CN105056908A - Biological purifying carrier for wastewater treatment, and preparation method thereof - Google Patents

Biological purifying carrier for wastewater treatment, and preparation method thereof Download PDF

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Publication number
CN105056908A
CN105056908A CN201510463278.7A CN201510463278A CN105056908A CN 105056908 A CN105056908 A CN 105056908A CN 201510463278 A CN201510463278 A CN 201510463278A CN 105056908 A CN105056908 A CN 105056908A
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attapulgite
solution
preparation
wastewater treatment
biological
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CN105056908B (en
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邵素英
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Wanzide Car Washing Equipment Shanghai Co ltd
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Priority to CN201711353047.6A priority Critical patent/CN108014759A/en
Priority to CN201711350915.5A priority patent/CN108079973A/en
Priority to CN201710793598.8A priority patent/CN107335414B/en
Priority to CN201510463278.7A priority patent/CN105056908B/en
Priority to CN201711354451.5A priority patent/CN107876028A/en
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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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
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    • 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
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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 invention provides a biological purifying carrier for wastewater treatment. A preparation method of the carrier comprises the following steps: mixing pretreated attapulgite with MBAA in brine, and stirring at 50-70DEG C for 1-3h; mixing a biopolymer solution with the above obtained mixed solution, heating the obtained solution to 40-60DEG C, adding activated sludge accounting for 2-5% of the mass of attapulgite and a nanometer iron-manganese composite oxide accounting for 1-3% of the mass of attapulgite, adding carbon nanotubes accounting for 2-5% of the mass of attapulgite, and stirring at a stirring speed of 5-10r/min for 1-3h; adding a cyclodextrin composite solution to the above obtained mixed solution, stirring at 20-30DEG C for 20-40min, standing at 10DEG C for 30min, adjusting the temperature to -5-7DEG C, maintaining for 40-60min, carrying out slow stirring for curing cross-linking, wrapping the above obtained mixture by using gauze, extruding to remove water, and flushing by using a 10-20% tannic acid solution 2-3 times; and processing the obtained mixture in a 50-70DEG C oven for 8-10h to obtain the carrier. The carrier can effectively improve the sewage treatment efficiency and the sewage treatment ability.

Description

A kind of biological cleaning carrier for wastewater treatment and preparation thereof
Technical field
The invention belongs to field of waste water treatment.
Background technology
Along with the develop rapidly of modern industry and urbanization, water pollutions is on the rise.Method of wastewater treatment mainly contains chemical precipitation method, electrolysis, ion-exchange, membrane processing method etc., but these methods exist complex process, complex operation when processing, and operating cost is high, produces the defects such as secondary pollution.Novel efficient, low toxicity, the inexpensive water technology of development and application is one of key solving water pollution problems.
Attapulgite (also known as palygorskite) is a kind of natural non-metallic mineral material, be a kind of have chain layer structure containing Shuifu County's magnesium silicate clay mineral, typical chemical formula is Si 8mg 6o 20(OH) 2(OH 2) 44H 2o, structure belongs to 2:1 type clay mineral, and in each 2:1 unit structure layer, tetrahedron wafer angle is pushed up direction at a certain distance and put upside down, and forms layer chain.The passage parallel with chain is formed, filling zeolite water and the crystallization water in passage at tetrahedron bar interband.Attapulgite fibre structure generally comprises three levels: 1. basic structural unit is micro-bar-shaped or fibrous monocrystal, is called for short rod brilliant.2. by the monocrystalline bundle of monocrystalline aggregate parallel.3. the aggregation mutually piled up by crystalline substance bundle (comprising rod brilliant).The special construction of attapulgite makes it have very large specific area, and physical absorption is very capable.On the other hand, attapulgite is with aspect negative electrical charge, and have the cation of interchangeability to make charge balance at Inter layer adsorption, such attapulgite is just provided with stronger ionic adsorption exchange capacity.
Attapulgite has good suspension in water, although therefore attapulgite has good adsorption capacity, for water treatment field, pulverous attapulgite directly cannot drop in water and use, and needs to take certain method to process.At present, good processing method adopts certain immobilized attapulgite of carrier, then drop in water and use.Have inventor disclose in invention preparation method of a kind of absorbent-type macromolecule composite aquogel and products thereof [ 201020595998.1], utilize macromolecule hydrogel to make carrier, immobilized attapulgite, thus the suction-operated playing attapulgite well.But, the efficiency of this attapulgite composite hydrogel Adsorption of Heavy Metal Ions is low, adsorbance is little, cleaning difficulty after gel adsorption heavy metal ion, and the pH value of gel to solution does not have sensitiveness, cannot be controlled the adsorbance of heavy metal ion by the pH value controlling solution.
A method for a large amount of production gamma-polyglutamic acid-, application number: 201110216717.6.A kind of production method of gamma-polyglutamic acid-of disclosure of the invention, particularly relates to a kind of method of gamma-polyglutamic acid-of a large amount of production high concentration.Technical scheme of the present invention is summarized as follows: 1. the activation of bacterial classification; 2. the preparation of seed liquor; 3. ferment tank; It is characterized in that, by adding the fed-batch medium be made up of glucose, ammonium nitrate, CaCl26H2O and FeCl36H2O during the fermentation, making fermentation production rate reach 1.18g/lh, thus reach the object of the large weight gamma-polyglutamic acid of efficient preparation.
Name is called the patent of invention of a kind of arsenic removal material of Nanoscale Iron manganese composite oxide and preparation method thereof, this invention relates to a kind of arsenic removal material of Nanoscale Iron manganese composite oxide, it is Nanoscale Iron manganese composite oxide, the atomic ratio of institute's iron content, manganese and oxygen is 4:3:(8 ~ 10), wherein manganese is+4 valencys, iron is+3 valencys, and the BET specific surface area of described arsenic removal material is 225 ~ 282m2/g, and average grain diameter is 10 ~ 20nm.The patent No.: CN201210237752.0.
Chen great Jun, Dong Aijuan, Jiang Zequan etc. the device of a kind of magnetic attapulgite wastewater treatment: China, this patent of 201120143921.5 [P] .2011-12-14. provides the device of a kind of magnetic attapulgite wastewater treatment, realize the Dynamic Adsorption of magnetic attapulgite in water treatment, and use with pulverulence, eliminate the trouble of granulation.And overcome attapulgite difficult difficult problem be separated in aqueous phase, the heavy agent of wadding need not being added magnetic attapulgite can be made to separate from aqueous phase, eliminating the secondary pollution likely brought because adding the heavy agent of wadding.Regulate wastewater flow can control the action time of magnetic attapulgite and waste water simultaneously, reach optimal adsorption effect, the addition of magnetic attapulgite can also be changed according to the concentration of useless impurities in water, optimum with the utilization ratio realizing magnetic attapulgite.
Li Yanhua. a kind of attapulgite modified and preparation method thereof for sewage disposal: China, a kind of attapulgite modified for sewage disposal of 201410383602.X [P] .2014-12-10. this patented invention, by adding acrylamide in attapulgite, add the flocculation reaction to water pollutant; By adding ammonium molybdate, ammonium chloride, softex kw, add adsorptivity.This attapulgite activation degree is high, and modification is even, excellent performance, is applicable to waste water control, excellent adsorption, does not produce secondary pollution.Can also be used for the filler of coating, rubber, not only suspension is good, and thixotropy is good, but also has rustless property simultaneously.
Surfactant-modified attapulgite removes the method for heavy metal in percolate: the patent No. 201410744321.2, this patent disclose a kind of method that surfactant-modified attapulgite removes heavy metal in percolate, utilize surfactant-modified after attapulgite the heavy metal in percolate is purified.The method can effectively be adsorbed the heavy metal in percolate, and its percolate removal efficiency of heavy metals uses the efficiency of original attapulgite to improve 30% than only, and is better than traditional adsorption method.
A kind of threonine modified attapulgite earth adsorbing and application .201410453968.X thereof, this patent disclose a kind of preparation method of threonine modified attapulgite earth adsorbing, utilizing conventional chemical agent threonine to carry out modification to selecting the attapulgite with specific dispersion, high temperature resistant, the anti-good colloidal nature such as saline and alkaline and higher adsorption bleaching ability, obtaining attapulgite modified absorption printing dye and heavy metal wastewater thereby being had to excellent adsorption capacity.The adsorbent of preparation has excellent adsorption capacity to dyeing waste water and heavy metal wastewater thereby, can, up to 650 and 1380mg/g, be wherein 143mg/g and 81mg/g to the saturated extent of adsorption of copper and chromium heavy metal wastewater thereby to methylene blue and acid fuchsin saturated extent of adsorption.
Bodied ferric sulfate composite flocculation agent application study in the treatment of waste water [J]. Information, 2012 (6): 77-79. these documents propose the preparation technology of a kind of attapulgite-bodied ferric sulfate composite flocculation agent, and result display bodied ferric sulfate and the attapulgite modified composite flocculation agent prepared for raw material have good flocculation and treatment effect to waste water.By comparing its CODcr clearance in sanitary wastewater and turbidity removal rate, obtain the optimum preparation process condition of composite flocculation agent: attapulgite heat treatment temperature is 400 DEG C, recombination reaction temperature 50 C, attapulgite dosage 2.0g/L, complex reaction time are 4h.
The preparation of the attapulgite clay/carbon composite of Xu Lingshu and water pollutions process application Primary Study thereof, be published in Yangzhou University, 2013. these documents pass through hydrothermal synthesis reaction, with attapulgite clay and sucrose for attapulgite clay/carbon composite prepared by raw material, can efficient adsorption and remove dissolubility micro quantity organic pollutant and toxic heavy metal ion in water.Result display carbon is coated on concave convex rod plane of crystal with the form of amorphous carbon, has occurred hydrophilic organofunctional group, its close organic performance is had significant improvement in material.In hydro-thermal reaction, the ratio of reaction time, temperature, pH and attapulgite clay and carbon source quality all has a significant impact the absorption property of attapulgite clay/carbon composite.
Chen Hui, Qiang Yinghuai, Yin Hui. the synthesis of attapulgite/polyacrylamide hybrid flocculant and flocculating properties research [J] thereof. nonmetallic ore, 2011,34 (2): 36-39. these documents adopt the method for ultrasonic wave dispersion, at N-methacryl-N '-pyrimidine piperazine (MPMP) and potassium peroxydisulfate (K 2s 2o 8) under the redox system that forms, there is graft polymerization reaction on acid attapulgite modified (ATP) surface in acrylamide triggered monomer (AM), generates attapulgite grafted polyacrylamide hybrid flocculant (ATP/PAM).By finding the actual domestic wastewater process of 2.5wt% kaolin, 5wt% bloodstone simulation sewage and solid content 5.2%, the alumen ustum sinking speed that ATP/PAM flocculation is formed is fast, flocculation time is short, the sludge quantity produced is few, within the scope of very large addition, be better than common PAM, effectively can improve efficiency and the ability of sewage disposal.
Summary of the invention
The object of this invention is to provide a kind of biological cleaning carrier for wastewater treatment, can prepare by the following method:
Pretreated attapulgite mixes in salt solution with MBAA, at 50-70 DEG C, stir 1-3h; Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 40-60 DEG C, add the activated sludge of attapulgite quality 2-5% and the Nanoscale Iron manganese composite oxide of 1-3%, add the CNT stir process 1-3 hour of attapulgite quality 2-5%, mixing speed is that 5-10 turns/min.Then cyclodextrin composite solution is added to above-mentioned mixed liquor, 20-40 minute is stirred at 20-30 DEG C, after placing 30 minutes at 10 DEG C, adjustment temperature slowly stirs curing cross-linked for 40-60 minute for-5-7 DEG C of maintenance, extrusion after said mixture gauze parcel is anhydrated.2-3 time is rinsed with 10-20% tannic acid solution; Said mixture placed 50-70 DEG C after oven 8-10 hour.
Preferred in the oven stage: mixture is placed 50-70 DEG C and is warmed up to 85 DEG C after oven 8-10 hour and keeps within 2-5 minute, cooling to 50-70 DEG C and keep 1 hour.
The ratio of pretreated attapulgite and MBAA is 10:4-8.
Described salt solution is KCL and polyvinyl alcohol mixing solution, and KCL mass concentration is 2-5%, and polyvinyl alcohol mass concentration is 3-8%.
The preparation method of CNT is: be the CNT adding methanol aqueous solution weight 20-30% in the methanol aqueous solution of 10-25% in volume ratio, and immersion treatment 30-50 minute is centrifugal subsequently, collecting precipitation thing.
The addition of described biological macromolecular solution is 2-8 times of attapulgite quality.
The preparation method of biological macromolecular solution is as follows:
Mixed according to 1:6-8 with Ganoderma Lucidum fermented and cultured liquid by the polyglutamic acid zymotic fluid that fermented and cultured obtains, heating is subsequently concentrated to the 10-40% of mixed volume.
Described polyglutamic acid zymotic fluid and Ganoderma Lucidum fermentation culture are conventionally cultivated.
The concentration of activated sludge is 3000-5000mg/L;
Containing weight ratio in cyclodextrin composite solution is the cyclodextrin of 8-15% and the boric acid of 35-45%.
The pretreatment of attapulgite.Particle diameter 300 order ~ 1000 object attapulgite, adds the methanol solution that volumetric concentration is 15-35% by attapulgite, control temperature is at 45-50 DEG C of Electric Pulse Treatment; Supernatant liquor is got after postprecipitation 1-2 hour, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then its supernatant liquor is got, after cyclic washing supernatant liquor like this 3 ~ 5 times, finally carry out centrifugation with 2000-3000, get its precipitation, vacuum drying 24h at 90 DEG C, sieve by particle diameter 200 order ~ 400 mesh sieve after grinding, collect attapulgite stand-by.
Electric Pulse Treatment condition is as follows: high-voltage pulse process 5-10 minute; High-pressure pulse electric (PEF) processes parameter: 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 in the present invention: (1) the inventive method gained adsorbent energy efficient adsorption removes the pollutant in waste water, as heavy metal ion, dyestuff and petrochemical industry pollutant etc.(2) crosslinking adsorbent has strength and stability, can not cause secondary pollution to water body, and adsorbent elastic effect is good, and abrasion strength resistance is high; (3) abundant raw material source, production technology is simple, and raw material is easily processed, and technique is easy to grasp.
Embodiment 1
The object of this invention is to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:
The preparation method of the described biological cleaning carrier for wastewater treatment is as follows:
Pretreated attapulgite mixes in salt solution with MBAA, at 60 DEG C, stir 2h; Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 50 DEG C, add the activated sludge of attapulgite quality 4% and the Nanoscale Iron manganese composite oxide of 2%, add the CNT stir process 2 hours of attapulgite quality 4%, mixing speed is 8 turns/min.Then add cyclodextrin composite solution to above-mentioned mixed liquor, stir 30 minutes at 25 DEG C, after placing 30 minutes at 10 DEG C, adjustment temperature slowly stirs curing cross-linked for 50 minutes for-7 DEG C of maintenances, extrusion after said mixture gauze parcel is anhydrated.3 times are rinsed with 15% tannic acid solution; Said mixture placed 60 DEG C of oven after 10 hours.
The ratio of pretreated attapulgite and MBAA is: 10:6.
Described salt solution is KCL and polyvinyl alcohol mixing solution, and KCL mass concentration is 4%, and polyvinyl alcohol mass concentration is 5%.
The preparation method of CNT is: be the CNT adding methanol aqueous solution weight 25% in the methanol aqueous solution of 15% in volume ratio, and immersion treatment 30-50 minute is centrifugal subsequently, collecting precipitation material.
The addition of described 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 obtains is mixed according to 1:7 with Ganoderma Lucidum fermented and cultured liquid, adopts concentrator to be concentrated to 30% of mixed volume subsequently.
Described polyglutamic acid zymotic fluid and Ganoderma Lucidum fermentation culture are conventionally cultivated.
The concentration of activated sludge is 4000mg/L;
Containing the cyclodextrin of 14% and the boric acid of 42% in cyclodextrin composite solution.
The pretreatment of attapulgite.Particle diameter 300 order ~ 1000 object attapulgite, adds the methanol solution that volumetric concentration is 25% by attapulgite, control temperature is at 45-50 DEG C of Electric Pulse Treatment; Supernatant liquor is got after 1 hour with postprecipitation, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then its supernatant liquor is got, after cyclic washing supernatant liquor like this 3 ~ 5 times, finally carry out centrifugation with 2200, get its precipitation, vacuum drying 24h at 90 DEG C, sieve by particle diameter 200 order ~ 300 mesh sieve after grinding, collect attapulgite stand-by.
Electric Pulse Treatment condition is as follows: high-voltage pulse process 6 minutes; High-pressure pulse electric (PEF) processes parameter: electric-field intensity 30KV/cm, burst length 500 μ S, pulse frequency 200Hz.
Embodiment 2
The object of this invention is to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:
The preparation method of the described biological cleaning carrier for wastewater treatment is as follows:
Pretreated attapulgite mixes in salt solution with MBAA, at 50 DEG C, stir 3h; Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 40 DEG C, add the activated sludge of attapulgite quality 5% and the Nanoscale Iron manganese composite oxide of 1%, add the CNT stir process 1 hour of attapulgite quality 5%, mixing speed is 5 turns/min.Then add cyclodextrin composite solution to above-mentioned mixed liquor, stir 40 minutes at 20 DEG C, after placing 30 minutes at 10 DEG C, adjustment temperature slowly stirs curing cross-linked for 60 minutes for-5 DEG C of maintenances, extrusion after said mixture gauze parcel is anhydrated.2 times are rinsed with 10% tannic acid solution; Said mixture placed 55 DEG C of oven after 10 hours.
The ratio of pretreated attapulgite and MBAA is: 10:4.
Described salt solution is KCL and polyvinyl alcohol mixing solution, and KCL mass concentration is 2%, and polyvinyl alcohol mass concentration is 3%.
The preparation method of CNT is: be the CNT adding methanol aqueous solution weight 30% in the methanol aqueous solution of 10% in volume ratio, and immersion treatment 30 minutes is centrifugal subsequently, collecting precipitation material.
The addition of described 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 obtains is mixed according to 1:8 with Ganoderma Lucidum fermented and cultured liquid, adopts concentrator to be concentrated to 10% of mixed volume subsequently.
Described polyglutamic acid zymotic fluid and Ganoderma Lucidum fermentation culture are conventionally cultivated.
The concentration of activated sludge is 5000mg/L;
Containing the cyclodextrin of 15% and the boric acid of 45% in cyclodextrin composite solution.
The pretreatment of attapulgite.Particle diameter 300 order ~ 1000 object attapulgite, adds the methanol solution that volumetric concentration is 35% by attapulgite, control temperature is at 45-50 DEG C of Electric Pulse Treatment; Supernatant liquor is got after 1 hour with postprecipitation, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then its supernatant liquor is got, after cyclic washing supernatant liquor like this 3 ~ 5 times, finally carry out centrifugation with 2000, get its precipitation, vacuum drying 24h at 90 DEG C, sieve by particle diameter 200 order ~ 400 mesh sieve after grinding, collect attapulgite stand-by.
Electric Pulse Treatment condition is as follows: high-voltage pulse process 10 minutes; High-pressure pulse electric (PEF) processes parameter: electric-field intensity 40KV/cm, burst length 400 μ S, pulse frequency 300Hz.
Embodiment 3
The object of this invention is to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:
The preparation method of the described biological cleaning carrier for wastewater treatment is as follows:
Pretreated attapulgite mixes in salt solution with MBAA, at 50 DEG C, stir 1h; Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 40 DEG C, add the activated sludge of attapulgite quality 2% and the Nanoscale Iron manganese composite oxide of 1%, add the CNT stir process 1 hour of attapulgite quality 2-5%, mixing speed is 5 turns/min.Then add cyclodextrin composite solution to above-mentioned mixed liquor, stir 20 minutes at 20 DEG C, after placing 30 minutes at 10 DEG C, adjustment temperature slowly stirs curing cross-linked for 60 minutes for-7 DEG C of maintenances, extrusion after said mixture gauze parcel is anhydrated.2 times are rinsed with 10% tannic acid solution; Mixture place 70 DEG C of oven be warmed up to after 8 hours 85 DEG C keep within 5 minutes, cool to 70 DEG C keep 1 hour.
The ratio of pretreated attapulgite and MBAA is: 10:4.
Described salt solution is KCL and polyvinyl alcohol mixing solution, and KCL mass concentration is 2%, and polyvinyl alcohol mass concentration is 3%.
The preparation method of CNT is: be the CNT adding methanol aqueous solution weight 20% in the methanol aqueous solution of 10% in volume ratio, and immersion treatment 50 minutes is centrifugal subsequently, collecting precipitation material.
The addition of described 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 obtains is mixed according to 1:7 with Ganoderma Lucidum fermented and cultured liquid, adopts concentrator to be concentrated to 10% of mixed volume subsequently.
Described polyglutamic acid zymotic fluid and Ganoderma Lucidum fermentation culture are conventionally cultivated.
The concentration of activated sludge is 3000mg/L;
Containing the cyclodextrin of 8% and the boric acid of 35% in cyclodextrin composite solution.
The pretreatment of attapulgite.Particle diameter 300 order ~ 500 object attapulgite, adds the methanol solution that volumetric concentration is 25% by attapulgite, control temperature is at 45-50 DEG C of Electric Pulse Treatment; Supernatant liquor is got after postprecipitation 1-2 hour, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then its supernatant liquor is got, after cyclic washing supernatant liquor like this 3 ~ 5 times, finally carry out centrifugation with 2000-3000, get its precipitation, vacuum drying 24h at 90 DEG C, sieve by particle diameter 200 order ~ 400 mesh sieve after grinding, collect attapulgite stand-by.
Electric Pulse Treatment condition is as follows: high-voltage pulse process 5 minutes; High-pressure pulse electric (PEF) processes parameter: electric-field intensity 20KV/cm, burst length 400 μ S, pulse frequency 300Hz.
The preparation method of polyglutamic acid zymotic fluid also can adopt with the following method:
Adopt bacillus licheniformis (Bacilluslicheniformis).
Described fermentation process is: 30L fermentation tank liquid amount is 15L, uses above-mentioned fermentation medium, and the inoculum concentration of seed liquor is 1.0% ~ 15.0%, fermentation temperature 30 ~ 40 DEG C, fermentation time 24 ~ 72 hours, ventilation 0.5 ~ 2.0vvm, dissolved oxygen 1 ~ 50%, rotating speed 200 ~ 400rpm.
Fermentation medium consists of (g/L): glucose 80, sodium glutamate 80, ammonium nitrate 18, NaCl10, MgSO 46H 2o0.5, CaCl 26H 2o1.0, FeSO 46H 2o0.01, arginine 0.44, histidine 0.26. threonine 0.5, methionine 0.4, choline 0.1, glutamine 0.5, pyridoxol 0.001.
Result of use is tested:
Test 1
Join 5L with this adsorbent 20g and contain Pb:150mg/L and Zn:260mg/L, Ni 2+: in 90mg/L waste water, be Pb:13.3mg/L and Zn:12.6mg/L.Ni by the ion concentration of inductance coupled plasma optical emission spectrographic determination heavy metal in waste water after 45 minutes 2+: 6.5mg/L
Test 2
Join 50L with this adsorbent 50g and contain Ni 2+: 850mg/L and Cu 2+: 100mg/L useless in, be Ni by the ion concentration of inductance coupled plasma optical emission spectrographic determination heavy metal in waste water after 30 minutes 2+: 5.8mg/L and Cu 2+: 3.3mg/L.
Test 3
Join 150L with this adsorbent 100g to contain and be in the composite waste of 125mg/L containing peacock green and crystal violet concentration, vibration absorption 30 minutes, recording percent of decolourization is 95% and 97%.
Test 4
Joining 100L with this adsorbent 60g contains in the wastewater containing phenol of 60mg/L, and 0.6h is 1.5mg/L by rear spectrophotometry phenol in wastewater concentration.

Claims (10)

1. one kind as follows for the preparation method of the biological cleaning carrier of wastewater treatment: pretreated attapulgite mixes in salt solution with MBAA, at 50-70 DEG C, stir 1-3h; Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 40-60 DEG C, add the activated sludge of attapulgite quality 2-5% and the Nanoscale Iron manganese composite oxide of 1-3%, add the CNT stir process 1-3 hour of attapulgite quality 2-5%, mixing speed is that 5-10 turns/min.Then cyclodextrin composite solution is added to above-mentioned mixed liquor, 20-40 minute is stirred at 20-30 DEG C, after placing 30 minutes at 10 DEG C, adjustment temperature slowly stirs curing cross-linked for 40-60 minute for-5-7 DEG C of maintenance, extrusion after said mixture gauze parcel is anhydrated.2-3 time is rinsed with 10-20% tannic acid solution; Said mixture placed 50-70 DEG C after oven 8-10 hour.
2. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1, is characterized in that, the ratio of described pretreated attapulgite and MBAA is 10:4-8.
3. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1 and 2, is characterized in that, described salt solution is KCL and polyvinyl alcohol mixing solution, and KCL mass concentration is 2-5%, and polyvinyl alcohol mass concentration is 3-8%.
4. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1, it is characterized in that, the preparation method of CNT is: be the CNT adding methanol aqueous solution weight 20-30% in the methanol aqueous solution of 10-25% in volume ratio, immersion treatment 30-50 minute, centrifugal subsequently, collecting precipitation thing.
5. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1 or 4, is characterized in that, the addition of described biological macromolecular solution is 2-8 times of attapulgite quality.
6. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1, it is characterized in that, the preparation method of biological macromolecular solution is as follows: mixed according to 1:6-8 with Ganoderma Lucidum fermented and cultured liquid by the polyglutamic acid zymotic fluid that fermented and cultured obtains, and heating is subsequently concentrated to the 10-40% of mixed volume.
7. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1, is characterized in that, containing weight ratio in cyclodextrin composite solution is the cyclodextrin of 8-15% and the boric acid of 35-45%.
8. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1, it is characterized in that, the pretreatment of attapulgite: particle diameter 300 order ~ 1000 object attapulgite, attapulgite is added the methanol solution that volumetric concentration is 15-35%, control temperature is at 45-50 DEG C of Electric Pulse Treatment; Supernatant liquor is got after postprecipitation 1-2 hour, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then its supernatant liquor is got, after cyclic washing supernatant liquor like this 3 ~ 5 times, finally carry out centrifugation with 2000-3000, get its precipitation, vacuum drying 24h at 90 DEG C, sieve by particle diameter 200 order ~ 400 mesh sieve after grinding, collect attapulgite stand-by.
9. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1, it is characterized in that, Electric Pulse Treatment condition is as follows: high-voltage pulse process 5-10 minute; High-pressure pulse electric process parameter is preferably: electric-field intensity 20-40KV/cm, burst length 400-600 μ S, pulse frequency 200-300Hz.
10. the preparation method of the biological cleaning carrier for wastewater treatment according to claim 1,
The object of this invention is to provide a kind of biological cleaning carrier for wastewater treatment.Technical scheme is as follows:
The preparation method of the described biological cleaning carrier for wastewater treatment is as follows:
Pretreated attapulgite mixes in salt solution with MBAA, at 50 DEG C, stir 1h; Biological macromolecular solution is mixed with above-mentioned mixed solution, above-mentioned solution is heated to 40 DEG C, add the activated sludge of attapulgite quality 2% and the Nanoscale Iron manganese composite oxide of 1%, add the CNT stir process 1 hour of attapulgite quality 2-5%, mixing speed is 5 turns/min.Then add cyclodextrin composite solution to above-mentioned mixed liquor, stir 20 minutes at 20 DEG C, after placing 30 minutes at 10 DEG C, adjustment temperature slowly stirs curing cross-linked for 60 minutes for-7 DEG C of maintenances, extrusion after said mixture gauze parcel is anhydrated.2 times are rinsed with 10% tannic acid solution; Mixture place 70 DEG C of oven be warmed up to after 8 hours 85 DEG C keep within 5 minutes, cool to 70 DEG C keep 1 hour.
The ratio of pretreated attapulgite and MBAA is: 10:4.
Described salt solution is KCL and polyvinyl alcohol mixing solution, and KCL mass concentration is 2%, and polyvinyl alcohol mass concentration is 3%.
The preparation method of CNT is: be the CNT adding methanol aqueous solution weight 20% in the methanol aqueous solution of 10% in volume ratio, and immersion treatment 50 minutes is centrifugal subsequently, collecting precipitation material.
The addition of described 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 obtains is mixed according to 1:7 with Ganoderma Lucidum fermented and cultured liquid, adopts concentrator to be concentrated to 10% of mixed volume subsequently.
Described polyglutamic acid zymotic fluid and Ganoderma Lucidum fermentation culture are conventionally cultivated.
The concentration of activated sludge is 3000mg/L;
Containing the cyclodextrin of 8% and the boric acid of 35% in cyclodextrin composite solution.
The pretreatment of attapulgite.Particle diameter 300 order ~ 500 object attapulgite, adds the methanol solution that volumetric concentration is 25% by attapulgite, control temperature is at 45-50 DEG C of Electric Pulse Treatment; Supernatant liquor is got after postprecipitation 1-2 hour, add a small amount of distilled water in supernatant liquor and mix the centrifugal 1min of rear continuation 500rpm, then its supernatant liquor is got, after cyclic washing supernatant liquor like this 3 ~ 5 times, finally carry out centrifugation with 2000-3000, get its precipitation, vacuum drying 24h at 90 DEG C, sieve by particle diameter 200 order ~ 400 mesh sieve after grinding, collect attapulgite stand-by.
Electric Pulse Treatment condition is as follows: high-voltage pulse process 5 minutes; High-pressure pulse electric (PEF) processes parameter: electric-field intensity 20KV/cm, burst length 400 μ S, pulse frequency 300Hz.
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