CN107399832A

CN107399832A - A kind of cleanser of efficient process heavy metals in industrial wastewater

Info

Publication number: CN107399832A
Application number: CN201710669566.7A
Authority: CN
Inventors: 王婧宁
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-08-08
Filing date: 2017-08-08
Publication date: 2017-11-28

Abstract

The present invention provides a kind of cleanser of efficient process heavy metals in industrial wastewater, and the cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, the first fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal flocbed, the 3rd fixation of microbe composite layer；The preparing raw material of the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution includes ferric chloride solution, manganese sulfate solution；The plant extracts includes green-tea extract, Schisandra chinens P.E, Galla halepensis extract, Ke's seed extract, pomegranate rind extract, Chinese rhubarb extract, folium eucalypti extract, Flos Caryophylli extract, Gentrin Knotweed P.E, uncaria extract.

Description

A kind of cleanser of efficient process heavy metals in industrial wastewater

Technical field

The present invention relates to sewage treatment area, in particular it relates to a kind of efficient process heavy metals in industrial wastewater Cleanser

Background technology

Current heavy metal wastewater thereby pollution problem annoyings human society always.Heavy metal is big to human body toxic action, to life State environment causes to seriously endanger.It is leaded, attach undue importance to one thing to the neglect of the other water from the industry such as plating, metallurgy, be to cause the major diseases such as mankind's Itai-itai diseases Arch-criminal.

The pollution that Heavy Metals in Waters is particularly in environment comes from human activity mostly, such as industrial enterprise's discharge of wastewater, Mining activity etc..In water body, heavy metal can also be suspended particulate matter and adsorb and sink to together in water body therewith, so as to as length The secondary source of heavy metal pollution of phase.

Heavy metal chemical property is more stable, is difficult to be completely removed in the environment, and can pass through the amplification of biological chain Hundreds and thousands of times of ground enrichments are acted on, finally enter human body, cause human enzymes and protein inactivation or accumulation in human organ In cause slow poisoning.

Immobilized microorganism technique can fix the superiority bacteria spp of the predetermined substance that can degrade through filtering out, the application of the technology Sewage disposal system selectivity can be made, tolerance enhancing, treatment effect is stable, and operational management is simple, and degradation efficiency is substantially better than Tradition.

Process for immobilizing enzyme/microbe mainly includes investment, cross-linking method and absorption method.Absorption method generally relies on biology Effect between body and carrier, it is that still the method stationarity is loosely, easily de- for a kind of simple and easy, mild condition fixing means Fall.Cross-linking method is also known as no-load immobilization method, is a kind of immobilization technology without carrier, and this method passes through chemistry, physical means Make the crosslinking that is attached to each other between biological cell.Investment principle is that biological cell is trapped in the gelatin polymer of water-insoluble In the network of hole, this method is simple to operate, and stationarity is good, is presently the most conventional process for fixation.

Immobilized microorganism technique has the advantages such as efficiency high, non-secondary pollution on processing heavy metal wastewater thereby, has good Environmental benefit and economic benefit.

Therefore, the present invention provides a kind of cleanser of efficient process heavy metals in industrial wastewater regarding to the issue above, and it is pacified It is complete stable, flocculation ability is strong, can effectively chelated metal ions reach wastewater treatment effect and immobilized microorganism it is steady It is qualitative good, there is the effect efficiently removed to heavy metal in waste water.

The content of the invention

In order to solve the above problems, first aspect present invention provides a kind of purification of efficient process heavy metals in industrial wastewater Agent, it is characterised in that the cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal wadding Solidifying layer, the first fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, the 3rd Heavy metal flocbed, the 3rd fixation of microbe composite layer；

The preparing raw material of the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed includes Hydroxymethyl cellulose, metal ion solution, plant extracts；

The metal ion solution includes ferric chloride solution, manganese sulfate solution；

The plant extracts includes green-tea extract, Schisandra chinens P.E, Galla halepensis extract, Ke's seed extract, stone Pomegranate bark extract, Chinese rhubarb extract, folium eucalypti extract, Flos Caryophylli extract, Gentrin Knotweed P.E, uncaria extract；

The first fixation of microbe composite layer, the second fixation of microbe composite layer and the 3rd fixation of microbe The preparing raw material of composite layer includes host material, alginate cross-linked gel, microbial cells, Sulfonated carbon nanotube；

The preparing raw material of the host material includes PLGA, ferroso-ferric oxide, polyvinyl alcohol；

The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad.

In one embodiment, the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal wadding The weight ratio of hydroxymethyl cellulose described in solidifying layer and the plant extracts is 1：(0.3-0.5).

In one embodiment, the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal wadding The weight ratio of hydroxymethyl cellulose described in solidifying layer and the plant extracts is 1：0.36.

In one embodiment, the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal wadding The weight ratio of hydroxymethyl cellulose described in solidifying layer and the metal ion solution is 1：(0.6-0.8).

In one embodiment, the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal wadding The weight ratio of hydroxymethyl cellulose described in solidifying layer and the metal ion solution is 1：0.72.

In one embodiment, calculate by weight, the plant extracts includes 5-10 parts green-tea extract, 1-3 Part Schisandra chinens P.E, 1-3 parts Galla halepensis extract, 2-5 part Ke seed extract, 3-5 parts pomegranate rind extract, 2-7 part rheum officinales Extract, 5-10 part folium eucalyptis extract, 1-3 parts Flos Caryophylli extract, 2-3 parts Gentrin Knotweed P.E, 1-3 part uncaria extracts.

In one embodiment, calculate by weight, the plant extracts includes 7 parts of green-tea extracts, 2 parts of five tastes Seed extract, 2 parts of Galla halepensis extracts, 4 parts of Ke's seed extracts, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalyptis Extract, 1 part of Flos Caryophylli extract, 3 parts of Gentrin Knotweed P.Es, 1 part of uncaria extract.

In one embodiment, ferroso-ferric oxide is the oxygen of magnetic nano-particle four in the preparing raw material of the host material Change three-iron.

In one embodiment, saccharomycete described in the microbial cells, the black-koji mould, the vesicle shortwave The strain quantity ratio of monad is 1：(0.2-0.5)：(0.6-1.2).

Another aspect of the present invention provides a kind of preparation method of the cleanser of efficient process heavy metals in industrial wastewater, including Following steps：

First heavy metal flocbed, the first fixation of microbe composite layer, the second heavy metal flocbed, second are fixed Microorganism composite layer, triple-heavy metal flocbed, the 3rd fixation of microbe composite layer pour into mould in sequence, Obtain the cleanser of the efficient process heavy metals in industrial wastewater.

The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.

Embodiment

Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.

As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or Such a composition, step, method, product or the intrinsic key element of device.

Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme, It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.

Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end Value and all integers and fraction within the range.

Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.

Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.

In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.

" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".

" EVA " means the polymer prepared by polymerizeing at least two different monomers.Generic term " EVA " includes (its is general with term " terpolymer " for term " copolymer " (its typically to refer to the polymer prepared by two kinds of different monomers) To refer to the polymer prepared by three kinds of different monomers).It is also included by polymerizeing more kinds of monomers the polymer that manufactures. " blend " means that two or more polymer mixes the polymer to be formed by physics or chemical method jointly.

First aspect present invention provides a kind of cleanser of efficient process heavy metals in industrial wastewater, it is characterised in that institute The cleanser for stating efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, the first micro- life of fixation Thing composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal flocbed, the 3rd Fixation of microbe composite layer；

The preparation method of the Sulfonated carbon nanotube comprises the following steps：

(1) it is acidified CNT：The concentrated sulfuric acid and sodium nitrate of mass concentration 98%, frozen water are added in dry reactor Bath is lower to be cooled down, and under the conditions of 0-5 DEG C, stirring adds CNT, is slowly added to potassium permanganate after well mixed, controlling reaction temperature For 10-15 DEG C, 2h is reacted, continues stirring reaction 2h under the conditions of 35 DEG C, adds deionized water, controls reacting liquid temperature at 98 DEG C, Continue to stir 0.5h, add the hydrogen peroxide that mass concentration is 30%, filter while hot, and product is entered with watery hydrochloric acid (1mol/L) Row washing is dried under reduced pressure 24h to neutrality under the conditions of 60 DEG C, that is, obtains being acidified CNT；It is described acidifying CNT with it is described Sodium nitrate, the weight ratio of the potassium permanganate are 1：0.6：3.4；The CNT and the dense sulphur of the mass concentration 98% Hydrogen peroxide that sour, described mass concentration is 30%, the mass volume ratio of the deionized water are 1：18：3：20；

(2) sodium borohydride reduction acidifying CNT：The acidifying CNT that step (1) obtains is added to deionized water In, it is ultrasonically treated 1h, the acidifying carbon nano tube suspension being evenly distributed, 5wt% aqueous sodium carbonate regulation acidifying carbon Then nanotube suspension pH value adds 4% sodium borohydride aqueous solution, reacts 1h under the conditions of 80 DEG C, be cooled to room to 9-10 Temperature；The acidifying CNT is 1 with the sodium borohydride weight ratio：8；

(3) sodium nitrite in aqueous solution that mass fraction is 2% is added into reactor, is added under the conditions of 0-5 DEG C to ammonia Base benzene sulfonic acid, HCl/water solution (1mol/L), 24h is reacted, obtains aryl diazonium salts；The natrium nitrosum and the p-aminophenyl Sulfonic acid, the weight ratio of the aqueous hydrochloric acid solution are 1：2.4：25；

(4) Sulfonated carbon nanotube：By the aryl diazonium salts that step (3) obtains slowly be added drop-wise to that step (2) obtains also In former carbon nano tube suspension, and under the conditions of 0-5 DEG C and at room temperature each reaction 2h, it is saturating with deionized water after the completion of reaction Analysis 10 days, is then sonicated 0.5h, filters, 80 DEG C are dried under reduced pressure 20h, obtain Sulfonated carbon nanotube.

Heretofore described PVA is polyvinyl alcohol；The PLGA is Poly(D,L-lactide-co-glycolide.

In the present invention, the preparation method of the host material comprises the following steps：

(1) PLGA/ ferroso-ferric oxide mixed solutions are prepared：PLGA, tetrahydrofuran are added into reactor, stirring, has been treated After fully dissolved, ferroso-ferric oxide is added, stirs 0.5h；The PLGA and the tetrahydrofuran, the weight of the ferroso-ferric oxide Than for 1：5：0.3；

(2) the PLGA/ ferroso-ferric oxides mixing obtained into PVA/ tetrahydrofuran mixed solution and dripping steps (1) is molten Liquid, after being added dropwise, after stirring 1h, 50 DEG C are removed under reduced pressure tetrahydrofuran, obtain loading the PLGA nanoparticles of ferroso-ferric oxide； The weight ratio of the PVA and the ferroso-ferric oxide is 1：0.12；PVA and institute described in the PVA/ tetrahydrofurans mixed solution The weight ratio for stating tetrahydrofuran is 1：3.

The preparation method of fixation of microbe composite in the fixation of microbe composite layer comprises the following steps：

(1) host material, Sulfonated carbon nanotube, sodium alginate, deionized water are mixed, is warming up to 85 DEG C, stir 2h, it is quiet Put and be cooled to 40 DEG C, add microbial cells, mix 1h, obtain the mixed solution of to be fixedization microorganism；The matrix Material and the weight ratio of the Sulfonated carbon nanotube, the sodium alginate, the deionized water are 1：0.01：0.012：20；Institute The weight ratio for stating host material and the microbial cells is 1：0.03；The microbial cells are saccharomycete, black-koji mould, bubble Capsule shortwave monad；

(2) calcium chloride is added in deionized water, stirred, is added dropwise into calcium chloride solution to be fixed in step (1) Change the mixed solution of microorganism, be allowed to form spheric granules, stand, soak 20h, spheric granules is filtered and taken out, deionized water Rinse, produce immobilization microorganism particles；The calcium chloride and the weight ratio of the deionized water are 0.02：1, the calcium chloride Weight ratio with the host material is 0.03：1.

In one embodiment, the concentration of the ferric chloride solution is 0.3mol/L, the concentration of the manganese sulfate solution For 0.13mol/L.

In one embodiment, the weight ratio of the ferric chloride solution and the manganese sulfate solution is 1：(0.1-0.4)； Preferably, the weight ratio of the ferric chloride solution and the manganese sulfate solution is 1：0.2.

Green-tea extract

Green tea is not fermented manufactured tea, remains the natural materials of fresh leaf, the Tea Polyphenols contained, catechin, Ye Lv Element, caffeine, amino acid, vitamins and other nutritious components are also more.These natural nutrition compositions in green tea are to anti-aging, anti- Cancer, anticancer, sterilization, anti-inflammatory etc. have special-effect.It is Tea Polyphenols, caffeine, fat that tealeaves, which has the Main Ingredients and Appearance of pharmacological action, Polysaccharide, theanine etc..

Extracting method：Load 2kg autumn and winter thick tea into steam distillation machine and infuse dust tea, thereto 35 DEG C of uniformly dispersing After water 1kg, stand 10 minutes and be allowed to moisten.- the 54kPaG based on gauge pressure is decompressed to after the completion of moistening, then in SV (space velocity) 325h^-1Lower carry out steam distillation, distillates 0.2kg distillate, obtains steam distillation liquid 1, then makes to return in containment system Normal pressure is returned to, carries out steam distillation at ambient pressure, distillates 2kg distillate, using obtained distillate as steam distillation Liquid 2, merge steam distillation liquid 1 and steam distillation liquid 2, be concentrated under reduced pressure into anhydrous, obtain green-tea extract.

Schisandra chinens P.E

Fruit of Chinese magnoliavine alias Chinese magnoliavine, meeting and, five plums, Chinese prickly ash, strengthen taste, the five tastes, kadsura longepedunculata, the southern five tastes, fructus schisandrae, Chinese Magnoliavine, schisandra chinensis, face vine, blood vine.The fruit of Chinese magnoliavine contains abundant organic acid, vitamin, flavonoids, phytosterol And there is the lignan (such as schizandrin, deoxyschizandrin or fruit of Chinese magnoliavine fat element) of potent reactivation.

Extracting method：The 80% ethanol solution ultrasound of 12 times of weight is added into dry fruit of Chinese magnoliavine pericarp and ripe kind skin 6h is extracted, extract is concentrated under reduced pressure, produced.

Galla halepensis extract

Nutgall alias ink stone, without infanticide, do not have stone, without stone, numb Cha Ze, the numb bitter edible plant pool, without minor；Chemical composition： 50-70% containing alkaloid, gallic acid 2-4% and benzoaric acid, resin etc..Collection：Generally between the 8-9 months, collection Still imperforated insect gall, is dried.

Extracting method：80% ethanol solution ultrasonic extraction 6h of 10 times of weight is added into dry imperforated insect gall, Extract is concentrated under reduced pressure, produced.

Ke's seed extract

Ke Zi alias great Jin fruits, fiber crops come, scold pears, scold multitude, myrobalan, fragrant bavin, with the wind microtriche myrobalan, son；For combretaceae olive Benevolence Pterostyrax plant Ke's subtree, with fruit medicine.Astringe the lung to stop cough, sending down abnormally ascending, cure mainly under protracted dysentery and diarrhea, prolapse of the anus of having blood in stool, uterine bleeding band, seminal emission The diseases such as night sweat.There is cultivation in the provinces such as Guangxi, Guangdong and Yunnan, area.

Extracting method：4.5h is boiled in the decocting for adding 12 times of weight into dry Ke Zi fruits, and decoction liquor is concentrated under reduced pressure, Produce.

Pomegranate rind extract

Granatum alias pomegranate shell, sour pomegranate skin, the real shell of pomegranate acid, sour pomegranate skin, western pomegranate skin；Granatum is planted for Punicaceae The pericarp of thing pomegranate, autumn pomegranate fruit is ripe, and top is plucked when ftractureing, and removes seed and is dried every flesh, valve cutting, or low baking temperature dries It is dry.Dry pericarp is in irregular shape or semicircular fragment shape, thick 2-3mm.Outer surface kermesinus or brownish red, coarse, tool White small salient point；The place calyx of top tool remaining；Base portion has carpopodium.Inner face foresythia or brown color, and it is in netted fruit to have protuberance The residual trace of the base of a fruit.Matter is crisp and hard, frangibility.Gas is faint, puckery.It is preferred with skin depth reality, the reddish brown person of color.Pericarp, stem skin, bark are containing life Alkaloids, it is separated go out：Granatenine, isopelletierine, pseudo- granatenine, N- methylisopelletierines etc..Again from contained by bark Isolated in tannin：Tannin in Punica granatum L, 2,3-O- connect two nutgall acyl Tannin in Punica granatum L, 2-O- nutgall acyl -4, and nutgall Acid connects two nutgall acyls-D-Glucose, 2,3- hexahydroxy biphenyl diformyls-D-Glucose, granatum gluconic acid, horse-tail Tannin, horse-tail tan are peaceful.

Extracting method：The EtOH Sonicate that the mass fraction that 12 times of weight is added into dry granatum is 90% extracts 6h, extract is concentrated under reduced pressure, produced.

Chinese rhubarb extract

Rheum officinale alias Huang is good, fiery ginseng, skin such as, general, Radixet Rhizoma Rhei, Sichuan troops, high, another name for Sichuan Province rheum officinale, cow tongue rheum officinale, bright and beautiful line, life Army, fragrant rheum officinale, R.hoofshaped；Rheum officinale contains anthracene derivative, glycosides compound, tannin class, organic acid, volatile oil etc., tan Matter class includes galloyl glucose, d- catechins, gallic acid, tetrarin (tetrann) etc..

Extracting method：The EtOH Sonicate that the mass fraction that 12 times of weight is added into dry roots and stems of rhubarb is 85% extracts 5h, extract is concentrated under reduced pressure, produced.

Folium eucalypti extract

Folium eucalypti alias ash willow, cajaput, bead walnut, blue oil wood, poplar tsaoko peach, bastard indigo eucalyptus；Chemical composition：Leaf is containing volatilization Oil 0.92~2.89%, its main component is that 1, 8-Cineole, firpene, aromadendrene, cumaldehyde, pinocarveol and 1- acetyl -4- are different Propylidene cyclopentene etc., again containing rutin, quercitrin, Quercetin, L (+)-homoserine, also separate eucalyptin.

Extracting method：3h is boiled in the decocting for adding 12 times of weight into air-dried fresh folium eucalypti, decoction liquor is concentrated under reduced pressure, i.e., .

Flos Caryophylli extract

Cloves, Oleaceae Genus Syringa machaka or dungarunga.Because of elongated such as the nail of cylindrical fireworks and perfume is therefore named, also known as cloves, ocean Cloves.Alias：Flos caryophylli [bud], Fructus Caryophylli [fruit].Bud is caryophyllus oil containing volatile oil.Eugenol is mainly contained in oil (Eugenol), acetyleugenol, B- carypohyllenes (Caryophyllene of B mono-), and methyl-n-amyl ketone, salicylic acid first Ester, Humuleno (Humuleno), benzaldehyde, benzylalcohol, m-methoxybenzaldehyde, benzyl acetate, chavicol (Chavicol), a mono- Ylangene (Ylangene of a mono-) etc..Also have without Eugenol (containing 64~85% in usual caryophyllus oil) in wild varieties, and contain Syringone (Eugenone) and eugenin (Eugenin).The also such as oleanolic acid (Oleanolic containing triterpenoid in spending Acid, flavones and chromone class rhamnetin (Rham-netin), Kaempferol (Kaempferol), eugenin, eugenin Booth (Eugenitin), isoeugenitin (Isoeugenitin) and its demethylation compound isoeugenitol (IsoeugenitoI)。

Extracting method：The EtOH Sonicate that the mass fraction that 10 times of weight is added into dry lilac is 85% extracts 4h, extract is concentrated under reduced pressure, produced.

Gentrin Knotweed P.E

Giant knotweed alias piebald bamboo, sour cylinder bar, sour bucket bamboo shoot, sour soup stalk, river muscle dragon, the spot village, spot cane root, veined rabdosia herb, Huang Garden burnet；Character：Cylindrical short section or irregular sheet, long 1~7cm, 0.5~2.5cm of diameter.Crust sepia, there is vertical wrinkle And mark of fibrous root, section skin zone is relatively thin, and woody part is broad, brown color, ray irradiation shape, and skin zone is more easily separated with woody part.In rhizome marrow Have every or in empty shape, matter is hard, and gas is micro-, mildly bitter flavor, puckery.Root and rhizome match somebody with somebody glucoside, predominantly rheum emodin containing dissociated anthraquinone and anthracene (emodin), Physcion (Physcion), Chrysophanol (chrysopha-nol), anthracene glucoside (anthraglycside) A are Physcion (8-O- β-D-Glucose glucoside (Physcion-8-O- β-D-glucoside), anthracene glucoside (anthraglycoside) B is rheum emodin 8-O- β-D-Glucose glucoside (emodin-8-O- β-D-glucoside), fallacinol (fallacinol), 6- hydroxyls Aloe-emodin (citreorsein), rheum emodin -8- methyl ethers (questin), 6- hydroxyl aloe-emodin -8- methyl ethers (questinol) etc.；Also contain stilbene compound：Resveratrol (resveratrol) is Resveratrol (3,4 ', 5- Tri-hydroxystilbene), Polydatin (Polydatin) is resveratrol 3-O- β-D-Glucose glucoside (rerveratrol- 3-O- β-D-glucoside), (Protocate-chuic acid) containing protocatechuic acid again, dextrorotation cachou extract (catechin), 2, 5- dimethyl -7- hydroxyls chromones (2,5-dimethyl-7-hydroxychromone), 7- hydroxyl -4- methoxyl group -5- methyl are fragrant Beans essence (7-hydroxyl-4-methoxy-5-methyl coumarin), 2- methoxyl group -6- acetyl group -7- methyl English walnuts are matched somebody with somebody (2-methoxy-6-acetyl-7-methyljuglone), Cassia anthrone -8- glycosides (torachrysone-8-O-D- Glucoside), cupreol glycoside (β-sitosterol glucoside) and glucose (glucose), rhamnose (rhamnose), polysaccharide, amino acid etc..

Extracting method：The mass fraction that 12 times of weight is added into dry polygoni cuspidati,radix or rhizome is 90% EtOH Sonicate 5h is extracted, extract is concentrated under reduced pressure, produced.

Uncaria extract

Yncaria stem with hooks alias ramulus uncariae rhynchophyllae, wang gambirplant branchlet, hang wind root, golden hook grass, projecting thorn；Character：Stem branch is in cylinder or class square column Shape, long 2-3cm, diameter 0.2-0.5cm.Surface rufous has thin longitudinal grin, Glabrous, yellow green to taupe to aubergine person Person's visible white point-like hole skin sometimes, by yellowish-brown pubescence.To raw two reclinate hook (sterile inflorescences in most minor matters Stalk), or only there is hook side, opposite side is raised scar；Hook is slightly flat or slightly round, tip apicule, and base portion is wealthyer；The branch of hook base portion The stipule trace of nest spot printing and ring-type after above visible petiole comes off.Matter is tough and tensile, section yellowish-brown, sheath fibers, marrow Yellow-white is hollow.It is odorless, it is lightly seasoned.Chemical composition：Buckle stem branches and leaves are containing rhynchophyllin, isorhynchophylline, corynoxeine, different Ke Nuo It is pungent because of alkali, corynantheine alkali, dihydrocorynantheine alkali, hirsutine, hirsuteine.

Extracting method：4h is boiled in the decocting for adding 10 times of weight into dry yncaria stem with hooks, and decoction liquor is concentrated under reduced pressure, produced.

The preparation method of the magnetic nano-particle ferroso-ferric oxide is as follows：

Ferric acetyl acetonade, oleic acid, the dihydric alcohols of 1,2- ten, oleyl amine, benzyl ether are added into reactor, and is passed through nitrogen, 0.5h is stirred, is warming up to 200 DEG C, insulation reaction 2h, then stops being passed through nitrogen, is warming up to 300 DEG C, insulation reaction 1h, stop Reaction, room temperature is cooled to, adds absolute ethyl alcohol, stir 0.5h, filtering, 60 DEG C are dried under reduced pressure 20h, obtain the magnetic nano particle Sub- ferroso-ferric oxide；The ferric acetyl acetonade, the oleic acid, the dihydric alcohols of 1, the 2- ten, the oleyl amine, the benzyl ether, The weight ratio of the absolute ethyl alcohol is 1：2.5：3：2.2：12：20.

In one embodiment, saccharomycete described in the microbial cells, the black-koji mould, the vesicle shortwave The strain quantity ratio of monad is 1：(0.2-0.5)：(0.6-1.2)；Preferably, saccharomycete described in the microbial cells, The black-koji mould, the strain quantity ratio of the vesicle shortwave monad are 1：0.3：1.0.

In one embodiment, the preparation method of heavy metal wastewater thereby flocculating composition includes in the heavy metal flocbed Following steps：

Into microwave reactor add hydroxymethyl cellulose, ferric chloride solution, the manganese sulfate solution, plant extracts, Citric acid, deionized water, after stirring, 90 DEG C, insulated and stirred 5min are warming up to, are cooled to room temperature, stood 2h, filtering, obtain To heavy metal wastewater thereby flocculating composition；The weight ratio of the hydroxymethyl cellulose and the citric acid is 1：0.24.

Heretofore described saccharomycete is brewer's yeast, is bought in Southwest Jiaotong University's Life Science College；

By black-koji mould spore, several are seeded in 100mL and potato culture medium (medium component are housed：200g/L potatoes, 20g/L C₆H₁₂O₆、0.5g/L MgSO₄·7H₂O、1g/L KH₂PO₄) conical flask in, shaking table culture 48h at 37 DEG C, whole behaviour Work need to be carried out in superclean bench.After black-koji mould amount reproduction, 4 DEG C of refrigerator storages are transferred into.

The vesicle shortwave monad is purchased from Shanghai Hu Zheng bio tech ltd.

In the present invention heavy metal flocbed by induced chemical reduction mechanism, pass through stimulating organism reduction mechanism or logical Cross chemistry and the combination purification sanitary sewage of biological reducing mechanism.Chemistry by polyhydric phenols unique structure in plant extracts is living Property and physiological property, the characteristic being complexed with various metals ion, except the metal, heavy metal, arsenic that may contain in decontaminated water Compound and chromium compound；Heavy metal ion is combined with the group such as hydroxyl, carboxyl in plant extracts, formed covalent bond or Ionic bond, this combination are quick；Heavy metal flocculating composition can be used as reducing agent to destroy for example high chlorine of oxidant compound Hydrochlorate and nitrate, further improve the effect of purification sewage.

In addition, containing substantial amounts of water-soluble polyphenols compound in the present invention in plant extracts, gone using plant extracts It is subject to certain restrictions, therefore needs plant extracts immobilization during heavy metal in water removal.Cured vegetable extract passes through chemistry Bond closes the new adsorbent prepared, and its carrier is the macromolecular scaffold of water-insoluble, aglucon is natural plant extracts.Locating Manage in heavy metal wastewater thereby, because being the insoluble substance using plant extracts as main body synthesis one kind, largely lived in its molecule Property group is retained, so alternatively its performance of the plant extracts of property adsorbent is greatly improved, Er Qieke With through regenerating Reusability.Cured vegetable extract not only has some new properties, as not soluble in water, alcohol and it is organic Solvent, and heavy metal ion and polymer substance have the compatibility of height, and can optionally adsorb heavy metal.

Host material described in the magnetic Nano prepared in the present invention has good loads bacterium amount, higher envelop rate and fine Stability.

Heavy metal ion can be combined with groups such as the hydroxyl on carrier (host material and Sulfonated carbon nanotube) surface, carboxyls, It is quick to form covalent bond or ionic bond, this combination；Meanwhile heavy metal ion is acted on into carrier by diffusion mass transfer Portion spreads, and carrier inside concentration forms certain concentration gradient, thereby reduce heavy metal ion to internal micro- life less than outside The poisonous effect of thing；The mechanism of microorganism heavy metal ion in carrier can be divided into two mistakes of biological accumulation and biological adsorption Journey, biological adsorption are to make cell negatively charged by cell surface functional group, will be heavy metal ion adsorbed using electrostatic adsorption In antimicrobial surface；It is right that the heavy metal ion of cell surface can enter cell interior by effects such as active transport, ion exchanges After be enriched with the cell, formed biological accumulation, biological accumulation by living cells metabolism, it is necessary to consumed energy, this mistake Cheng Tongchang is slower, and according to the selectivity of microbial cell just for individual other heavy metal ion.In addition, cell metabolism produces Cucumber enter waste water in after also can with heavy metal ion occur complex reaction, generate other materials, reduce heavy metal Ion toxicity.

The group such as mesostroma material of the present invention and the hydroxyl on Sulfonated carbon nanotube surface, carboxyl and uniqueness hollow structure and Nano-scale and huge specific surface area, promote the removal of heavy metal in waste water.

The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.

In addition, if without other explanations, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.

Embodiment 1

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.72；The plant extracts include 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts Ke's seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds Extract, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of 3rd fixation of microbe composite layer includes host material, alginate cross-linked gel, microbial cells, sulphur Carbon nano tube；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad, in the microbial cells The saccharomycete, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad are 1：0.3：1.0；The iron chloride The concentration of solution is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the ferric chloride solution and the sulfuric acid The weight ratio of manganese solution is 1：0.2；

The preparation method of the cleanser of the efficient process heavy metals in industrial wastewater, comprises the following steps：

The preparation method of the host material comprises the following steps：

The preparation method of heavy metal wastewater thereby flocculating composition comprises the following steps in the heavy metal flocbed：

Embodiment 2

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.3, the first heavy metal flocbed, second The weight ratio of hydroxymethyl cellulose described in heavy metal flocbed and triple-heavy metal flocbed and the metal ion solution is 1：0.72；The plant extracts includes 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts of Ke Seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds carry Take thing, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of three fixation of microbe composite layers includes host material, alginate cross-linked gel, microbial cells, sulfonation CNT；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad, institute in the microbial cells It is 1 to state saccharomycete, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad：0.3：1.0；The iron chloride is molten The concentration of liquid is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the ferric chloride solution and the manganese sulfate The weight ratio of solution is 1：0.2；

The preparation method of the cleanser of the efficient process heavy metals in industrial wastewater, the preparation side of the host material Method, the preparation method of fixation of microbe composite in the fixation of microbe composite layer and the heavy metal flocbed The preparation method of middle heavy metal wastewater thereby flocculating composition is the same as embodiment 1.

Embodiment 3

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.5, the first heavy metal flocbed, second The weight ratio of hydroxymethyl cellulose described in heavy metal flocbed and triple-heavy metal flocbed and the metal ion solution is 1：0.72；The plant extracts includes 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts of Ke Seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds carry Take thing, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of three fixation of microbe composite layers includes host material, alginate cross-linked gel, microbial cells, sulfonation CNT；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad, institute in the microbial cells It is 1 to state saccharomycete, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad：0.3：1.0；The iron chloride is molten The concentration of liquid is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the ferric chloride solution and the manganese sulfate The weight ratio of solution is 1：0.2；

Embodiment 4

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.6；The plant extracts includes 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts of Ke Seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds carry Take thing, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of three fixation of microbe composite layers includes host material, alginate cross-linked gel, microbial cells, sulfonation CNT；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad, institute in the microbial cells It is 1 to state saccharomycete, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad：0.3：1.0；The iron chloride is molten The concentration of liquid is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the ferric chloride solution and the manganese sulfate The weight ratio of solution is 1：0.2；

Embodiment 5

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.8；The plant extracts includes 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts of Ke Seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds carry Take thing, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of three fixation of microbe composite layers includes host material, alginate cross-linked gel, microbial cells, sulfonation CNT；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad, institute in the microbial cells It is 1 to state saccharomycete, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad：0.3：1.0；The iron chloride is molten The concentration of liquid is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the ferric chloride solution and the manganese sulfate The weight ratio of solution is 1：0.2；

Embodiment 6

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.72；The plant extracts includes 37 parts of folium eucalypti extracts；The first fixation of microbe composite layer, second are consolidated Determining the preparing raw material of microorganism composite layer and the 3rd fixation of microbe composite layer includes host material, alginate friendship Join gel, microbial cells, Sulfonated carbon nanotube；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave unit cell Bacterium, saccharomycete described in the microbial cells, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad are 1： 0.3：1.0；The concentration of the ferric chloride solution is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the chlorine The weight ratio for changing ferrous solution and the manganese sulfate solution is 1：0.2；

Embodiment 7

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.72；The plant extracts includes 37 parts of green-tea extracts；The first fixation of microbe composite layer, second are consolidated Determining the preparing raw material of microorganism composite layer and the 3rd fixation of microbe composite layer includes host material, alginate friendship Join gel, microbial cells, Sulfonated carbon nanotube；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave unit cell Bacterium, saccharomycete described in the microbial cells, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad are 1： 0.3：1.0；The concentration of the ferric chloride solution is 0.3mol/L, the concentration of the manganese sulfate solution is 0.13mol/L, the chlorine The weight ratio for changing ferrous solution and the manganese sulfate solution is 1：0.2；

Comparative example 1

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer；First huge sum of money Belong to flocbed, the preparing raw material of the second heavy metal flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts； The metal ion solution includes ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the flocculation of the second heavy metal The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and the metal ion solution is 1：0.72；The plant carries Thing is taken to include 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts of Ke's seed extracts, 5 parts of granatums Extract, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of Gentrin Knotweed P.Es, 1 part of uncaria extract； The first fixation of microbe composite layer, the second fixation of microbe composite layer preparing raw material include host material, Alginate cross-linked gel, microbial cells, Sulfonated carbon nanotube；The microbial cells include saccharomycete, black-koji mould, bubble Capsule shortwave monad, saccharomycete described in the microbial cells, the black-koji mould, the strain of the vesicle shortwave monad Quantity ratio is 1：0.3：1.0；The concentration of the ferric chloride solution is 0.3mol/L, the concentration of the manganese sulfate solution is The weight ratio of 0.13mol/L, the ferric chloride solution and the manganese sulfate solution is 1：0.2；

Fixation of microbe composite in the preparation method of the host material, the fixation of microbe composite layer Preparation method and the heavy metal flocbed in heavy metal wastewater thereby flocculating composition preparation method with embodiment 1.

The preparation method of the cleanser of the efficient process heavy metals in industrial wastewater is as follows：

First heavy metal flocbed, the first fixation of microbe composite layer, the second heavy metal flocbed, second are fixed Microorganism composite layer is poured into mould in sequence, obtains the cleanser of the efficient process heavy metals in industrial wastewater.

Comparative example 2

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer, the 4th heavy metal flocbed, the 4th fixation of microbe composite layer；It is described First heavy metal flocbed, the second heavy metal flocbed, triple-heavy metal flocbed, the preparing raw material of the 4th heavy metal flocbed Including hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution includes ferric chloride solution, sulfuric acid Manganese solution；The first heavy metal flocbed, the second heavy metal flocbed, triple-heavy metal flocbed and the flocculation of the 4th heavy metal The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, Two heavy metal flocbeds, triple-heavy metal flocbed, hydroxymethyl cellulose described in the 4th heavy metal flocbed and the metal The weight ratio of solion is 1：0.72；The plant extracts include 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts Galla halepensis extract, 4 parts of Ke's seed extracts, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of fourth Fragrant extract, 3 parts of Gentrin Knotweed P.Es, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation are micro- Biocomposite material layer, the 3rd fixation of microbe composite layer, the preparing raw material bag of the 4th fixation of microbe composite layer Include host material, alginate cross-linked gel, microbial cells, Sulfonated carbon nanotube；The microbial cells include saccharomycete, Black-koji mould, vesicle shortwave monad, saccharomycete described in the microbial cells, the black-koji mould, the vesicle shortwave The strain quantity ratio of monad is 1：0.3：1.0；The concentration of the ferric chloride solution is 0.3mol/L, the manganese sulfate solution Concentration is 0.13mol/L, and the weight ratio of the ferric chloride solution and the manganese sulfate solution is 1：0.2；

First heavy metal flocbed, the first fixation of microbe composite layer, the second heavy metal flocbed, second are fixed Microorganism composite layer, triple-heavy metal flocbed, the 3rd fixation of microbe composite layer, the 4th heavy metal flocbed, 4th fixation of microbe composite layer pours into mould in sequence, obtains the efficient process heavy metals in industrial wastewater Cleanser.

Comparative example 3

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, Two heavy metal flocbeds, triple-heavy metal flocbed；The first heavy metal flocbed, the second heavy metal flocbed and are triple The preparing raw material of metal flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution Including ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal wadding The weight ratio of hydroxymethyl cellulose described in solidifying layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight of hydroxymethyl cellulose described in second heavy metal flocbed and triple-heavy metal flocbed and the metal ion solution Than for 1：0.72；The plant extracts includes 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 Part Ke seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 portions of tigers Cane extract, 1 part of uncaria extract；

The preparation of heavy metal wastewater thereby flocculating composition in the preparation method of the host material and the heavy metal flocbed Method is the same as embodiment 1.

First heavy metal flocbed, the second heavy metal flocbed, triple-heavy metal flocbed are poured into mould in sequence In, obtain the cleanser of the efficient process heavy metals in industrial wastewater.

Comparative example 4

It is compound that the cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first fixation of microbe Material layer, the second fixation of microbe composite layer, the 3rd fixation of microbe composite layer；First fixation of microbe is answered The preparing raw material of condensation material layer, the second fixation of microbe composite layer and the 3rd fixation of microbe composite layer includes matrix Material, alginate cross-linked gel, microbial cells, Sulfonated carbon nanotube；The microbial cells include saccharomycete, aspergillus niger Bacterium, vesicle shortwave monad, saccharomycete described in the microbial cells, the black-koji mould, the vesicle shortwave monad Strain quantity ratio be 1：0.3：1.0；The concentration of the ferric chloride solution is 0.3mol/L, the concentration of the manganese sulfate solution is The weight ratio of 0.13mol/L, the ferric chloride solution and the manganese sulfate solution is 1：0.2；

First fixation of microbe composite layer, the second fixation of microbe composite layer, the 3rd fixation of microbe are answered Condensation material layer is poured into mould in sequence, obtains the cleanser of the efficient process heavy metals in industrial wastewater.

Comparative example 5

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.72；The plant extracts include 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts Ke's seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds Extract, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of 3rd fixation of microbe composite layer includes host material, alginate cross-linked gel, microbial cells；Institute Stating microbial cells includes saccharomycete, black-koji mould, vesicle shortwave monad, saccharomycete described in the microbial cells, institute State black-koji mould, the strain quantity ratio of the vesicle shortwave monad is 1：0.3：1.0；The concentration of the ferric chloride solution is 0.3mol/L, the concentration of the manganese sulfate solution are 0.13mol/L, the ferric chloride solution and the manganese sulfate solution weight Than for 1：0.2；

Comparative example 6

The cleanser of the efficient process heavy metals in industrial wastewater is from top to bottom followed successively by the first heavy metal flocbed, One fixation of microbe composite layer, the second heavy metal flocbed, the second fixation of microbe composite layer, triple-heavy metal wadding Solidifying layer, the 3rd fixation of microbe composite layer；The first heavy metal flocbed, the second heavy metal flocbed and the 3rd huge sum of money Belonging to the preparing raw material of flocbed includes hydroxymethyl cellulose, metal ion solution, plant extracts；The metal ion solution bag Include ferric chloride solution, manganese sulfate solution；The first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocculation The weight ratio of hydroxymethyl cellulose described in layer and the plant extracts is 1：0.36, the first heavy metal flocbed, The weight ratio of hydroxymethyl cellulose described in two heavy metal flocbeds and triple-heavy metal flocbed and the metal ion solution For 1：0.72；The plant extracts include 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts Ke's seed extract, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of giant knotweeds Extract, 1 part of uncaria extract；The first fixation of microbe composite layer, the second fixation of microbe composite layer and The preparing raw material of 3rd fixation of microbe composite layer includes alginate cross-linked gel, microbial cells, sulfonation carbon nanometer Pipe；The microbial cells include saccharomycete, black-koji mould, vesicle shortwave monad, yeast described in the microbial cells Bacterium, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad are 1：0.3：1.0；The ferric chloride solution it is dense The concentration spent for 0.3mol/L, the manganese sulfate solution is 0.13mol/L, the ferric chloride solution and the manganese sulfate solution Weight ratio is 1：0.2；

Performance test：

The cleanser of efficient process heavy metals in industrial wastewater is added to the heavy metal of the 2.4mM through Tris (10mM) modulation The aqueous solution (CdCl₂, NiCl₂, PbCl₂, CrCl₃, CuCl₂) in 500ml.Reaction is centrifuged after terminating, with atom absorption photometric Heavy metal concentration in the supernatant of meter measure separation.

The performance test results of table 1

As can be seen that the cleanser of the efficient process heavy metals in industrial wastewater provided by the invention from above-mentioned data Its safety and stability, flocculation ability is strong, effectively can reach effect and the immobilized microorganism of wastewater treatment by chelated metal ions Stability it is good, there is the effect that efficiently removes to heavy metal in waste water.

Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim covers.

Claims

1. a kind of cleanser of efficient process heavy metals in industrial wastewater, it is characterised in that in the efficient process industrial wastewater The cleanser of heavy metal is from top to bottom followed successively by the first heavy metal flocbed, the first fixation of microbe composite layer, the second weight Metal flocbed, the second fixation of microbe composite layer, triple-heavy metal flocbed, the 3rd fixation of microbe composite Layer；

The preparing raw material of the first heavy metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed includes hydroxyl first Base cellulose, metal ion solution, plant extracts；

The plant extracts includes green-tea extract, Schisandra chinens P.E, Galla halepensis extract, Ke's seed extract, granatum Extract, Chinese rhubarb extract, folium eucalypti extract, Flos Caryophylli extract, Gentrin Knotweed P.E, uncaria extract；

The first fixation of microbe composite layer, the second fixation of microbe composite layer and the 3rd fixation of microbe are compound The preparing raw material of material layer includes host material, alginate cross-linked gel, microbial cells, Sulfonated carbon nanotube；

2. the cleanser of efficient process heavy metals in industrial wastewater according to claim 1, it is characterised in that first weight Hydroxymethyl cellulose described in metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed and the plant extract The weight ratio of thing is 1：(0.3-0.5).

3. the cleanser of efficient process heavy metals in industrial wastewater according to claim 2, it is characterised in that first weight Hydroxymethyl cellulose described in metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed and the plant extract The weight ratio of thing is 1：0.36.

4. the cleanser of efficient process heavy metals in industrial wastewater according to claim 1, it is characterised in that first weight Hydroxymethyl cellulose described in metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed and the metal ion The weight ratio of solution is 1：(0.6-0.8).

5. the cleanser of efficient process heavy metals in industrial wastewater according to claim 4, it is characterised in that first weight Hydroxymethyl cellulose described in metal flocbed, the second heavy metal flocbed and triple-heavy metal flocbed and the metal ion The weight ratio of solution is 1：0.72.

6. the cleanser of efficient process heavy metals in industrial wastewater according to claim 1, it is characterised in that by weight Calculate, the plant extracts includes 5-10 parts green-tea extract, 1-3 parts Schisandra chinens P.E, 1-3 parts Galla halepensis extract, 2-5 Part Ke seed extract, 3-5 parts pomegranate rind extract, 2-7 parts Chinese rhubarb extract, 5-10 part folium eucalyptis extract, the extraction of 1-3 parts cloves Thing, 2-3 parts Gentrin Knotweed P.E, 1-3 part uncaria extracts.

7. the cleanser of efficient process heavy metals in industrial wastewater according to claim 6, it is characterised in that by weight Calculate, the plant extracts includes 7 parts of green-tea extracts, 2 parts of Schisandra chinens P.Es, 2 parts of Galla halepensis extracts, 4 parts of Ke Zi and carried Take thing, 5 parts of pomegranate rind extracts, 3 parts of Chinese rhubarb extracts, 9 parts of folium eucalypti extracts, 1 part of Flos Caryophylli extract, 3 parts of Gentrin Knotweed P.Es, 1 part of uncaria extract.

8. the cleanser of efficient process heavy metals in industrial wastewater according to claim 1, it is characterised in that the matrix material Ferroso-ferric oxide is magnetic nano-particle ferroso-ferric oxide in the preparing raw material of material.

9. the cleanser of efficient process heavy metals in industrial wastewater according to claim 1, it is characterised in that the microorganism Saccharomycete described in thalline, the black-koji mould, the strain quantity ratio of the vesicle shortwave monad are 1：(0.2-0.5)： (0.6-1.2)。

10. according to the preparation method of the cleanser of efficient process heavy metals in industrial wastewater described in claim 1-9, its feature exists In comprising the following steps：

First heavy metal flocbed, the first fixation of microbe composite layer, the second heavy metal flocbed, second are fixed into micro- life Thing composite layer, triple-heavy metal flocbed, the 3rd fixation of microbe composite layer pour into mould in sequence, obtain The cleanser of the efficient process heavy metals in industrial wastewater.