biological cleaning carrier for wastewater treatment Download PDF

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CN108079973A
CN108079973A CN201711350915.5A CN201711350915A CN108079973A CN 108079973 A CN108079973 A CN 108079973A CN 201711350915 A CN201711350915 A CN 201711350915A CN 108079973 A CN108079973 A CN 108079973A
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attapulgite
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邵素英
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4868—Cells, spores, bacteria
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

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Abstract

The preparation method that the present invention provides a kind of biological cleaning carrier for wastewater treatment is as follows：The attapulgite of pretreatment is mixed with MBAA in brine, and 1 3h is stirred at 50 70 DEG C；Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 40 60 DEG C, add in the activated sludge and 1 3% nanometer ferro manganese composite oxides of attapulgite quality 2 5%, when the carbon nanotubes stir process 13 of addition attapulgite quality 2 5% is small, mixing speed is 5 10 turns/min.Mixed liquor is stated then up adds in cyclodextrin composite solution, it is stirred 20 40 minutes at 20 30 DEG C, after 10 DEG C are placed 30 minutes, adjustment temperature keeps carrying out within 40 60 minutes being slowly stirred curing crosslinking for 57 DEG C, water is removed into extrusion after said mixture gauze wrapped, is rinsed 23 times with 10 20% tannic acid solutions；Said mixture place 50 70 DEG C of ovens 8 10 it is small when after, the present invention can effectively improve the efficiency and ability of sewage disposal.

Description

A kind of preparation method of biological cleaning carrier for wastewater treatment
The application is the divisional application of following application：The applying date be on July 31st, 2015, Application No. CN201510463278.7, a kind of preparation method of entitled biological cleaning carrier for wastewater treatment.
Technical field
The invention belongs to field of waste water treatment.
Background technology
As modern industry and the rapid development of urbanization, water pollution are on the rise.Wastewater treatment method mainly has chemistry The precipitation method, electrolysis, ion-exchange, membrane processing method etc., but these methods in processing there are complex process, it is cumbersome, The defects of operating cost is high, generation secondary pollution.Develop and using new efficient, less toxic, inexpensive water technology be 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 to have chain layer structure The clay mineral of magnesium silicate containing Shuifu County, typical chemical formula Si8Mg6O20(OH)2(OH2)4·4H2O, structure belong to 2:1 type clay pit Object, each 2:In 1 unit structure layer, tetrahedron chip angle top overturns in direction at a certain distance, forming layer chain.In tetrahedron Interband forms the passage parallel with chain, filling zeolite water and the crystallization water in passage.Attapulgite fibre structure generally comprises three A level：1. basic structural unit is micro- rodlike or fibrous monocrystal, abbreviation stick is brilliant.2. the list formed by monocrystalline aggregate parallel Brilliant beam.3. the aggregation formed is mutually accumulated by brilliant beam (brilliant including stick).The special construction of attapulgite makes it have very big Specific surface area, physical absorption are very capable.On the other hand, attapulgite carries level negative electrical charge, and having in Inter layer adsorption can The cation of exchangeability is so that charge balance, such attapulgite are just provided with stronger ionic adsorption exchange capacity.
Attapulgite has good suspension in water, therefore although attapulgite has good adsorption capacity, for For water treatment field, powdered attapulgite can not be direct plungeed into water using, it is necessary to take at certain method Reason.At present, preferable processing method is to use certain immobilized attapulgite of carrier, then puts into water and use.There is inventor to exist A kind of preparation method of absorbent-type macromolecule composite hydrogel 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 the bumps Stick soil composite hydrogel absorption heavy metal ion efficiency is low, adsorbance is small, cleaned after gel adsorption heavy metal ion it is difficult, and Gel does not have sensibility to the pH value of solution, can not be by the absorption that controls the pH value of solution to control to heavy metal ion Amount.
A kind of method of mass production gamma-polyglutamic acid, 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 mass production high concentration.The skill of the present invention Art plan explanation is as follows:1. the activation of strain；2. the preparation of seed liquor；3. ferment tank；It is characterized in that by fermenting The fed-batch medium being made of glucose, ammonium nitrate, CaCl26H2O and FeCl36H2O is added in the process, makes fermentation production rate Reach 1.18g/lh, so as to achieve the purpose that efficiently to prepare 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 relate 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 are 10~20nm.The patent No.：CN201210237752.0.
A kind of devices of magnetic attapulgite wastewater treatment of the such as Chen great Jun, Dong Aijuan, Jiang Zequan：China, A kind of device of magnetic attapulgite wastewater treatment of 201120143921.5 [P] .2011-12-14. this patent offers, is realized Dynamic Adsorption of the magnetic attapulgite in water process, and used with pulverulence, eliminate the trouble of granulation.And it overcomes Attapulgite difficult separated problem in water phase can be such that magnetic attapulgite is isolated from water phase without adding in heavy agent of wadding a quilt with cotton Come, eliminate when heavy agent is wadded a quilt with cotton because adding in it is possible that the secondary pollution brought.It is i.e. controllable magnetic concave-convex that wastewater flow is adjusted simultaneously Stick soil and the action time of waste water, reach optimal adsorption effect, can also be changed magnetic recessed according to the concentration of useless impurities in water The addition of convex stick soil, to realize that the utilization ratio of magnetic attapulgite is optimal.
Li Yan China 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 Acrylamide is added, adds the flocculation reaction to water pollutant；By adding ammonium molybdate, ammonium chloride, cetyl front three Base ammonium bromide, adds adsorptivity.The attapulgite activation degree is high, it is modified uniformly, have excellent performance, suitable for waste water control, Excellent adsorption does not generate secondary pollution.It can also be used to the filler of coating, rubber simultaneously, not only suspension is good, and thixotropy is good, But also with rustless property.
The method of heavy metal in surfactant-modified attapulgite removal landfill leachate：The patent No. 201410744321.2 this patent disclose heavy metals in a kind of surfactant-modified attapulgite removal landfill leachate Method, heavy metal in landfill leachate is purified using the attapulgite after surfactant-modified.This method energy Effectively the heavy metal in landfill leachate is adsorbed, landfill leachate removal efficiency of heavy metals ratio is used only original recessed The efficiency of convex stick soil improves 30%, and better than traditional adsorption method.
A kind of threonine modified attapulgite earth adsorbing and its using .201410453968.X, this patent disclose one The preparation method of kind threonine modified attapulgite earth adsorbing has unique point using common chemical agent threonine to selecting Dissipate, the attapulgite of the good colloidal nature such as high temperature resistant, salt resistance alkali and higher adsorption bleaching ability is modified, obtain pair 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, the saturated extent of adsorption to copper and chromium heavy metal wastewater thereby are 143mg/g and 81mg/g.
Application study [J] the Informations of bodied ferric sulfate composite flocculation agent in the treatment of waste water, 2012 (6)：77-79. This document proposes a kind of preparation process of attapulgite-bodied ferric sulfate composite flocculation agent, the results show bodied ferric sulfate There are good flocculation and treatment effect to waste water with the attapulgite modified composite flocculation agent prepared for raw material.By to it CODcr removal rates and turbidity removal rate in sanitary wastewater are compared, and obtain the optimal preparation process item 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 for attapulgite clay/carbon composite that Xu Ling relaxes and its water pollution processing are published in using Primary Study Yangzhou University, 2013. this document are prepared concave convex rod as raw material using attapulgite clay and sucrose and are glued by hydrothermal synthesis reaction Soil/carbon composite, can efficient absorption and go in water removal dissolubility micro quantity organic pollutant and toxic heavy metal from Son.The results show carbon is coated on concave convex rod plane of crystal in the form of amorphous carbon, hydrophilic organofunctional occurs 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 and the ratio of carbon source quality have a significant impact to the absorption property of attapulgite clay/carbon composite.
The synthesis of Chen Hui, Qiang Yinghuai, Yin Hui attapulgites/polyacrylamide hybrid flocculant and its flocculating properties research [J] nonmetallic ores, 2011,34 (2):36-39. this document uses the method that ultrasonic wave disperses, N- methacryls-N '- Pyrimidine piperazine (MPMP) and potassium peroxydisulfate (K2S2O8) composition redox system under, trigger acrylamide monomer (AM) in acid Graft polymerization reaction occurs for attapulgite modified (ATP) surface, generates 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 additive amount, the efficiency and ability of sewage disposal can be effectively improved.
The content of the invention
The object of the present invention is to provide a kind of biological cleaning carriers for wastewater treatment, can prepare by the following method：
The attapulgite of pretreatment is mixed with MBAA in brine, and 1-3h is stirred at 50-70 DEG C；Boiomacromolecule is molten Liquid is mixed with above-mentioned mixed solution, and above-mentioned solution is heated to 40-60 DEG C, adds in the activated sludge of attapulgite quality 2-5% With the nanometer ferro manganese composite oxides of 1-3%, the carbon nanotubes stir process 1-3h of attapulgite quality 2-5% is added in, is stirred Speed is 5-10r/min.Mixed liquor is stated then up and adds in cyclodextrin composite solution, is stirred 20-40 minutes at 20-30 DEG C, After 10 DEG C are placed 30 minutes, adjustment temperature keeps carrying out within 40-60 minutes being slowly stirred curing crosslinking for -5-7 DEG C, by above-mentioned mixing Water is removed in extrusion after object gauze wrapped.It is rinsed 2-3 times with 10-20% tannic acid solutions；Said mixture places 50-70 DEG C of baking oven After handling 8-10h.
Preferably in the oven stage：Mixture is warming up to 85 DEG C of holding 2- after placing 50-70 DEG C of oven 8-10h Cool within 5 minutes 50-70 DEG C of holding 1h.
The attapulgite of pretreatment and the ratio of MBAA are 10:4-8.
The brine 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 carbon nanotubes is：Methanol aqueous solution weight is added in the methanol aqueous solution for being 10-25% in volume ratio The carbon nanotubes of 20-30% is measured, immersion treatment 30-50 minutes then centrifuges, and collects sediment.
The additive amount of the biological macromolecular solution is 2-8 times of attapulgite quality.
The preparation method of biological macromolecular solution is as follows：
By the polyglutamic acid zymotic fluid that fermented and cultured obtains with Ganoderma Lucidum fermented and cultured liquid according to 1:6-8 is mixed, then 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；
Contain the cyclodextrin that weight ratio is 8-15% and the boric acid of 35-45% in cyclodextrin composite solution.
The pretreatment of attapulgite.Attapulgite addition volumetric concentration is by the attapulgite of the mesh of 300 mesh of grain size~1000 The methanol solution of 15-35%, control temperature is in 45-50 DEG C of Electric Pulse Treatment；Supernatant liquor then is taken after precipitation 1-2h, upper strata is clear In liquid plus a small amount of distilled water continues 500rpm centrifugation 1min after mixing, its supernatant liquor is then taken, so repeatedly in washing After layer clear liquid 3~5 times, finally it is centrifuged with 2000-3000, takes its precipitation, be dried in vacuo at 90 DEG C for 24 hours, after grinding By the sieving of the mesh sieve of 200 mesh of grain size~400, it is for use to collect attapulgite.
Electric Pulse Treatment condition is as follows：High-voltage pulse is handled 5-10 minutes；High-pressure pulse electric (PEF) processing parameter is preferable Ground is：Electric field strength 20-40KV/cm, burst length 400-600 μ s, pulse frequency 200-300Hz.
Advantageous effect：
Compared with prior art, the present invention its remarkable advantage is：(1) adsorbent energy efficient absorption obtained by the method for the present invention 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 water body secondary pollution, 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 are easy to grasp.
Embodiment 1
The object of the present invention is to provide a kind of biological cleaning carriers for wastewater treatment.Technical solution is as follows:
The preparation method of the biological cleaning carrier for wastewater treatment is as follows：
The attapulgite of pretreatment is mixed with MBAA in brine, and 2h is stirred at 60 DEG C；By biological macromolecular solution with Above-mentioned mixed solution mixing, 50 DEG C are heated to by above-mentioned solution, add in the activated sludge of attapulgite quality 4% and 2% receive Rice ferro manganese composite oxides add in carbon nanotubes the stir process 2h, mixing speed 8r/min of attapulgite quality 4%.So Backward above-mentioned mixed liquor adds in cyclodextrin composite solution, is stirred 30 minutes at 25 DEG C, after 10 DEG C are placed 30 minutes, adjusts temperature It keeps carrying out within 50 minutes being slowly stirred curing crosslinking for -7 DEG C, water is removed into extrusion after said mixture gauze wrapped.With 15% Tannic acid solution rinses 3 times；After said mixture places 60 DEG C of oven 10h.
The attapulgite of pretreatment and the ratio of MBAA are：10:6.
The brine is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 4%, and polyvinyl alcohol mass concentration is 5%.
The preparation method of carbon nanotubes is：Methanol aqueous solution weight is added in the methanol aqueous solution for being 15% in volume ratio 25% carbon nanotubes, immersion treatment 30-50 minutes then centrifuge, and collect deposit.
The additive amount of the biological macromolecular solution is 6 times of attapulgite quality.
The preparation method of biological macromolecular solution is as follows：
By the polyglutamic acid zymotic fluid that fermented and cultured obtains with Ganoderma Lucidum fermented and cultured liquid according to 1:7 mixing, are then adopted 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.Attapulgite addition volumetric concentration is by the attapulgite of the mesh of 300 mesh of grain size~1000 25% methanol solution, control temperature is in 45-50 DEG C of Electric Pulse Treatment；Then supernatant liquor is taken after precipitation 1h, in supernatant liquor A small amount of distilled water is added to continue 500rpm centrifugation 1min after mixing, then takes its supernatant liquor, it is clear so to wash upper strata repeatedly It after liquid 3~5 times, is finally centrifuged with 2200, takes its precipitation, be dried in vacuo at 90 DEG C for 24 hours, grain size 200 is pressed after grinding The sieving of the mesh sieve of mesh~300, it is for use to collect attapulgite.
Electric Pulse Treatment condition is as follows：High-voltage pulse is handled 6 minutes；High-pressure pulse electric (PEF) processing parameter is preferably For：Electric field strength 30KV/cm, 500 μ s of burst length, pulse frequency 200Hz.
Embodiment 2
The object of the present invention is to provide a kind of biological cleaning carriers for wastewater treatment.Technical solution is as follows:
The preparation method of the biological cleaning carrier for wastewater treatment is as follows：
The attapulgite of pretreatment is mixed with MBAA in brine, and 3h is stirred at 50 DEG C；By biological macromolecular solution with Above-mentioned mixed solution mixing, 40 DEG C are heated to by above-mentioned solution, add in the activated sludge of attapulgite quality 5% and 1% receive Rice ferro manganese composite oxides add in carbon nanotubes the stir process 1h, mixing speed 5r/min of attapulgite quality 5%.So Backward above-mentioned mixed liquor adds in cyclodextrin composite solution, is stirred 40 minutes at 20 DEG C, after 10 DEG C are placed 30 minutes, adjusts temperature It keeps carrying out within 60 minutes being slowly stirred curing crosslinking for -5 DEG C, water is removed into extrusion after said mixture gauze wrapped.With 10% Tannic acid solution rinses 2 times；After said mixture places 55 DEG C of oven 10h.
The attapulgite of pretreatment and the ratio of MBAA are：10:4.
The brine is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 2%, and polyvinyl alcohol mass concentration is 3%.
The preparation method of carbon nanotubes is：Methanol aqueous solution weight is added in the methanol aqueous solution for being 10% in volume ratio 30% carbon nanotubes, immersion treatment 30 minutes then centrifuge, and collect deposit.
The additive amount of the biological macromolecular solution is 8 times of attapulgite quality.
The preparation method of biological macromolecular solution is as follows：
By the polyglutamic acid zymotic fluid that fermented and cultured obtains with Ganoderma Lucidum fermented and cultured liquid according to 1:8 mixing, are then adopted 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.Attapulgite addition volumetric concentration is by the attapulgite of the mesh of 300 mesh of grain size~1000 35% methanol solution, control temperature is in 45-50 DEG C of Electric Pulse Treatment；Then supernatant liquor is taken after precipitation 1h, in supernatant liquor A small amount of distilled water is added to continue 500rpm centrifugation 1min after mixing, then takes its supernatant liquor, it is clear so to wash upper strata repeatedly It after liquid 3~5 times, is finally centrifuged with 2000, takes its precipitation, be dried in vacuo at 90 DEG C for 24 hours, grain size 200 is pressed after grinding The sieving of the mesh sieve of mesh~400, it is for use to collect attapulgite.
Electric Pulse Treatment condition is as follows：High-voltage pulse is handled 10 minutes；High-pressure pulse electric (PEF) processing parameter is preferably For：Electric field strength 40KV/cm, 400 μ s of burst length, pulse frequency 300Hz.
Embodiment 3
The object of the present invention is to provide a kind of biological cleaning carriers for wastewater treatment.Technical solution is as follows:
The preparation method of the biological cleaning carrier for wastewater treatment is as follows：
The attapulgite of pretreatment is mixed with MBAA in brine, and 1h is stirred at 50 DEG C；By biological macromolecular solution with Above-mentioned mixed solution mixing, 40 DEG C are heated to by above-mentioned solution, add in the activated sludge of attapulgite quality 2% and 1% receive Rice ferro manganese composite oxides add in carbon nanotubes the stir process 1h, mixing speed 5r/min of attapulgite quality 2-5%. Mixed liquor is stated then up and adds in cyclodextrin composite solution, is stirred 20 minutes at 20 DEG C, after 10 DEG C are placed 30 minutes, adjustment temperature It spends and keeps carrying out within 60 minutes being slowly stirred curing crosslinking for -7 DEG C, water is removed into extrusion after said mixture gauze wrapped.With 10% tannic acid solution rinses 2 times；85 DEG C are warming up to after 70 DEG C of oven 8h of mixture placement to keep cooling to 70 DEG C in 5 minutes Keep 1h.
The attapulgite of pretreatment and the ratio of MBAA are：10:4.
The brine is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 2%, and polyvinyl alcohol mass concentration is 3%.
The preparation method of carbon nanotubes is：Methanol aqueous solution weight is added in the methanol aqueous solution for being 10% in volume ratio 20% carbon nanotubes, immersion treatment 50 minutes then centrifuge, and collect deposit.
The additive amount of the biological macromolecular solution is 4 times of attapulgite quality.
The preparation method of biological macromolecular solution is as follows：
By the polyglutamic acid zymotic fluid that fermented and cultured obtains with Ganoderma Lucidum fermented and cultured liquid according to 1:7 mixing, are then adopted 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.Attapulgite addition volumetric concentration is by the attapulgite of the mesh of 300 mesh of grain size~500 25% methanol solution, control temperature is in 45-50 DEG C of Electric Pulse Treatment；Then supernatant liquor, supernatant liquor are taken after precipitation 1-2h In plus a small amount of distilled water continue after mixing 500rpm centrifugation 1min, then take its supernatant liquor, so wash upper strata repeatedly It after clear liquid 3~5 times, is finally centrifuged with 2000-3000, takes its precipitation, be dried in vacuo at 90 DEG C for 24 hours, pressed after grinding The sieving of the mesh sieve of 200 mesh of grain size~400, it is for use to collect attapulgite.
Electric Pulse Treatment condition is as follows：High-voltage pulse is handled 5 minutes；High-pressure pulse electric (PEF) processing parameter is preferably For：Electric field strength 20KV/cm, 400 μ s of burst length, pulse frequency 300Hz.
Following method can also be used in the preparation method of polyglutamic acid zymotic fluid：
Using bacillus licheniformis (Bacillus licheniformis).
The fermentation process is：30L fermentation tanks liquid amount is 15L, uses above-mentioned fermentation medium, the inoculum concentration of seed liquor For 1.0%~15.0%, 30~40 DEG C of fermentation temperature, when fermentation time 24~72 is small, 0.5~2.0vvm of ventilation quantity, dissolved oxygen 1~ 50%, 200~400rpm of rotating speed.
Fermentation medium composition is (g/L)：Glucose 80, sodium glutamate 80, ammonium nitrate 18, NaCl 10, MgSO4· 6H2O0.5, 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：
Experiment 1
5L, which is added to, with this adsorbent 20g contains 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
Experiment 2
50L, which is added to, with this adsorbent 50g contains Ni2+:850mg/L and Cu2+:100mg/L it is useless in, used after 30 minutes The ion concentration that inductively coupled plasma emission spectrography measures heavy metal in waste water is Ni2+:5.8mg/L and Cu2+: 3.3mg/L。
Experiment 3
Be added to 150L with this adsorbent 100g and contain containing peacock green and crystal violet concentration be 125mg/L composite waste In, vibration absorption 30 minutes measures percent of decolourization as 95% and 97%.
Experiment 4
It is added to this adsorbent 60g in the wastewater containing phenol that 100L contains 60mg/L, 0.6h uses spectrophotometry after It is 1.5mg/L to measure phenol in wastewater concentration.

Claims (3)

1. the preparation method of a kind of biological cleaning carrier for wastewater treatment, which is characterized in that as follows：
The attapulgite of pretreatment is mixed with MBAA in brine, and 2h is stirred at 60 DEG C；By biological macromolecular solution with it is above-mentioned Mixed solution mixes, and above-mentioned solution is heated to 50 DEG C, adds in the activated sludge and 2% Nanoscale Iron of attapulgite quality 4% Manganese composite oxide adds in carbon nanotubes the stir process 2h, mixing speed 8r/min of attapulgite quality 4%；Then to Above-mentioned mixed liquor adds in cyclodextrin composite solution, is stirred 30 minutes at 25 DEG C, and after 10 DEG C are placed 30 minutes, adjustment temperature is -7 It DEG C keeps carrying out within 50 minutes being slowly stirred curing crosslinking, water is removed into extrusion after said mixture gauze wrapped；With 15% tannin Acid solution rinses 3 times；After said mixture places 60 DEG C of oven 10h；
The attapulgite of pretreatment and the ratio of MBAA are：10:6；
The brine is KCL and polyvinyl alcohol solution, and KCL mass concentrations are 4%, and polyvinyl alcohol mass concentration is 5%；
The preparation method of biological macromolecular solution is as follows：
By the polyglutamic acid zymotic fluid that fermented and cultured obtains with Ganoderma Lucidum fermented and cultured liquid according to 1:7 mixing, then using dense Contracting equipment is concentrated to the 30% of mixed volume；
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 the mesh of 300 mesh of grain size~1000, it is 25% that attapulgite is added in volumetric concentration Methanol solution, control temperature in 45-50 DEG C of Electric Pulse Treatment；Supernatant liquor is then taken after precipitation 1h, is added in supernatant liquor few Amount distilled water continue after mixing 500rpm centrifugation 1min, then take its supernatant liquor, so repeatedly wash supernatant liquor 3~ After 5 times, be finally centrifuged with 2200, take its precipitation, be dried in vacuo at 90 DEG C for 24 hours, after grinding by 200 mesh of grain size~ 300 mesh sieve are sieved, and it is for use to collect attapulgite；
Electric Pulse Treatment condition is as follows：High-voltage pulse is handled 6 minutes；High-pressure pulse electric (PEF) processing parameter is preferably：Electricity Field intensity 30KV/cm, 500 μ s of burst length, pulse frequency 200Hz.
2. the preparation method of the biological cleaning carrier according to claim 1 for wastewater treatment, which is characterized in that carbon is received The preparation method of mitron is：The carbon of methanol aqueous solution weight 20-30% is added in the methanol aqueous solution for being 10-25% in volume ratio Nanotube, immersion treatment 30-50 minutes then centrifuge, and collect sediment.
3. the preparation method of the biological cleaning carrier according to claim 1 or 2 for wastewater treatment, which is characterized in that The additive amount of the biological macromolecular solution is 2-8 times of attapulgite quality.
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