CN104057096B - In biological adsorption solution, valuable metal ions prepares the method for superfine powdery material - Google Patents
In biological adsorption solution, valuable metal ions prepares the method for superfine powdery material Download PDFInfo
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- CN104057096B CN104057096B CN201410283723.7A CN201410283723A CN104057096B CN 104057096 B CN104057096 B CN 104057096B CN 201410283723 A CN201410283723 A CN 201410283723A CN 104057096 B CN104057096 B CN 104057096B
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- biological adsorption
- superfine
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000035922 thirst Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention proposes valuable metal ions in a kind of biological adsorption solution and prepares the method for superfine powdery material, comprise: the pH value of the solution of adjustment metal ion, biomass adsorbent is added to solution, the addition of described biomass adsorbent is often liter of solution 0.1-150 gram, stir after 5-1200 minute, filter; Afterwards after washing 2-3 time, dry in the hot bellows of 20 degrees Celsius to 80 degrees Celsius, it is carried out pyrolysis in tube furnace, and obtain pressed powder under passing into protective gas, carbon dioxide or active gases; Grinding obtains superfine metal powder material.Present invention achieves the higher value application new way of the various industrial wastewaters containing low concentration valuable metal ions, by this technological means that is economic, that remove the metal ion in low-concentration industrial waste water efficiently of biological adsorption, combine with the preparation production of ultrafine function powder material and application industry, have that absorption is fast, cost is low, flour mill flow is short, output is large, easily go up the outstanding advantages such as scale.
Description
Technical field
The present invention relates to the Industry Waste water purification of metal ion and the novel preparation method of superfine metal or alloy and oxide powder material, in particular, provide a kind of new solution making existing industrial waste water purifying processing procedure significantly increase surcharge and reduce costs.
Background technology
The industries such as mining, ore dressing, metallurgy, intermetallic composite coating and recovery all can produce a large amount of valuable metals that is rich in, and (in the present invention, valuable metal refers in particular to except alkali metal ion is if lithium, sodium, potassium and alkaline-earth metal ions are as other metal cations except magnesium, calcium etc., as copper, iron, zinc, manganese, nickel, cobalt, lead, silver, indium, chromium, bismuth, rare earth, titanium, zirconium, vanadium, niobium, tantalum etc.) industrial wastewater of ion, if these waste water do not add control, do not add the rationally extraterrestrial row of process, serious environmental pollution, the wasting of resources will be caused, directly have influence on the sustainable development of these industries.
In order to solve the qualified discharge problem of the industrial wastewater containing valuable metal ions, the method for treating water of usual employing has moderate water-cut stage, sulfurization-precipitation method, coagulation sedimentation etc., have that process is convenient, efficiency fast, strong adaptability, comparatively economic dispatch advantage, such as moderate water-cut stage adopts NaOH, sodium carbonate, calcium hydroxide or calcium oxide, calcium carbonate, magnesium carbonate, the alkaline reagent such as magnesium hydroxide to be added in waste water, makes that the acid in waste water is neutralized, valuable metal ions precipitated one-tenth solid slag form and being separated concentrates; Sulfide precipitation then adopts vulcanized sodium, NaHS, hydrogen sulfide, Polymer Synthesizing sulfide etc. as precipitation reagent, has the advantage such as deep, thorough of deposition removal metal ion; To be then the cotton-shaped iron hydroxide (aluminium) that adopts high price molysite, aluminium salt to be formed as ferric sulfate, iron chloride, aluminum sulfate, aluminium chloride etc. or Polyferric Sulfate, the poly-hydrolysis such as aluminium and iron content biologic product (Biology-iron) comparatively popular in recent years remove the hydrolytic precipitation thing reunion sedimentation of the valuable metal ions absorption in waste water or valuable metal ions and sweeping along coagulant precipitation, thus reach the object of water purification.The shortcoming of above processing method is also obvious, such as be difficult to up to standard to the metal removal degree of depth of some waste water, especially the how Non-toxic safe handling of a large amount of moisture sediment produced, and often need the residual problem of chemical reagent in water of adding several times to ensure the purification of water treatment up to standard more, from the whole process angle of wastewater treatment, in fact these methods remain in the problem being much difficult to overcome.From the theory of the utilization of resources, more than process the method for industrial wastewater, substantially only water purification and reuse is paid close attention to, dangerous substance valuable metal resource in water being then still considered to a kind of hostile environment is transferred in sediment, and do not obtain rational recycling, obviously, this is not an advanced person, reasonably Industrial Wastewater Treatment thinking and the choice of technology.If can by industrial waste water purifying reuse, and valuable metal resource wherein also can obtain rationally, reclaims easily and realize higher value application, is so just only concerned about that the reuse of water resource and the way of purification are come more advanced and more reasonable than traditional.Obviously, how economical from industrial wastewater, effectively extract and reclaim valuable metal ions, be then be related to above Advanced Idea and the whether practicable key of technical thought.
According to above thinking, have and above precipitation slag is sent to non-ferrous metals smelting works enter its existing extraction process production line together practice as batching, but due to water content in precipitation slag is large, valuable metal content is too low and these valuable metals as the prices such as lead, zinc, cadmium, the arsenic generally shortcoming such as lower, make this roadmap in fact not have operability economically.Add the valuable metal extracting these low contents from precipitation slag, turn increase extra equipment investment and technique lengthening, therefore, impracticable in the industrial practice pilot scale of reality.And if can develop and design a kind of method, can not only by the heavy metal ion efficient removal purification in industrial wastewater, can also simultaneously easily, short route ground, simply, little amplitude increases running cost and equipment cost extraly, can also concentrate out these heavy metal ion higher degree, the industrial wastewater be so just expected to realize economy veritably, processing metal ion efficiently.
Directly valuable metal ions is reclaimed from industrial wastewater, the technology of comparative maturity has the technology such as ion-exchange and absorption, UF membrane, electrodialysis, and these technology to be particularly suitable in the industrial wastewater of low-concentration metallic ion reclaiming comparatively cost-effectively, enrichment and extraction metal.Ion-exchange-resin process is enriched in metals ion from industrial wastewater, has been very ripe technology, but ion-exchange-resin process also exists more significant problems:
1) resin is expensive;
2) the selective or anti-interference of resin extraction metal ion is not so good;
3) finite capacity of resin concentration metal ion;
4) micropore of resin easily blocks and lost efficacy.Namely resin property is very sensitive to the solid micelle, floccule, organic substance etc. that are mingled with in industrial wastewater, its surperficial macropore or micropore easily by the various complicated ingredient in industrial wastewater and impurity block and lose or weaken the performance of enriched in metals ion;
5) preservation of resin is more exquisite, generally can not dehydration (overdrying);
6) process that how safe, innoxious the resin after scrapping is, not yet finds a good method.So from full-range angle, ion-exchange also exists the problem such as environment is unfriendly.Absorption rule mainly adopts active carbon, also exists and problem like resinae the adsorption and enrichment of valuable metal ions, expensive, selective enrichment is poorer, the adsorption capacity generally problem such as lower, post processing trouble.Then there is the shortcomings such as facility costliness, maintenance cost is high, fenestra easily blocks in UF membrane, equally, electrodialysis also exists the problems such as cost is high, maintenance requirement is high.
Compare above all kinds of technology, biological adsorption then has quite outstanding comprehensive advantage---cheap, be easy to get, the advantage such as advantages of good adsorption effect, alternative raw material are many, pure natural raw material is environmentally friendly.Particularly along with the research and development of Past 30 Years, the mechanism that people occur biological adsorption and law study obtain more deep, understand and systematization, both provide a large amount of abundant knowledge to the exploitation of the raw-material source can selected as biological adsorption and method of modifying to support and practice accumulation, make this new material with outstanding comprehensive advantage and new technology be expected to have given play to its original and special effect in the high efficiente callback utilization and circular regeneration of Industry Waste water purification and valuable metal resource.The biomass material that can use on a large scale as biological adsorption material industrialization and modification method for preparing should have following feature:
1) biomass material wide material sources, abundant, sufficient and cheap, preferably present stage is seldom by higher value application;
2) method of modifying simply, safely, effectively, and had better not use poisonous, harmful chemical reagent, and also do not produce poisonous, harmful accessory substance, whole process is environmentally friendly;
3) adsorptive selectivity is good, and adsorption capacity is large, and adsorption rate is fast, and adsorbed material is reclaimed in easy desorb;
4) the biological adsorption agent material made is rotten and easily keeping not easily.
There are the various biomass materials of above feature after various chemical modification, just may obtain adsorbant function material metal ion to better adsorption and enrichment usefulness, for the purified treatment of the industrial wastewater of industry-by-industry and valuable material wherein as the adsorption and enrichment recycling of valuable metal ions.To biological adsorption method that is economic like this, cheap, enriched in metals ion efficiently, in the decontamination process of a lot of industrial wastewater, should be got more and more, applied more and more widely.
Such as disclosed in patent (granted patent number: ZL201210019530.1), modified chemical method prepares biomass absorbent agent material; The preparation method of this biomass absorbent agent material mainly comprises: 1. get biomass material, washes, for subsequent use; 2. the biomass material after washing and alkali, water are carried out being uniformly mixed reaction according to the mass ratio of 1:0.05-0.2:0.5-2, stir 12-24 hour, filter, obtain solid product, wherein, described alkali is one or two or more kinds mixing in lithium, sodium, potassium, calcium, the oxide of magnesium, hydroxide, carbonate, bicarbonate or ammonium carbonate, carbonic hydroammonium, urea, ammoniacal liquor; 3. above solid product is washed with water until neutral, feeding vacuum drying oven, be 60-120 DEG C of drying in temperature, drying object smashed, sieve, namely the following powder collection of 40 order can be used as biomass adsorbent of the present invention, specifically see ZL201210019530.1 description.Although this invention merely stated that the preparation method carrying out biomass absorbent agent material using garlic as biomass material, adopt marine alga, vinasse, tangerine slag, apple skin etc. containing-COOH ,-SH ,-NH
2,-(phenol) OH isoreactivity functional group other substitute biomass material also can generate the biomass absorbent agent material with suitable adsorption effect according to same ratio.
From whole process, the adsorbent that adsorption and enrichment is stripped of valuable metal ions how economical, carry out post processing effectively and reasonably, safely, process the method being applied to industrial wastewater also has important impact.Generally speaking, the thinking easily expected is adopted by the metal ion of adsorption and enrichment the method for desorb to reclaim to concentrate, again by additive method as electrolytic deposition etc. realizes the further extraction of metal ion, sorbent material then can return to the purified treatment being used further to industrial wastewater.Should say, such way is industrially feasible and has good economic benefit.But consider the low cost of biological adsorption agent itself and ready availability, we disclose the Utilizing question that another kind of technical thought carrys out to solve more dexterously metal ion after absorption in this patent, and its basic ideas are the powder body materials biomass adsorbent adsorbing valuable metal ions being transformed into various superfine function through the technological approaches of high temperature pyrogenic process or low temperature wet method.Particularly, pyrogenic process method is ined succession after adsorbent washs together, dries by adsorption and enrichment to the metal ion on biological adsorption agent material, high temperature thermal decomposition under controlled atmosphere, remove all or part of for living beings wherein, thus obtain the metal of higher degree or the chemical combination powder of metal compound powders or metal and residual biomass catabolite.Control the condition of biological adsorption and the process conditions of thermal decomposition well, just can obtain the superfine metal with the physicochemical characteristics such as heterogeneity and different grain size or alloy and oxide powder.Wet process is then, to the biomass adsorbent powder dispersion of valuable metal ions be enriched in aqueous medium, add reproducibility chemical reagent as hydrazine hydrate, potassium borohydride, sodium hypophosphite, ascorbic acid, formaldehyde etc., make metal ion be reduced into corresponding metal dust or alloy powder.
Adopt above technical thought to prepare metal or alloy and the oxide powder of these Ultra-fines, generally mainly there are these following advantages:
1) this method can economic from the low-concentration industrial waste water of metal ion, biosorption process enriching and recovering metal element effectively, both the purified treatment of waste water had been achieved, reclaim again metals resources wherein, and biological adsorption agent also can utilize the discarded object of various living beings to make raw material, thus achieve comprehensive benefit and the resource reusing object of " arrow three is carved ".
2) ultrafine function powder material prepared of this method, has that outstanding technique is simple, flow process is short, powder size is tiny, preparation technology's simple and fast, a many advantages such as with low cost.Because metal is absorbed and fixed in the active function group on biological particles surface in the form of an ion and first, therefore, in follow-up washing, dry, the living beings structure that the superfine metal formed in low-temperature reduction process in high temperature thermal decomposition or aqueous medium or alloy and oxide powder particle are easily stayed by some or all of decomposition and skeleton are to keeping apart, process dispersion, discrete state, even if in the case of a high temperature or be also less likely to occur common reunion and phenomenon of growing up in aqueous medium, the high activity being very beneficial for sub-micron-powder material is preserved.
3) this legal system is standby or produce that superfine metal or alloy and oxide powder particle are not easy to reunite and granularity is tiny, and thing phase constituent easily regulates.Regulate by the amount of adsorbing metal ions, by the kind of absorption many kinds of metal ions and quantitative proportion by absorbing process parameter, and the technological parameter condition such as reduction concentration-temperature and time in the atmosphere of thermal decomposition, temperature and time or aqueous medium, the superfine powdery materials such as the metal of different grain size and composition characteristics, alloy, oxide can be obtained.Visible the method has very strong adaptability and flexibility, especially the powder size prepared can be easy to just keep Ultra-fine as the sub-micron even mid-scale level of nanometer, and because it is first absorbed and fixed at the feature of the biomass adsorbent surface of solids, even if being also difficult to adjacent to each other, sintering, Caragana seed pests composition in thermal decomposition (or reduction) process is big particle, the preparation and the production that are therefore very suitable for all kinds of ultrafine function powder material are selected.
4) the method is expected to become a kind of general, the preparation of practical superfine function powder is newly selected, according to preparing a large amount of accordingly, types of functionality powder body material, under the prerequisite not affecting its main application function, be expected to adopt high purity metal for substituting those, alloy, the superfine powdery materials such as oxide, thus greatly save metal consumption and the performance of powder body material can also be kept simultaneously, such as catalysis material, this dispersion, being fixed on superfine powdery material on biomass solid or its thermal decomposition residual solid thing thirsts for having than the better catalytic activity of pure superfine powdery material and reactivity, such as do electromagnetic shielding material again, the superfine powdery material these being mingled with biomass solid or its thermal decomposition residual solid thing is used for sizing mixing, brush and make electromagnetic shielding material, also be expected that there is similar electromagnet shield effect and but there is obviously much lower powder preparation cost, the coating of sterilization sanitary ceramics or hospital's materials for wall is such as used for again as the raw material of sterilizing industry.The application of various functions powder body material and so on, the function powder material all can attempting the specific characteristic prepared by this method substitutes or Some substitute, thus greatly saves entity, the use amount of high-purity metal or alloy or oxide ultra fine powder body material and cost.
5) the method has above significant many advantages, both can be used alone adsorbing metal ions in the aqueous solution of high pure metal preparation of reagents and through thermal decomposition to prepare ultrafine function powder material, also may be used for metal biosorption enrichment in industrial wastewater thus also originally prepared ultrafine function powder material in thermal decomposition or aqueous medium.Consider from the full-range increment of Industrial Wastewater Treatment, and the outstanding feature of new method disclosed in this patent and comprehensive advantage, patent inventor is more prone to rear one application, because the raw material preparing ultrafine function powder material just comes from industrial wastewater, just greatly the cost of raw metal has been saved from source, the general selective absorption accumulation ability preferably of biological adsorption agent itself is expected to make the valuable metal ions by adsorbing have higher degree simultaneously, thus the ultrafine function powder material being conducive to preparing higher degree therefore, this technical thought is very beneficial for biosorption process to be had significant Technological Economy competitive advantage and obtains and promote the use of widely in industrial wastewater treatment because its cost greatly reduces, thus be conducive to the consciousness of the purified treatment of every profession and trade metal ion waste water, retrain and promote practitioners' active of these industries by economic lever, consciously reduce the illegal outer row of metal ion industrial wastewater.
Generally speaking, the practical experience of this new technology thinking is high-valued recycling and the recycling of the industrial wastewater of metal ion, provide a kind of brand-new process theory and the choice of technology, be expected metal (alloy or the oxide) superfine powdery material of the high additive value prepared by biological adsorption-thermal decomposition method or biological adsorption-solution reduction, significantly improve economy and the competitive advantage of whole metal ion industrial wastewater treatment flow process.These powder body materials prepared often well can be applied in fields such as coating, catalysis, electronic conduction slurry, pigment, pottery, magnetic materials, for these industrial application provide sufficient powder function raw material, thus bring extra increment to the technical process of whole biological adsorption concentration method process industrial wastewater, the processing cost being greatly conducive to all types of industries waste water of metal ion reduce and biological adsorption method purifying water process field quick, to put it over application widely.Metal (alloy or the oxide) superfine powdery material that above method prepares, than existing various metal (alloy or oxide) superfine powdery material except the competitive advantage in cost of manufacture also, perhaps the active and function of the better special reaction of various superfine powdery materials prepared by the inventive method can also be had (because of by the original position confinement reduction of adsorbing metal ions or chemical combination, effectively can stop the unordered reunion between fine particle), thus obtain the material product that special application and making make new advances.
Summary of the invention
Key technical problem to be solved by this invention is, change traditional main removing of valuable metal ions around low concentration in industrial wastewater and the traditional method of purifying waste water, then removing of low concentration valuable metal ions in industrial wastewater is produced with the preparation of the ultrafine function powder material of high additive value the new technology closely integrated, form the reuse of collection water purification, metal enrichment, the short route that the various functions such as powder preparation are integrated, the new technological process of high additive value, also good promotion and progradation must be played for the widespread adoption of this new technology of biological adsorption in actual industrial waste water treatment.Because this invention has also solved how to realize the problem of higher value application from containing the biological adsorption agent material of adsorption and enrichment valuable metal ions the industrial wastewater of low-concentration metallic ion.
The invention discloses a kind of new technology thinking, change traditional being transferred in residue by metal ion abandon or give second extraction through troublesome operation again, or metal ion is concentrated and the method for the conventional concentrated utilization such as electrolytic deposition and affect the way of full-range performance driving economy, and metal ion is got up by the method enrichment of biological adsorption and through absorption, dry, the high temperature thermal decomposition under controlled atmosphere or the reduction in solution medium and prepare ultra-fine metal (alloy or oxide) superfine powdery material.This powder body material can be metal (alloy or the oxide) occurrence status of higher degree, also can be the occurrence status of the metal (alloy or oxide) remaining with biomass solid in various degree or its thermal decomposition product.Above superfine powdery material can further according to industry-by-industry application require and directly be supplied as raw material use or through various processing as compacting, sinter block into and use.
The first object of the present invention is that proposing valuable metal in a kind of biological adsorption waste water prepares the method for superfine metal powder material, is characterized in that, said method comprising the steps of:
The solution of step one, acquisition metal ion, the pH value range adjusting described solution is 2-12, biomass adsorbent is added to solution, the addition of described biomass adsorbent is often liter of solution 0.1-150 gram, stir after 5-1200 minute, filter and obtain the biomass adsorbent powder being enriched with metal ion;
Step 2, by the biomass adsorbent powder being enriched with metal ion that obtains after washing 2-3 time, dry in the hot bellows of 20 degrees Celsius to 80 degrees Celsius, obtain the biological adsorption agent oven dry powder of load metal ion;
Step 3, by load, the biological adsorption agent of metal ion is dried powder and is evenly laid in iron boat or porcelain boat, puts into heating furnace and carries out pyrolysis, obtain pressed powder; Wherein, the pyrolysis time is 10-1500 minutes, and pyrolysis temperature is 200-1000 degree Celsius, and described pyrolysis is passing into protective gas, or carries out under the environment passing into carbon dioxide or active gases;
Step 4, pressed powder carried out fragmentation, screening, classification, obtain superfine metal powder material.
Preferably, described protective gas is hydrogen, argon gas, nitrogen or carbon monoxide etc.; Described active gases is air.
Preferably, described heating furnace is in cabinet type closed electric furnace or chain type at the uniform velocity stepping thermal decomposition tube furnace.
The second object of the present invention is that proposing valuable metal in a kind of biological adsorption waste water prepares the method for superfine metal powder material, is characterized in that, said method comprising the steps of:
The solution of step one, acquisition metal ion, the pH value range adjusting described solution is 2-12, biomass adsorbent is added to solution, the addition of described biomass adsorbent is often liter of solution 0.1-150 gram, stir after 5-1200 minute, filter and obtain the biomass adsorbent powder being enriched with metal ion;
Step 2, by the biomass adsorbent powder being enriched with metal ion that obtains after washing 2-3 time, dry in the hot bellows of 20 degrees Celsius to 80 degrees Celsius, obtain the biological adsorption agent oven dry powder of load metal ion;
Step 3, the solution that the biological adsorption agent of metal ion dries powder by load be ratio and the concentration of 1:1-10 according to mass ratio is the reproducibility reagent of 0.1-10M mix, and described reducing agent reagent is hydrazine hydrate, potassium borohydride, sodium hypophosphite, ascorbic acid, formaldehyde, sodium sulfite; Be react 10-1000 minute under the cryogenic conditions of 20 degrees Celsius to 400 degrees Celsius in temperature, metal ion is reduced;
Step 4, step 3 is reacted after the solution that obtains carry out filtering, wash, dry and obtain superfine metal powder material.
Preferably, after the solution that the biological adsorption agent of metal ion dries powder by load be ratio and the concentration of 1:1-10 according to mass ratio is the reproducibility reagent of 0.1-10M mixes, the pH value of adjustment mixed solution is 9-12.5.
Preferably, the stirring in described step one is mechanical agitation or air stirring.
Preferably, described superfine metal powder material is silver, metal oxide, or described superfine metal powder material is the composite powder material of metal or alloy and biomass adsorbent or biomass adsorbent pyrolysis residual components.
In biological adsorption waste water as described in any one of claim 1-5, valuable metal prepares the method for superfine metal powder material, it is characterized in that, also comprises the preparation process of biomass adsorbent before described step one, and the preparation process of described biomass adsorbent comprises:
1) get biomass material, wash;
2) biomass material after washing and alkali, water are carried out being uniformly mixed reaction according to the mass ratio of 1:0.05-0.2:0.5-2, stir 12-24 hour, filter, obtain solid product, wherein, described alkali is one or two or more kinds mixing in lithium, sodium, potassium, calcium, the oxide of magnesium, hydroxide, carbonate, bicarbonate or ammonium carbonate, carbonic hydroammonium, urea, ammoniacal liquor;
3) above solid product is washed with water until neutral, feeding vacuum drying oven, be 60-120 DEG C of drying in temperature, drying object smashed, sieves, obtain the following particle of 40 order as biomass adsorbent.
Preferably, described biomass material comprises containing-COOH ,-SH ,-NH
2,-(phenol) biomass material of OH isoreactivity functional group.
It should be noted that, in the biological adsorption waste water proposed for the present invention first object, valuable metal is prepared in the method for superfine metal powder material, described superfine powdery material, the composite powder material of the product obtained under protective atmosphere (passing into protective gas) mainly metal (or alloy) and biomass adsorbent pyrolysis residual components; (pass into air) in air atmosphere decomposing what obtain is then metal oxide powder (except silver powder); In the biological adsorption waste water proposed for the present invention second object, valuable metal is prepared in the method for superfine metal powder material, the superfine powdery material obtained the then mainly composite powder material that forms of metal (or alloy) and biomass adsorbent.
The beneficial effect that the present invention is compared to the prior art had is:
Present invention achieves the higher value application new way of the various industrial wastewaters containing low concentration valuable metal ions, this invention gathered the new approaches and new concept that biomass absorbent, industrial waste water purifying, the short route of metal ion superfine function powder, the feature such as simple fully utilize at interior new type resource, break traditional with regard to water purification water purification, with regard to powder body material preparation the respective segmentation of preparation independently different field do not exchange, do not have the conservative manner of close cooperation.The appearance of this invention achievement, new promotion will be brought respectively for these three applications, that is: the metal ion in traditional industry waste water is expected to concentrate by biological adsorption enrichment that this is simple, cheap method is used to prepare the ultrafine function powder material producing high additive value, superfine powdery material application then obtains abundant, sufficient, inexpensive metal ion source resource, biological adsorption then by above two fields high value-added application and make itself to obtain high additive value and applying on a large scale, more fully demonstrate the synthetic competitive advantages of its uniqueness, in a word, biosorption technology is used through above one, really achieve the effect of " arrow three is carved ".
The present invention is that all subsequent treatment of biosorption process from industrial wastewater after adsorption and enrichment valuable metal ions that relate to provide a remarkable value-added short-cut method, for this economy of biological adsorption, efficient method for treating water provide a good new source, be different from traditional simple burning facture (secondary pollution of containing metal flying dust and the combustion energy of at substantial may be caused), also need not desorb reuse repeatedly (troublesome poeration, and the value of metal recovery is general not high).The method makes the various valuable metal ions of the low concentration in industrial wastewater change one's identity suddenly rapidly from the state being close to " discarded object " and become the huge metals resources source of production " function powder material ", is expected as industry-by-industry provides abundant various ultrafine function powder materials.The resource comprehensive utilization technology thought of many-sided like this, various dimensions " turning waste into wealth ", new roadmap and source will be provided for the high value of the industrial wastewater resource of various biomass castoff, metal ion utilizes, thus remove with making traditional passive type by the valuable metal ions in industrial wastewater the emerging industry that way is transformed into very likely " lucrative ", even " makes big profits with a small capital ".By this economy of biological adsorption, remove the technological means of the metal ion in low-concentration industrial waste water efficiently, combine with the preparation production of ultrafine function powder material and application industry, there is absorption fast, cost is low, flour mill flow is short, output is large, the outstanding advantages such as easy upper scale, this method for treating water of biological adsorption will be made to have general chemical neutralization precipitation, coagulating sedimentation, ion exchange resin, the method such as UF membrane and electrodialysis be difficult to the unique advantage that possesses, therefore will become a great key development direction of the water treatment field of the various industrial wastewaters containing valuable metal ions from now on and cause the concern of increasing people and participate in.
Detailed description of the invention
Following case study on implementation is to help those skilled in the art to understand core technology main points of the present invention better, it is raw material that the those of ordinary skill comprising biological adsorption field all knows the biological adsorption agent having an absorption property to metal ion that can be detailed, carry out the adsorption operations to valuable metal ions, and adopt the mode of various atmosphere at high temperature thermal decomposition or the mode of solution dispersion in-situ reducing to prepare superfine metal, alloy and even oxide powder.The detailed content for core technology of the present invention above describes, and those skilled in the art can not produce ambiguity to core technology main points of the present invention.Biomass absorbent material wherein, makes a general reference all sorbent materials valuable metal ions to the biomass material of adsorption effect; Valuable metal mainly refers to except alkali metal as lithium, sodium, potassium etc., alkaline-earth metal ions such as other except beryllium, magnesium, calcium, strontium etc. have the metal of valency in patent of the present invention; The waste water containing valuable metal ions herein in embodiment both can be the valuable metal ions simulated wastewater of artificial preparation, also can be the industrial wastewater containing valuable metal ions that actual industry spot is fetched.
Embodiment one:
The copper nitrate solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 6 with the hydrochloric acid of 0.1M and sodium hydroxide solution, drop into 200 grams, apple skin adsorbent, stirring reaction is after 30 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain cupric oxide powder, grinding further, screening, classification, can obtain granularity at the following ultrafine copper oxide powder-product of 200 order.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 600 DEG C, metallic copper powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal copper (Cu) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment two:
The nickel nitrate solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 6 with the hydrochloric acid of 0.1M and sodium hydroxide solution, have high input 100 grams, garlic skin adsorbent, stirring reaction is after 300 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 420 DEG C, can obtain nickel oxide powder, grinding further, screening, classification, can obtain granularity ultra-fine nickel oxide powder product below 200 orders.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic nickel powder and biomass adsorbent pyrolysis residual components powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal nickel (Ni) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment three:
The silver nitrate solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 4 with the nitric acid of 0.1M and sodium hydroxide solution, drop into 300 grams, beer wheat tooth vinasse adsorbent, stirring reaction is after 500 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain silver powder, grinding further, screening, classification, can obtain granularity at 200 order following superfine metal silver powder product.Also argon gas can be passed in tube furnace, argon gas flow velocity is 1 liter per minute, heat resolve at 600 DEG C, argent powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal silver (Ag) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment four:
Preparation is respectively containing copper nitrate and the nickel nitrate solion 10 liters of 0.1M concentration, the pH of metal ion solution is regulated to be after 6 with the hydrochloric acid of 0.1M and sodium hydroxide solution, drop into tangerine slag adsorbent 400 grams, stirring reaction is after 240 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain copper nickel oxide powder, grinding further, screening, classification, can obtain granularity at 200 order following ultra-fine copper nickel oxide powder-product.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 600 DEG C, metallic copper Ni alloy powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at 200 order following superfine metal copper nickel (CuNi) alloy powder product and biomass adsorbent pyrolysis residual components powder.
Embodiment five:
Preparation is respectively containing copper nitrate and the silver nitrate solion 10 liters of 0.2M concentration, the pH of metal ion solution is regulated to be after 5 with the nitric acid of 0.1M and sodium hydroxide solution, have high input 600 grams, garlic skin adsorbent, stirring reaction is after 400 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 90 DEG C dries 16 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 450 DEG C, can obtain copper silver oxide powder, grinding further, screening, classification, can obtain granularity at 200 order following ultra-fine copper silver oxide powder product.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 550 DEG C, metallic copper silver alloy powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, granularity can be obtained at 200 order following superfine metal copper silver (CuAg) alloy powder product and biomass adsorbent pyrolysis residual components powder (Kufil does not at room temperature dissolve each other, so adopt this method to have very original advantage).
Embodiment six:
The waste water 20 liters that the copper electroplating workshop obtaining certain flexible PCB is on the spot arranged outward, wherein copper ions is 400mg/L, the pH of metal ion solution is regulated to be after 5.5 with the hydrochloric acid of 1M and sodium hydroxide solution, drop into shaddock peel adsorbent 100 grams, stirring reaction is after 90 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain cupric oxide powder, grinding further, screening, classification, can obtain granularity at the following ultrafine copper oxide powder-product of 200 order.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic copper powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal copper (Cu) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment seven:
The waste water 20 liters that the nickel electroplating workshop obtaining certain flexible PCB is on the spot arranged outward, wherein containing nickel ion is 30mg/L, the pH of metal ion solution is regulated to be after 5.5 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into marine alage adsorption agent 100 grams, stirring reaction is after 120 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain nickel oxide powder, grinding further, screening, classification, can obtain granularity ultra-fine nickel oxide powder product below 200 orders.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic nickel powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal nickel (Ni) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment eight:
Obtain the industrial wastewater 10 liters of certain iron content on the spot, wherein containing iron ion is 300mg/L, the pH of metal ion solution is regulated to be after 2.5 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into tangerine slag adsorbent 100 grams, stirring reaction is after 120 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain croci, grinding further, screening, classification, can obtain granularity at the following superfine iron oxide powder-product of 200 order.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic iron powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal iron (Fe) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment nine:
Obtain the metal plating waste water 10 liters that certain contains chromium on the spot, be wherein 60mg/L containing chromium ion, regulate the pH of metal ion solution to be after 2 with the hydrochloric acid of 1M and sodium hydroxide solution, after dropping into sodium sulfite 20 grams, stirring reaction is after 60 minutes, and hydro-oxidation sodium solution regulates pH value of solution to be after 5.6, drops into mangosteen slag adsorbent 100 grams, stirring reaction is after 120 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain chromium oxide powder, grinding further, screening, classification, can obtain granularity ultra-fine chromium oxide powder product below 200 orders.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, crome metal powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at following superfine metal chromium (Cr) powder-product of 200 order and biomass adsorbent pyrolysis residual components powder.
Embodiment ten:
Obtain the mine acidic industrial effluent 10 liters of certain iron content, copper ion on the spot, wherein iron content, copper ion are respectively 300mg/L and 50mg/L, the sodium hydroxide solution adding 1M concentration regulates pH value of solution to be after 2.5, drop into chitosan absorbent 150 grams, stirring reaction is after 60 minutes, the sodium hydroxide solution adding 1M concentration again regulates pH value of solution to be after 6, drop into garlic slag adsorbent 100 grams again, stirring reaction is after 120 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain iron copper oxide powder, grinding further, screening, classification, can obtain granularity ultra-fine iron copper oxide powder product below 200 orders.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic iron copper alloy powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at 200 order following superfine metal iron copper (FeCu) powder-product and biomass adsorbent pyrolysis residual components powder.
Embodiment 11:
Obtain the Rare-earth Mine industrial wastewater 10 liters that certain contains lanthanum ion on the spot, wherein containing lanthanum ion is 50mg/L, hydro-oxidation sodium solution regulates pH value of solution to be after 2.5, drop into garlic slag adsorbent 300 grams, stirring reaction is after 60 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours; Dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, can obtain lanthanum oxide powder, grinding further, screening, classification, can obtain granularity at the following ultrafine lanthanum oxide (La of 200 order
2o
3) powder-product.
Embodiment 12:
Obtain certain iron content on the spot, nickel, the mine acidic industrial effluent of copper ion 20 liters, wherein iron content, nickel, copper ion is respectively 300mg/L, 50mg/L and 100mg/L, hydro-oxidation sodium solution regulates pH value of solution to be after 2.7, drop into garlic slag adsorbent 500 grams, stirring reaction is after 60 minutes, repeated hydrogenation sodium hydroxide solution regulates pH value of solution to be after 4, drop into 100 grams, apple skin adsorbent again, stirring reaction is after 120 minutes, repeated hydrogenation sodium hydroxide solution regulates pH value of solution to be after 6, drop into chitosan absorbent 100 grams again, stirring reaction is after 120 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours, dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, iron ambrose alloy oxide powder can be obtained, further grinding, screening, classification, can obtain granularity ultra-fine iron ambrose alloy oxide powder product below 200 orders.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic iron monel powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at 200 order following superfine metal iron ambrose alloy (FeCuNi) powder-product and biomass adsorbent pyrolysis residual components powder.
Embodiment 13:
Obtain certain iron content on the spot, manganese, the metallurgy industry waste water of zinc ion 15 liters, wherein iron content, manganese, zinc ion is respectively 300mg/L, 100mg/L and 200mg/L, hydro-oxidation sodium solution regulates pH value of solution to be after 2.5, drop into garlic slag adsorbent 400 grams, stirring reaction is after 60 minutes, repeated hydrogenation sodium hydroxide solution regulates pH value of solution to be after 5, drop into tangerine slag adsorbent 100 grams again, stirring reaction is after 120 minutes, repeated hydrogenation sodium hydroxide solution regulates pH value of solution to be after 6, drop into garlic slag adsorbent 100 grams again, stirring reaction is after 120 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 6 hours, dry for gained adsorbent is put into porcelain dish tiling open, put into tube furnace, heat resolve at 400 DEG C, ferrimanganic zinc oxide powder can be obtained, further grinding, screening, classification, can obtain granularity ultra-fine ferrimanganic zinc oxygen oxide powder product below 200 orders.Also argon gas or hydrogen can be passed in tube furnace, argon gas or hydrogen flow rate are 1 liter per minute, heat resolve at 500 DEG C, metallic iron MnZn alloy powder and biomass adsorbent pyrolysis residual components powder can be obtained, further grinding, screening, classification, can obtain granularity at 200 order following superfine metal ferrimanganic zinc (FeMnZn) powder-product and biomass adsorbent pyrolysis residual components powder.
Embodiment 14:
The nickel chloride solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 6 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into garlic slag adsorbent 300 grams, stirring reaction is after 500 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 2 hours; By the hydrazine hydrate solution 1 liter of dry for gained adsorbent and 1M, when hydro-oxidation sodium solution regulates pH value of solution to be 12.5, be heated to 80 degrees Celsius, stirring reaction is after 3 hours, solution is filtered obtain atrament washing, dry, ultra-fine nickel (Ni) metal dust of granularity below 200 orders and biomass adsorbent powder can be obtained.
Embodiment 15:
The copper sulphate solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 5.5 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into garlic slag adsorbent 400 grams, stirring reaction is after 420 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 12 hours; By the hydrazine hydrate solution 1 liter of dry for gained adsorbent and 1M, when hydro-oxidation sodium solution regulates pH value of solution to be 12, be heated to 90 degrees Celsius, stirring reaction is after 3 hours, solution filtered and obtains solid matter washing, dry, ultra-fine copper (Cu) powder that granularity is below 200 orders and biomass adsorbent powder can be obtained.
Embodiment 16:
Nickel chloride, the copper chloride solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 5.5 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into mangosteen slag adsorbent 200 grams, stirring reaction is after 200 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 2 hours; By the solution of potassium borohydride 1 liter of gained adsorbent and 1M, be heated to 80 degrees Celsius, stirring reaction is after 3 hours, solution is filtered obtain atrament washing, dry, ultra-fine ambrose alloy (CuNi) powder and biomass adsorbent powder can be obtained.
Embodiment 17:
The copper chloride solion 10 liters of preparation 0.1M concentration, the pH of metal ion solution is regulated to be after 6 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into garlic slag adsorbent 300 grams, stirring reaction is after 500 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 2 hours; By dry for gained adsorbent and the sodium hypophosphite solution 1 liter of 2M, be heated to 150 degrees Celsius, reduction reaction is after 3 hours, solution filtered the atrament obtained washs, oven dry, can obtain ultra-fine copper (Cu) powder and biomass adsorbent powder.
Embodiment 18:
Get the copper ions solution 10 liters of certain electroplating wastewater factory on the spot, wherein copper ions concentration is 50mg/L, the pH of metal ion solution is regulated to be after 6 with the hydrochloric acid of 0.5M and sodium hydroxide solution, drop into garlic slag adsorbent 250 grams, stirring reaction is after 150 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 2 hours; By dry for gained adsorbent and the formalin 500 milliliters of 1M, be heated to 80 degrees Celsius, stirring reaction is after 5 hours, solution filtered the solid matter obtained washs, oven dry, can obtain ultra-fine copper (Cu) powder and biomass adsorbent powder.
Embodiment 19:
Get certain copper mine acid waste water solution 10 liters on the spot, wherein iron content and copper ion concentration are respectively 1520mg/L and 150mg/L, the pH of metal ion solution is regulated to be after 2.45 with the hydrochloric acid of 1M and sodium hydroxide solution, drop into garlic slag adsorbent 500 grams, stirring reaction is after 90 minutes, the pH of metal ion solution is regulated to be 6 with the hydrochloric acid of 1M and sodium hydroxide solution again, drop into garlic slag adsorbent 300 grams again, stirring reaction is after 90 minutes, by absorbent filtering, after washing 3 times with distilled water, the baking oven hot blast putting into 60 DEG C dries 2 hours; By dry for gained adsorbent and the sodium sulfite solution 500 milliliters of 3M, be heated to 80 degrees Celsius, stirring reaction is after 5 hours, solution filtered the solid matter obtained washs, oven dry, can obtain ultra-fine cuprous oxide iron (CuFe
2o
4) powder.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalency thereof.
Claims (10)
1. in biological adsorption solution, valuable metal ions prepares a method for superfine metal powder material, it is characterized in that, said method comprising the steps of:
The solution of step one, acquisition metal ion, the pH value range adjusting described solution is 2-12, biomass adsorbent is added to solution, the addition of described biomass adsorbent is often liter of solution 0.1-150 gram, stir after 5-1200 minute, filter and obtain the biomass adsorbent powder being enriched with metal ion;
Step 2, by the biomass adsorbent powder being enriched with metal ion that obtains after washing 2-3 time, dry in the hot bellows of 20 degrees Celsius to 80 degrees Celsius, obtain the biological adsorption agent oven dry powder of load metal ion;
Step 3, by load, the biological adsorption agent of metal ion is dried powder and is evenly laid in iron boat or porcelain boat, puts into heating furnace and carries out pyrolysis, obtain pressed powder; Wherein, the pyrolysis time is 10-1500 minutes, and pyrolysis temperature is 200-1000 degree Celsius, and described pyrolysis is passing into protective gas, or carries out under the environment passing into active gases;
Step 4, pressed powder carried out fragmentation, screening, classification obtain superfine metal powder material.
2. in biological adsorption solution as claimed in claim 1, valuable metal ions prepares the method for superfine metal powder material, and it is characterized in that, described protective gas is hydrogen, argon gas, nitrogen, carbon monoxide or carbon dioxide; Described active gases is air.
3. in biological adsorption solution as claimed in claim 1, valuable metal ions prepares the method for superfine metal powder material, and it is characterized in that, described heating furnace is cabinet type closed electric furnace or chain type at the uniform velocity stepping thermal decomposition tube furnace.
4. in biological adsorption solution, valuable metal ions prepares a method for superfine metal powder material, it is characterized in that, said method comprising the steps of:
The solution of step one, acquisition metal ion, the pH value range adjusting described solution is 2-12, biomass adsorbent is added to solution, the addition of described biomass adsorbent is often liter of solution 0.1-150 gram, stir after 5-1200 minute, filter and obtain the biomass adsorbent powder being enriched with metal ion;
Step 2, by the biomass adsorbent powder being enriched with metal ion that obtains after washing 2-3 time, dry in the hot bellows of 20 degrees Celsius to 80 degrees Celsius, obtain the biological adsorption agent oven dry powder of load metal ion;
Step 3, the solution that the biological adsorption agent of metal ion dries powder by load be ratio and the concentration of 1:1-10 according to mass ratio is the reproducibility reagent of 0.1-10M mix, and described reducing agent reagent is hydrazine hydrate, potassium borohydride, sodium hypophosphite, ascorbic acid, formaldehyde or sodium sulfite; Be react 10-1000 minute under the cryogenic conditions of 20 degrees Celsius to 400 degrees Celsius in temperature, metal ion is reduced;
Step 4, step 3 is reacted after the solution that obtains carry out filtering, wash, dry and obtain superfine metal powder material.
5. in biological adsorption solution as claimed in claim 4, valuable metal ions prepares the method for superfine metal powder material, it is characterized in that, after the solution that the biological adsorption agent of metal ion dries powder by load be ratio and the concentration of 1:1-10 according to mass ratio is the reproducibility reagent of 0.1-10M mixes, the pH value of adjustment mixed solution is 9-12.5.
6. in the biological adsorption solution as described in any one of claim 1-5, valuable metal ions prepares the method for superfine metal powder material, it is characterized in that, the stirring in described step one is mechanical agitation or air stirring.
7. in the biological adsorption solution as described in any one of claim 1-5, valuable metal ions prepares the method for superfine metal powder material, it is characterized in that, described superfine metal powder material is silver, metal oxide, or described superfine metal powder material is the composite powder material of metal and biomass adsorbent or biomass adsorbent pyrolysis residual components.
8. in the biological adsorption solution as described in any one of claim 1-5, valuable metal ions prepares the method for superfine metal powder material, it is characterized in that, also comprise the preparation process of biomass adsorbent before described step one, the preparation process of described biomass adsorbent comprises:
1) get biomass material, wash;
2) biomass material after washing and alkali, water are carried out being uniformly mixed reaction according to the mass ratio of 1:0.05-0.2:0.5-2, stir 12-24 hour, filter, obtain solid product, wherein, described alkali is one or two or more kinds mixing in lithium, sodium, potassium, calcium, the oxide of magnesium, hydroxide, carbonate, bicarbonate or ammonium carbonate, carbonic hydroammonium, urea, ammoniacal liquor;
3) above solid product is washed with water until neutral, feeding vacuum drying oven, be 60-120 DEG C of drying in temperature, drying object smashed, sieves, obtain the following particle of 40 order as biomass adsorbent.
9. in biological adsorption solution as claimed in claim 8, valuable metal ions prepares the method for superfine metal powder material, and it is characterized in that, described biomass material comprises containing-COOH ,-SH ,-NH
2or the biomass material of-(phenol) OH active function group.
10. in the biological adsorption solution as described in any one of claim 1-5, valuable metal ions prepares the method for superfine metal powder material, it is characterized in that, the solution of described metal ion is industrial wastewater.
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101215019A (en) * | 2008-01-15 | 2008-07-09 | 中国科学院化学研究所 | Method for degrading organic contaminant catalyzed by ultrasonic wave |
| CN101658944A (en) * | 2009-09-18 | 2010-03-03 | 陕西科技大学 | Preparation method of nano-silver |
| CN102557181A (en) * | 2012-01-20 | 2012-07-11 | 北京科技大学 | Method for adsorption and removal of heavy metals and dye of waste water by garlic waste |
| CN102528075A (en) * | 2012-03-15 | 2012-07-04 | 中南大学 | Method for preparing ultrafine silver powder by directly performing thermal decomposition on silver nitrate |
| CN103449623A (en) * | 2013-08-30 | 2013-12-18 | 武汉市硕隽科技有限公司 | Method for preparing metal nanometer material by recovering from industrial waste water |
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