CN103466731A - Fiber radical sewage decoloration and purification material and preparing method thereof - Google Patents
Fiber radical sewage decoloration and purification material and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a fiber radical sewage decoloration and purification material which is characterized by comprising a component (I) and a component (II). The component (II) occupies 5%-10% of the total mass. The component (1) is a product obtained by reaction of 36% formaldehyde solutions, dicyandiamide, ammonium chloride and property-modifying additives A, wherein the mass ratios of the 36% formaldehyde solutions, the dicyandiamide, the ammonium chloride and the property-modifying additives A are sequentially 1.0-1.3:0.50-0.65:0.60-0.70:0.06-0.09. The property-modifying additives A are a mixture obtained by mixing magnesium sulfate and magnesium chloride according to a proportion, wherein the mass ratio of the magnesium sulfate and the magnesium chloride is 2.0-3.5:8.0-6.5. The component (II) is a natural fiber (plant and/or animal) which is modified by cation modifiers. The fiber radical sewage decoloration and purification material integrates multiple functions such as decoloration, flocculation, entanglement and COD removing. The decoloration ratio of sewage can reach more than 93%, the COD value removing rate is higher than that of the prior art by more than 10%, reclaimed water reusing can be achieved, and sewage discharging is reduced.
Description
One, technical field
The present invention relates to the sewage treating material preparation, specifically a kind of for fiber base sewage decoloring scavenging material preparation method for dyeing sewage decoloration.
Two, background technology
Because industrialization, Development of China's Urbanization are accelerated, China's water scarcity, distributed pole imbalance, surface water, groundwater pollution are on the rise, and have become the restraining factors of building beautiful China, sustainable economic development, social harmonious development, and the water be on the rise pollutes the shortage of heavy water resource more.China is textile printing and dyeing processing base the biggest in the world, and annual processing fiber amount reaches more than 2,000 ten thousand tons, relates to cotton, fiber crops, silk, hair, chemical fibre etc., the coloured sewage discharge expanding day of textile printing and dyeing.
Wherein the dyeing and printing sewage dye discoloration is the most serious, and more than Chinese dyestuff Year's consumption few hundred thousand tonnes of, kind reaches hundreds of, and in dyeing process, the tinctorial yield of dyestuff on fabric only has 70-80%, and the dyestuff dyed on not forms the sewage of high-concentration and high-chromaticity.Dyeing and printing sewage is industrial sewage discharge rich and influential family, and quantity discharged accounts for 1/10 of industrial sewage total release, and China approximately has 6 * 10 every year
8～7 * 10
8the discharge of t dyeing and printing sewage, constantly dilution, repeated contamination, be difficult to process.Realize the Sustainable development of dyeing, must thoroughly solve the dyeing and printing sewage pollution problem!
The characteristics of dyeing and printing sewage are that quantity discharged is large, complicated component, organic content is high, colourity is dark, chemical oxygen demand (COD) (CODcr) height, and biochemical oxygen demand (BOD) (BOD5) is relatively low, biodegradability is poor, except containing dyestuff, auxiliary agent and slurry, also contain the toxic organic pollutant that heavy metal ion, aniline, oil of mirbane, O-phthalic acids etc. contain the groups such as phenyl ring, amido, azo in sewage, be difficult to biological degradation, serious environment pollution, mostly be carcinogenic substance, process more general sewage more difficult.The decolouring of coloured sewage is processed has become one of domestic and international environmental protection circle urgent need to solve the problem.
At present domestic and international dyeing sewage decoloration method has summed up following several:
1, adsorption bleaching
A major advantage of adsorption bleaching is dyestuff can be removed from water by the effect of absorption, and adsorption process has retained the structure of dyestuff.Gac is widely used in coloured sewage disposal already as a kind of superior adsorbent, so far be still the best sorbent material of coloured dyeing waste water, gac has selectivity to dyestuff, and its decoloration performance sequentially is followed successively by basic dyestuff, substantive dyestuff, matching stain and thioxine dyes.Gac is expensive, and regeneration difficulty in addition generally only is applied to treatment of dyeing wastewater or the advanced treatment that concentration is lower.Molecular sieve, active aluminum, granulated active carbon (GAC), diatomite and wood sawdust can be as the sorbent materials of dispersed dyestuff.The greatest problem of sorbent material is to be difficult to realize situ regeneration.S karcher: developed a kind of novel reproducible sorbent material Cucurbituril, it is a kind of cyclic condensation polymer formed by glycoluril and formaldehyde condensation polymer.Through great many of experiments, show, this material is nontoxic, and at Ca
2+concentration 1～100mmol/L, in solution, the total concn of salt is less than 100-1000mmol/L.The time, can obtain high adsorptive capacity, remaining colourity is very low.
2, redox decolouring
The conjugated system or the chromophoric group that destroy dyestuff by redoxomorphism are the effective ways that the printing and dyeing decolouring is processed.Except conventional oxychlorination method, research emphasis mainly concentrates on ozone oxidation, hydrogen peroxide oxidation, electrolytic oxidation and photoxidation aspect both at home and abroad.
Ozone is good decolouring oxygenant, for the containing water-soluble dyestuff as active, directly, positively charged ion and the waste water from dyestuff such as acid, its percent of decolourization is very high; Dispersed dye are also had to better decolorizing effect; But other are present in to reduction, sulfuration and the coating in waste water with suspended state, and decolorizing effect is poor.Ozone oxidation also can be combined with other treatment technologies application.As use FeSO
4, Fe
2(SO
4)
3, and FeCl
3, can improve decolouring by ozonize again after cohesion and process; The ozone electrolysis treatment can make directly, the percent of decolourization of matching stain increases by 25～40% than simple ozonize, and alkalescence and reactive dyestuffs are increased to 10%.Ozone adds uv-radiation or carries out ionizing rays simultaneously and also can improve oxidation efficiency.Because ozone oxidation is high to dye species wide adaptability, decolorizing efficiency, while O
3reduzate in waste water and superfluous O
3, can be decomposed into O rapidly in solution and air
2, can not cause secondary pollution to environment.So O
3decolouring technology has certain industrial applications prospect.The main drawback of ozone oxidation is that working cost is relatively higher at present.
Fenton reagent except having oxygenizement, also have coagulation concurrently, so decolorizing efficiency is higher in processing the waste water process.In processing, the decolouring of dye well waste water obtained increasingly extensive application, traditional H in recent years
2o
2oxidation all occurs with the form of Fenton reagent at present.In order to fully understand the decoloring ability of Fenton reagent to various dyestuffs, Kuo W G has selected the representative compound that covers 90% common dyes kind to carry out modeling effort.Result shows, under acidic conditions (pH<3), average percent of decolourization reaches 97%, COD clearance and also can reach 90%.
The advanced oxidation processes decolouring is considered to a kind of up-and-coming method.So-called advanced oxidation processes is as UV+H
2o
2, UV+O
3because produce hydroxyl radical free radical in oxidising process, its strong oxidizing property makes decoloring dye waste water.The decolouring of finding after deliberation its azo dyes is very effective.Can improve decolorizing effect with some chemical auxiliary in actual production. and UV+H
2o
2the degraded product that method processing azo reactive dye produces is fully harmless to environment.Nearest research finds that dichloro diazine fundamental mode azo reactive dyestuffs are used UV+H
2o
2the method decolouring also has good effect.
A wretched insufficiency part of advanced oxidation processes is that processing costs is higher.Thereby limited being widely used of it.
3, coagulation decoloration treatment technology
(1) inorganic coagulant
The inorganic coagulant occurred at present comprises metallic salt and inorganic polymer polyelectrolyte, wherein take the compound of molysite, magnesium salts, aluminium salt and silicon, calcium constituent as main.According to applicable cases, all the percent of decolourization to some water-soluble dye wastewaters is not high for the simple aluminium salt such as aluminium chlorohydroxide, Tai-Ace S 150, trivalent iron salt, and the pH scope of using is narrower.FeSO
4all have decolorizing effect preferably for most of water-soluble dye, for example process sulphur dyes wastewater, chroma removal rate is 95%, and sulfide and BOD clearance are 96% and 59%.But due to FeSO
4the mechanism of decolouring is by the chromophoric group reduction, and reduzate is effectively coagulation removal of organic molecule, so the clearance of CODcr is not high, and larger to the consumption of basicity in solution, and the consumption of coagulating agent is also larger.
MgO, MgSO
4deng magnesium salts, the Mg that utilizes it to generate in the aqueous solution (OH)
2the strong adsorption effect, to containing the water-soluble dye of sulfonic acid group, thering is good treatment effect, percent of decolourization, CODcr clearance, can reach respectively more than 98% and 70%; .Adopt MgCl
2and Ca (OH)
2process reactive dyestuffs and dispersed dyestuff waste water, its effect is better than A1
2(SO
4)
3, PAC, FeSO
4/ Ca (OH)
2.Its mechanism is Mg
2+with hydroxyl, carboxyl or SO
4 2-reaction generates stable inner complex, and these inner complexs can be removed by throwing out from waste water.But also there is the shortcoming of pH narrow range in magnesium salts.
The a lot of research and application practice shows, adopt inorganic coagulant to comprise that molysite, aluminium salt, magnesium salts and inorganic wadding agent have good decolorizing effect to the dyestuff be present in waste water with colloid or suspended state, as the vat dyes after dispersed dye, thioxine dyes, oxidation, larger substantive dyestuff and the neutral dye of glacial dye, pigment and molecular weight after coupling; To the water-soluble dye substantive dyestuff waste water as micromolecular as matching stain, reactive dyestuffs and part that be difficult for to form colloidal particle, coagulate decoloring effect is undesirable.
(2) organic floculant
Tensio-active agent: tensio-active agent is a lot of for the report for the treatment of of dyeing wastewater, and pure dissolubility acetic acid stearylamine can be used for processing insoluble dyes, as what process Containing Sulfur Black B dyestuff, dyes cotton wastes water, and the dyestuff clearance can reach 99.2%.Octadecyl trimethyl ammonium chloride and hexadecyl pyridinium bromide salt binding Al for Stoica L
2(SO
4)
3in the pH value, be the silk dyeing waste water containing acid and substantive dyestuff to be carried out to the coagulation air-float processing at 4～11 o'clock, percent of decolourization can reach 90～100%.But the charge neutrality effect of cats product and dye molecule has stronger selectivity, use and be difficult to reach good effect separately, need and the composite use of aluminium salt.
Natural polymer and modified flocculant thereof: natural organic high-molecular flocculant is because raw material sources are extensive.Cheap, nontoxic, be easy to the characteristics such as biological degradation and shown good application prospect.Mainly contain the three major types such as native starch and derivative thereof, lignin derivative, chitin derivativ for the natural macromolecule flocculating agent for the treatment of of dyeing wastewater.
In wastewater treatment, most of subparticle and colloid are all with negative charge, and in order to improve starch and the lignin molecule ability to function to these small-molecule substances, carrying out cation-modified is an important research direction.Cation modifying starch and xylogen can be processed anionic dyestuff, substantive dyestuff and Acid Dye Wastewater, and percent of decolourization is all over 90%.
Syn-Organic flocculants: synthetic organic polymer coargulator molecular weight is high. in molecular chain with active function groups many, range of extension in water is large, and flocculating property is good, and consumption is few, the pH scope is wide, all has superior performance in solid-liquid separation operating aspects such as filtration, dehydrations simultaneously.At present polymeric flocculant PAN-the DCD effect is best, and it is to take polyacrylonitrile as main chain, carries out modified side chain under alkaline condition by Dicyanodiamide, make it to become water miscible, with the polyamphoteric electrolyte of various active group.The decolorizing effect of PAN-DCD centering dyestuff, reactive dyestuffs, matching stain is good, percent of decolourization all reaches more than 90%, dyeing waste water is had concurrently decolouring and removes the double effects of COD, if with the polymerize aluminum chloride compound use, removal effect is better, and the highest COD clearance is 63%.Another kind of noticeable discoloring agent is the Dyhard RU 100 formaldehyde condensation products occurred in recent years, and it has excellent decolorizing effect for dyeing waste water, but the dosage conference improves processing cost.
About flocculating decoloring agent, disclosed Chinese patent has CN101935094A, CN101759264A, CN102515331A, CN101851018A, CN1607185A etc.
For the sulfonic group and the carboxyl that contain strongly hydrophilic in reactive dyestuffs and substantive dyestuff molecular structure, after dissolving in water all with the characteristics of negative charge, key is to destroy or seal the hydrophilic radical of dyestuff, reduce its hydration, then de-steady under the effect of flocculation agent, coagulation, flocculation. reach the purpose of separating from solution.Tongji University pollutes to control with Resource analysis National Key Laboratory and succeeds in developing TJ series discoloring agent recently, it has flocculation and precipitation dual function, can the various activity of effective elimination, the soluble dye such as acidity, percent of decolourization reaches 98-100%, for China's treatment of dyeing wastewater provides a good approach; This serial discoloring agent is to adopt guanidine like polymer, the hydrophilic radical of sealing dyestuff, by dye precipitated out.All can use this discoloring agent after biochemical treatment or in preprocessing process, for water processing establishment, there is no specific requirement.
4, other decolouring treatment technology
Except absorption, oxidation and coagulation decoloration, both at home and abroad ion-exchange decolouring, ultra-filtration membrane decolouring and biological decolouring technology are also studied.Wherein, the water-soluble dye that ordinary method is difficult to decolouring adopts the method processing of ion-exchange to be studied, and obtains certain progress.Its research concentrates on ion exchange resin and ion-exchange decolouring two aspects of fiber.
Can adopt the processing of decolouring of ultrafiltration or reverse osmosis technology for microsolubility dyestuff and the larger dyestuff component of molecular weight, but consider economic feasibility, at present ultra-filtration technique is multiplex processes in high density dye well dyeing waste-water, especially to the recycling of insoluble dyes.
Because the biodegradability of dye component in dyeing waste water is poor, the routine biochemistry method always can not be satisfactory aspect decolouring.Current solution, except taking pre-treatment to improve wastewater biodegradability, is mainly the good Decolourization Bacteria of screening and enhanced bio-treatment.With regard to it in general, biological decolouring there is no breakthrough, also must be combined with other treatment process.
In sum, synthesize and produce a kind of efficient, environment-friendly sewage purification and decoloration material that cost performance is excellent and apply it to tool in the processing of high chroma sewage and be of great significance.
Three, summary of the invention
The present invention is directed to the difficult problem of sewage decoloring, particularly dyeing sewage decoloration, aim to provide a kind of new sewage decoloring scavenging material, technical problem to be solved is given the material several functions, and Here it is, and collection decolours, flocculates, tangles, falls to all over the body, and removes COD simultaneously.
Described new sewage decoloring scavenging material is a kind of fiber base sewage decoloring scavenging material, and this material is mixed and formed by component (I) and component (II), and component (II) accounts for the 5-10% of total mass; Described component (I) is to be followed successively by by mass ratio the product (resin) that 36% formaldehyde solution, Dyhard RU 100, ammonium chloride, the property-modifying additive A reaction of 1.0～1.3:0.50～0.65:0.60～0.70:0.06～0.09 obtain, and described property-modifying additive A is sal epsom and magnesium chloride according to the mixture that mass ratio 2.0～3.5:8.0～6.5 ratios are mixed to get; Described component (II) is the natural fiber through the cation modifier modification.
Described natural fiber is selected from plant cellulose or animal protein fiber.
Described vegetable fibre is selected from one or more mixed plant fibers in shell (Pericarppium arachidis hypogaeae, nut-shell etc.), rice husk, cotton seed hulls, crop material, waste of flax, reed, bagasse, corn cob, rice bran, sawdust etc.
Described animal fibre is selected from one or more in chicken feather, goose feather, drake feather, the rabbit hair, wool etc. and lint thereof, short fiber and mixes animal fibres.
The modification of the protein fibre described in the present invention and cellulosic fibre, hydroxyl in the vegetable fibre Mierocrystalline cellulose is the energy partial ionization in water, make the cellulosic strip negative charge, due to the coloured sewage of printing and dyeing and cellulosic strip identical charges, have certain repulsive force, in sewage, colored component is difficult for being combined with Mierocrystalline cellulose, for this reason, by the cellulose graft cation group, make the cellulosic strip positive charge, the colored component that so just can improve in sewage is combined with Mierocrystalline cellulose fast, reaches the purpose that removes color.Cellulosic graft copolymerization can be divided into 3 classes: radical polymerization, ionic polymerization and condensation or addition polymerization, graft copolymerization can improve the structure and properties of Mierocrystalline cellulose and derivative thereof, give its new performance when can make the intrinsic advantage of Mierocrystalline cellulose not be destroyed, the modified cellulosic materials obtained by graft copolymerization, have the function of decolouring preferably.
Protein in animal fibre, containing-NH2 and=amino acid of the side groups such as NH, they can react by salt with epoxy season, the modified protein fiber is given its new performance, has adsorption bleaching function preferably.
The preparation method of this decolorizing purification material comprises the synthetic of component (I), preparation and the mixing of component (II), the synthetic of described component (I) is to add successively 36% formaldehyde solution of 1/3rd proportional quantities and the Dyhard RU 100 of proportional quantity in reactor, ammonium chloride, after stirring and dissolving, be warmed up to 40-50 ℃, reaction 0.5-1.5h, 36% formaldehyde solution that adds again property-modifying additive A and 1/3rd proportional quantities of proportional quantity, react again 1.5-2.5h at this temperature, 36% formaldehyde solution that finally adds remaining 1/3rd proportional quantities, thermopositive reaction is warming up to 70-85 ℃ naturally, reaction 3.0-4.0h, cool to room temperature, the reaction product obtained is component (I), the component (II) of component (I) and preparation is uniformly mixed is fiber base sewage decoloring scavenging material.
Product of the present invention is the pasty state fluid, and pH=6.0～7.0 are a kind of sewage decoloring scavenging materials that integrate the functions such as decolouring, flocculation, entanglement, removal COD.Product is rich in the high-density positive charge, aqueous synthetic-resin and modification adsorbing fiber etc., have the special efficacy that removes the sewage color, purifies water, on aqueous synthetic-resin, a large amount of positively charged ions can make electric charge on the anionic dyestuff molecule be neutralized and unstability, flocculation, sedimentation fast.Tangle and form stable flocs unit by the absorption of fibrillation fiber, mutually tangle, can accelerate separate and subside speed, a large amount of organic or inorganic gel component of disperseing adsorbing fiber absorption that is modified in water body, tangle agglomerating, together with floss, from water body, separate fast, reach the purpose that removes the sewage color, removes COD of sewage, purifies water.Water reuse in can realizing, reduce sewage and reduce discharging, and improves water body environment.Product of the present invention has that the efficiency of disposing of sewage is high, mud is few, and the aftertreatment cost is low, the expense of reduce mud transportation, non-secondary pollution, Nonpoisonous, non-environmental-pollution.
The present invention passes through the selection of raw material, the optimization of technique, utilized discarded stalk, waste feathers plumage silk etc. to reduce production cost, improved the flocculation ability of product, have that preparation process is easy to control, simple to operate, product stable, produce while being applied to sewage disposal that flco is large, settling velocity fast, percent of decolourization and COD clearance advantage high and with low cost, the decolouring that can be widely used in various dyeing waste waters is processed and is reduced COD.
Product of the present invention has following advantage:
1) raw material sources are extensive, and preparation or extraction are convenient, cheap.Applied range, be used in directly, the coloured sewage of printing and dyeing and other coloured sewage disposals such as active, acidity and dispersed dye.
2) flocculation time short (0.5～1min flocculation), form flocks fast, and the closely knit volume of throw out is little, is easy to filter-press dehydration, the reduce mud trucking costs.
3) this product is rich in the high-density positive charge, so, when water temperature is low, still can keep stable treatment effect.
4) this product is rich in primitive fiber hole sorbing material, broad variety organic composition in adsorbable removing water body, high-efficiency broad spectrum.
5) low cost product of the present invention, easy and simple to handle, take up an area less, processing efficiency is high.
6) product Nonpoisonous, non-environmental-pollution of the present invention, apply this product non-secondary pollution, belongs to environment-friendly sewage purification and decoloration novel material.
7) production technique of the present invention is simple, and top temperature is not higher than 80 ℃, with low cost.
8) have unique flocculation decoloration, the ability that purifies water, the percent of decolourization of sewage is reached more than 93%, COD value clearance exceeds more than 10% than prior art, and water reuse in can realizing reduces sewage discharge.
9) the product suitability is wide, both can be applicable to dyeing sewage decoloration and has processed, and also is applicable to the purifying treatment in the waters such as river course, streams, lake, ecological water seedbed, natural landscape waters and water factory's intake.
Four, embodiment
Non-limiting examples is described below.For sake of convenience, hereinafter to be referred as mass parts, be part.
(1) preparation of property-modifying additive A
Getting 725 parts, 275 parts, sal epsom and magnesium chloride mixes and get final product.
(2) preparation of modified fibre
1, the preparation of modified-cellulose vegetable fibre
By the cellulose graft cation group, make positively charged, can significantly improve in sewage electronegative dyestuff fast with the plain combination of sorbent fibers, reach the purpose of decolouring from water.
The preparation of modified-cellulose vegetable fibre: cellulosic graft copolymerization can be divided into 3 classes: radical polymerization ionic polymerization and condensation or addition polymerization graft copolymerization can improve the structure and properties of Mierocrystalline cellulose and derivative thereof, and the present invention can obtain by Mierocrystalline cellulose and epoxy chloropropane, dimethylamine reaction intermediate.(referring to " polymer material science and engineering " the 23rd volume fourth phase of July in 2007 " performance of carboxymethyl cellulose and acrylic amide graft copolymerization and multipolymer " author: Yang Fang Li Gang etc.).
2, the preparation of modified protein fiber
Some contain-NH in animal fibre
2with the amino acid of=side groups such as NH, they can react by salt with epoxy season, and the modified protein fiber is given its new performance, has the function of decolouring preferably.Protein fibre and cation modifier-epoxy season is seen figure by the reactant salt equation: (referring to the 31st volume fourth phase of " textile journal " April in 2010 " reactive chitosan quaternary ammonium salt synthetic and the application in the tussah silk antibacterial finish thereof " author: Lu Yanhua Liu Zhi plum etc.)
(3) preparation of decolorizing purification material
1, (1) adds successively 33.3 part of 36% formaldehyde solution, 50 parts of Dyhard RU 100s, 60 parts of ammonium chlorides in reactor, after stirring and dissolving, is warmed up to 40 ℃, reaction 1h, add again 33.3 part of 36% formaldehyde solution and 6 parts of property-modifying additive A, react again 2h at this temperature, finally add 33.4 part of 36% formaldehyde solution, thermopositive reaction is warming up to 70 ℃ naturally, reaction 3.0h, cool to room temperature obtains component (I), the transparent thick liquid of appearance colorless, pH=6.0～7.0,20 ℃ proportion 1.15g/mL.
(2) production equipment is the same, and above-mentioned (1) products obtained therefrom and 11 parts of modified plant fibers (fibrillation vegetable fibre through the cation modifier modification) add in reactor successively, and the normal temperature stirring at low speed, mix and obtain product.
Product is the fibre-bearing viscous fluid, pH=6.0～7.0.
Formulary
| Sequence number | Title | Umber |
| 1 | 36% formaldehyde | 100 |
| 2 | Property-modifying additive A | 6 |
| 3 | Dyhard RU 100 | 50 |
| 4 | Ammonium chloride | 60 |
| 5 | Modified cellulose fibre | 11 |
2, (1) adds successively 43 part of 36% formaldehyde solution, 65 parts of Dyhard RU 100s, 70 parts of ammonium chlorides in reactor, after stirring and dissolving, is warmed up to 50 ℃, reaction 1h, add again 43 part of 36% formaldehyde solution and 9 parts of property-modifying additive A, react again 2h at this temperature, finally add 44 part of 36% formaldehyde solution, thermopositive reaction is warming up to 85 ℃ naturally, reaction 4.0h, cool to room temperature obtains component (I), and outward appearance is the water white transparency thick liquid, pH=6.0～7.0,20 ℃ proportion 1.15g/mL.
(2) production equipment is the same, and above-mentioned (1) products obtained therefrom and 27.4 parts of modified protein fibers (fibrillation is through the cation modifier modification) add in reactor successively, and the normal temperature stirring at low speed, mix and obtain product.
Product is fibre-bearing pasty state fluid, pH=6.0～7.0.
Formulary
| Sequence number | Title | Umber |
| 1 | 36% formaldehyde | 130 |
| 2 | Property-modifying additive A | 9 |
| 3 | Dyhard RU 100 | 65 |
| 4 | Ammonium chloride | 70 |
| 5 | The modified protein fiber | 27.4 |
3, (1) adds successively 40 part of 36% formaldehyde solution, 58 parts of Dyhard RU 100s, 65 parts of ammonium chlorides in reactor, after stirring and dissolving, is warmed up to 45 ℃, reaction 1h, add again 40 part of 36% formaldehyde solution and 8 parts of property-modifying additive A, react again 2h at this temperature, finally add 40 part of 36% formaldehyde solution, thermopositive reaction is warming up to 78 ℃ naturally, reaction 3.5h, cool to room temperature obtains component (I), the transparent thick liquid of appearance colorless, pH=6.0～7.0,20 ℃ proportion 1.15g/mL.
(2) production equipment is the same, and above-mentioned (1) products obtained therefrom and 18 parts of modified cellulose fibres (fibrillation through the cation modifier modification) add in reactor successively, and normal temperature carries out stirring at low speed, mixes and unanimously obtains product.
Product is fibre-bearing pasty state fluid, pH=6.0～7.0.
Formulary
| Sequence number | Title | Umber |
| 1 | 36% formaldehyde | 120 |
| 2 | Property-modifying additive A | 8 |
| 3 | Dyhard RU 100 | 58 |
| 4 | Ammonium chloride | 65 |
| 5 | Modified cellulose fibre | 18 |
(4) Application Example
This decolorizing purification material send relevant enterprise to carry out the sewage decoloring purifying treatment, and its treatment effect is the discoloring agent in use far above enterprise.Concrete outcome sees the following form.
Annotate: above tested sewage is the sewage produced in the daily production process of factory separately.Get representative sewage 1L, add product 1mL of the present invention, stir 3min, get supernatant liquor after standing, test colourity, calculate percent of decolourization %, COD and COD clearance.
(5) appendix
The testing method of colourity, percent of decolourization and COD and COD clearance.
1, colourity testing method: trade effluent by certain extension rate, is diluted with water to and approaches when colourless, record extension rate, mean the colourity of this water sample with this, unit times.Instrument: the 50ml color-comparison tube, it is consistent that its graticule height is wanted.Step: 1, get 100～150 clarification water samples and put in beaker, take white porcelain plate as background, observe and describe its color category.2, divide the water sample of getting clarification, be diluted with water to different multiples, minute get 50ml to be placed in respectively the 50ml colorimetric cylinder, pipe bottom lining one white porcelain plate, observe from top to bottom the color of water sample after diluting, and compare with distilled water, until just do not see color, record extension rate now.
2, percent of decolourization (%) method of calculation:
Front Colority of Sewage Water is processed in (decolouring is processed front Colority of Sewage Water-decolouring and processed the colourity of rear water)/decolouring
3, the COD testing method: applied chemistry oxygen requirement (COD) Quick testing instrument 5B-3C is measured, by Lanzhou Lian Hua Environmental Protection Technology Co., Ltd, manufactured, step: prepare on empty cooling tank that number side reaction pipe is placed in cooling frame → prepare but to measure 2.5ml distilled water to be added to " 0 " number reaction tubes → measure respectively each water sample 2.5ml and to join successively other reaction tubess → with the 1ml batchmeter, add 0.7ml special use consumptive material D reagent → with the 5ml batchmeter, add the special-purpose consumptive material E reagent of 4.8ml and mix → each reaction tubes is put into successively the hole of clearing up of digestion device to each reaction tubes successively to each reaction tubes successively, cover spray guard and press " 10 minutes " key (being preheating in advance 165 ℃) → open photometer switch, it is carried out to 10 minutes timing alarms of preheating → digestion device point out → is put into each sample on the air cooling groove of cooling frame successively, then press 2 minutes timing alarms of " 2 minutes " key → digestion device prompting → successively to adding 2.5ml distilled water in each reaction tubes and mixing → each reaction tubes is put in the water-cooling groove of cooling frame (adding tap water in advance in water-cooling groove), and press 2 minutes timing alarms of " 2 minutes " key → digestion device and point out → each reaction tubes is taken out from water-cooling groove, and solution is poured into successively in the cuvette of reference numeral.Adjust the photometer wavelength to 610nm, selecting optical path is 30mm cuvette → " 0 " number cuvette is put into to cell, close upper cover, according to photometric working method, regulate T/100% → other each cuvettes are put into successively to cell and closed upper cover, record the COD value of each sample.
4, COD clearance (%) method of calculation: front COD of sewage is processed in (decolouring is processed front COD of sewage-decolouring and processed the COD of rear water)/decolouring.
Claims (4)
1. a fiber base sewage decoloring scavenging material, it is characterized in that: this material is consisted of component (I) and component (II), and component (II) accounts for the 5-10% of total mass; Described component (I) is to be followed successively by by mass ratio the product that 36% formaldehyde solution, Dyhard RU 100, ammonium chloride, the property-modifying additive A reaction of 1.0～1.3:0.50～0.65:0.60～0.70:0.06～0.09 obtain, and described property-modifying additive A is sal epsom and magnesium chloride according to the mixture that mass ratio 2.0～3.5:8.0～6.5 ratios are mixed to get; Described component (II) is the natural fiber (plant and/or animal) through the cation modifier modification.
2. material according to claim 1, it is characterized in that: described vegetable fibre is selected from one or more mixed plant fibers in shell, rice husk, cotton seed hulls, crop material, waste of flax, reed, bagasse, corn cob, rice bran, sawdust.
3. material according to claim 1 is characterized in that: described animal fibre is selected from one or more in chicken feather, goose feather, drake feather, the rabbit hair, wool and lint thereof, short fiber and mixes animal fibres.
4. the preparation method of a kind of fiber base sewage decoloring scavenging material as claimed in claim 1, comprise the synthetic of component (I), preparation and the mixing of component (II), it is characterized in that: the synthetic of described component (I) is to add successively 36% formaldehyde solution of 1/3rd proportional quantities and the Dyhard RU 100 of proportional quantity in reactor, ammonium chloride, be warmed up to 40-50 ℃ after stirring and dissolving, reaction 0.5-1.5h, 36% formaldehyde solution that adds again property-modifying additive A and 1/3rd proportional quantities of proportional quantity, continue reaction 1.5-2.5h under 40-50 ℃, 36% formaldehyde solution that finally adds remaining 1/3rd proportional quantities, be warming up to 70-85 ℃, reaction 3.0-4.0h, cool to room temperature, the reaction product obtained is component (I), described property-modifying additive A is sal epsom and the magnesium chloride mixture that the ratio of 2.0～3.5:8.0～6.5 is mixed to get in mass ratio.
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