CN102500331A - Preparation method of distiller's grain adsorbing material for heavy metal ion adsorption - Google Patents
Preparation method of distiller's grain adsorbing material for heavy metal ion adsorption Download PDFInfo
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- CN102500331A CN102500331A CN201110318616XA CN201110318616A CN102500331A CN 102500331 A CN102500331 A CN 102500331A CN 201110318616X A CN201110318616X A CN 201110318616XA CN 201110318616 A CN201110318616 A CN 201110318616A CN 102500331 A CN102500331 A CN 102500331A
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- sorbing material
- metal ion
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Abstract
The invention discloses a preparation method of a distiller's grain adsorbing material for heavy metal ion adsorption. The preparation method is characterized by comprising the following steps of: selecting byproduct grains from production of Luzhou-flavor distilled spirit, naturally drying, crushing, screening by a screen of 20-100 meshes, and collecting screen underflow to obtain pre-treated grains; and adding 1-30 parts by weight of pre-treated grains to 1-300 parts by weight of 1-20wt% acid aqueous solution, soaking at the temperature of 50-150 DEG C for 0.1-6 hours, filtering, washing solid with water to be neutral, drying at the temperature of 30-60 DEG C for 12-48 hours, and grinding to obtain the distiller's grain adsorbing material. According to the invention, the adsorbing material is prepared by adopting distiller's grains with wide sources, thus the process is simple and the cost is low; and the prepared adsorbing material is used for treatment of wastewater containing heavy metal ions, and the adsorption rate is up to 80-95%, thus the resource utilization of grain waste is realized and the purpose of treating a waste with another waste is achieved.
Description
Technical field
The invention belongs to the recycling field and the water treatment of discarded object, relate to a kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material.The spirit distiller grain sorbing material that makes is specially adapted to containing heavy metal ion (Pb
2+, Cd
2+, Hg
2+, Cr
3+, Cr
6+, Ag
+, Cu
2+, Zn
2+Deng) adsorption treatment of waste water.
Background technology
Along with fast development of modern industry, heavy metal containing sewage is serious day by day to the harm of environment and human health, and this problem has caused the degree of depth concern of various circles of society.Heavy metal wastewater thereby is mainly derived from industries such as mining, ore dressing, smelting, plating, chemical industry, machinery.After the heavy metal wastewater thereby that these industries produce enters natural water body, not only aquatile is constituted a threat to, and possibly pass through deposition, absorption and food chain and constantly enrichment, destroy ecological environment, and finally jeopardize human beings'health.Development heavy metal containing wastewater treatment technology not only helps environmental protection, and can promote the progress of industrial development and human society.The method of removing heavy metal ion at present mainly contains chemical precipitation, permeable membrane, ion-exchange, charcoal absorption and co-precipitation/absorption etc., but because the cost of these methods is generally higher, is difficult to admitted and popularize.Absorption method is to handle the heavy metal wastewater thereby most effectual way, has advantages such as wide accommodation, good, the recyclable useful heavy metal of treatment effect and sorbing material be reusable, therefore seeks the emphasis that cost-effective biomass adsorbent becomes research.
The living beings sorbing material has wide material sources, low, the renewable and easy degraded of cost, and uses characteristics such as back environmental friendliness, and therefore, the research of living beings sorbing material is very active in recent years.Natural biomass such as microorganism, shitosan and agricultural solid residue are used for heavy metal containing wastewater treatment and the water heavy metal ion reclaims existing many research reports.The modified biomass sorbing material has extremely strong selection adsorption capacity and high-adsorption-capacity to the heavy metal of low concentration.Spirit distiller grain is the biomass resource of discarding; Utilize the spirit distiller grain biomass resource; Through modification, exploitation high-performance, low cost, eco-friendly heavy metal sorbing material, substituting sorbing material expensive or the dependence petroleum is one of current novel absorption material developing direction.
China is a wine brewing big country, and spirit distiller grain is a maximum byproduct in the liquor production.Losing and poor be meant that the poor fermentation of face in the liquor production gets after drinking residual through solid state distillation and be pickled with grains or in wine, lose away the no longer that part of vinasse of usefulness, and the poor unstrained spirits that vinasse refer generally to ferment; Compare with vinasse, lose and do not contain wine part in poor, and content of organics such as starch, cellulose are low relatively.According to statistics, have every year ten million ton lose to be pickled with grains or in wine unprocessed or to handle a little approximately and just be discharged in the environment, so both wasted resource, again environment is caused severe contamination, this is the brewing industry problem demanding prompt solution.Therefore, comprehensively the comprehensive high-efficiency utilization lose poor, prevent to pollute, avoid waste, turn waste into wealth imperative.In the prior art, lose poor comprehensive utilization technique and patent mainly concentrate on losing poor fertile as feed, farming, produce glycerine, cultivate aspects such as edible mushroom, extraction compound amino acid and trace element.But Shang Weijian is about removing to handle the reports such as document of heavy metal ion in the aqueous solution with losing to be pickled with grains or in wine as sorbing material.
Summary of the invention
The object of the invention is intended to overcome deficiency of the prior art, and a kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material is provided; Thereby realization is lost poor utilization of waste as resource, the approach of an effective treatment of wastes with processes of wastes against one another is provided for the wastewater treatment that contains heavy metal ion.
Content of the present invention is: a kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material; It is characterized in that comprising the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose poor; After air dry, pulverize, cross 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; It is in 1～20% the aqueous acid that the poor weight percent concentration that joins 1～300 weight portion is lost in the preliminary treatment of 1～30 weight portion; The water washing of after soaking 0.1～6 hour under 50～150 ℃ the temperature, filter, solids being used 2～5 times of solids weight again is to neutral; Under 30～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
The said preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material of content of the present invention is characterized in that: it is poor to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; It is in 1～20% the aqueous acid that the poor weight percent concentration that joins 10～300 weight portions is lost in the preliminary treatment of 1～30 weight portion; After soaking 1～6 hour under 50～150 ℃ the temperature, filter, solids use again the moisture of 2～5 times of solids weight wash for 2～6 times to pH be 6～8, under 40～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
In the content of the present invention: described acid can be hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
In the content of the present invention: described acid can replace with alkali.
In the content of the present invention: described alkali can be NaOH, potassium hydroxide or ammoniacal liquor.
In the content of the present invention: described acid can also replace with salt.
In the content of the present invention: described salt can be one or both the mixture in sodium chloride, zinc chloride, the sodium carbonate.
In the content of the present invention: described spirit distiller grain sorbing material is specially adapted to the heavy metal ion (Pb in the aqueous solution
2+, Cd
2+, Hg
2+, Cr
3+, Cr
6+, Ag
+, Cu
2+, Zn
2+Deng) adsorption treatment.
In the content of the present invention: said vinasse are fragrant yeast vinasse, and aquatic foods are lost poor composition and are: moisture about 64% (mass percentage content, back are together), starch about 7.0%.Detection is dried after oven dry loses poor crude protein for being generally 10～15%, and crude fibre is 17～27%, and crude fat is 2～7%, and no nitrogen exudate is 26～49%, and cinder is divided into 12～18%.
When the spirit distiller grain sorbing material that the present invention makes is used for the heavy metal ion adsorbed processing of the aqueous solution; Adsorption treatment process can for: to be 0.1～2.0:100 (weight ratio) add initial concentration with the spirit distiller grain sorbing material by solid-to-liquid ratio is in the heavy metal ion solution of 1 mg/L～200 mg/L, uses HNO
3Transfer solution to pH2～7 with NaOH, after 1～24 hour, filter 20～60 ℃ of constant temperature adsorption treatment; The solubility of heavy metal in the solution of absorption front and back be can measure with atomic absorption spectrophotometer, thereby its adsorbance and adsorption rate calculated.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) lose rice husk content in poor up to 40%～50%, and the SiO of moisture 10%～12% in the general dried rice husk, polysaccharide 16%～20%, cellulose 26%～36%, crude fat 0.14%～0.18%, ash content 18%～20%, lignin 20%～24% and 14%～16%
2, SiO wherein
2With distributed in grid wherein, play a part skeleton, lignin, cellulose etc. is filled in the grid, and after quilt part degradeds such as cellulose, the rice husk surface is the micropore shape, SiO
2Mesh node expose, become the raw material of comparatively ideal preparation adsorbent.With the solid white spirit waste lees is raw material, through physical and chemical modified, it is prepared into environmental friendliness, sorbing material with low cost, well behaved; And use it for heavy metal containing wastewater treatment; The treatment of wastes with processes of wastes against one another is turned waste into wealth, and realizes efficient, environmental protection, the scale utilization of spirit distiller grain industry byproduct; To solving the difficult problem that rice husk is handled in the spirit distiller grain new approach is provided, will brings huge economic benefit and social benefit.Not only solve problem of environmental pollution but also realized changing waste into resources, met the sustainable development requirement, had bigger practical value and wide application prospect;
(2) of the present invention are the acid, base or salt as an activator, the surface of the liquor Grains chemical modification; Grains surface was removed before the modification of cellulose, hemicellulose and lignin, but also contains a certain percentage The ash can be hydrolyzed, dissolved organic or inorganic component, of these substances attached to the wrapped cellulose, lignin surface modification, in addition to these impurities, while Grains of protein, polysaccharides, lignin and hemicellulose partial hydrolysis of cellulose and lignin connection between the structural part has been destroyed, Grains of rice husk from the inside out in a burst of expansion occurred, so the modified surface structure and Grains groups underwent significant changes, more conducive to adsorption characteristics improve; modified with an acid liquor Grains surface acidic groups increased surface hydrophilicity, pH reduction, easing the oxidizer surface modification can Grains containing groups increases, the specific surface area, pore other changes, resulting in changes in the adsorption capacity; modified with alkali liquor Grains increase the number of surface hydroxyl groups, it is beneficial for the adsorption of heavy metal ions; zinc salts, such as cellulose in plants have swelling, gum melting and dissolution ability of the modified, Liquor Grains voids are formed in the dissolution of the cellulose, increasing the specific surface area of spent grains to enhance the adsorption capacity;
(3) adopt the present invention, contain functional groups such as a large amount of phenolic hydroxyl groups, methoxyl group, carbonyl, carboxyl in the spirit distiller grain sorbing material, these functional groups provide a large amount of participations heavy metal ion adsorbed avtive spot; Lose poor structure has characteristics very much, the SiO that it is contained
2With network-like distribution, play the skeleton supporting role, and lignin, cellulose and hemicellulose are filled in wherein, this space structure makes loses the poor potential quality as superior adsorbent that possessed; Spirit distiller grain is the maximum accessory substance of brewing industry; Directly be discharged in the environment contaminated environment not only but also cause the waste of resource; At present the vinasse comprehensive utilization technique mainly concentrate on losing poor fertile as feed, farming, produce glycerine, cultivate edible mushroom, extract aspects such as compound amino acid and trace element, do not see report as the heavy metal sorbing material; Compared with prior art; Spirit distiller grain goes heavy metal ion in the adsorption treatment aqueous solution as sorbing material; Can reduce sorbing material and cost of water treatment, can also reclaim heavy metal and oxide thereof through wash-out with burning simultaneously, reach the treatment of wastes with processes of wastes against one another; The purpose that turns waste into wealth realizes losing poor waste resource higher value application;
When (4) the spirit distiller grain sorbing material that makes of the present invention is used for the heavy metal ion adsorbed processing of the aqueous solution; Because heavy metal ion exists chemical valence, molal weight, ionic radius, have the difference of form etc.; And lose poor adsorbent complicated component; So its action mode with different heavy metal ion is various; Wherein to have form be the principal element that influences its absorption property to hydrated metal ion; On the one hand the bridge joint effect make lose hydroxy functional groups a large amount of in the poor adsorbent can with the hydroxyl effect of hydrated metal ion; Form comparatively stable ligand, thereby improve the adsorbance of metal ion; If the bridge joint effect of metal ion self is strengthened, the metal ion condensate of bridge joint is sterically hindered more at most big more on the other hand, with lose poor adsorbent cooperate chance just little, thereby cause the reduction of adsorbance; The relative stability of many complexs is influenced by ionic charge and ionic size, and the electric charge on the ion is bigger big more with the more little then stability of ion; Therefore, lose poor and complex that metal ion forms stability should along with the metal ion radius reduce increase with the increase of metal ion electric charge; The surface texture of spirit distiller grain and group are influential to its absorption property; The spirit distiller grain surface is rough and uneven in surface; Surface area is bigger; And contain functional groups's (seeing Fig. 1,2) such as a large amount of phenolic hydroxyl groups, methoxyl group, carbonyl, carboxyl, these functional groups provide a large amount of participations heavy metal ion adsorbed avtive spot; In addition, other environmental factors also affect the absorption property of spirit distiller grain to a certain extent, and the pH value of solution value has very big influence to the stability that has form and complex of heavy metal ion; The variation of inventory mainly is the ratio that has changed adsorption site and heavy metal ion; Temperature then has similar part with the effect of pH value, promptly changes the form that exists that has form and heavy metal ion of each component in the spirit distiller grain simultaneously; Different metal ion mixed solution then makes various heavy metal ion interactions strengthen, and the competitiveness of absorption and concertedness are fierce more;
The SEM electron-microscope scanning image of the spirit distiller grain sorbing material that (5) makes from the present invention can be found out, spirit distiller grain sorbing material rough surface, and internal structure is loose; The infared spectrum of the spirit distiller grain sorbing material that makes from the present invention can know that it has hydroxyl, amide groups, SiO
2Groups such as silicon hydroxyl, therefore, the spirit distiller grain sorbing material is a kind of cheap and eco-friendly sorbing material that can effectively remove heavy metal ion in the aqueous systems;
(6) adopt the present invention, the spirit distiller grain sorbing material is in the absorption that directly is used for the aqueous systems heavy metal ion that is applied as in heavy metal ion adsorbed field, and technology is simple, with low cost, and the heavy metal absorption property is high, adsorption rate reaches 80～95%; Preparation of spirit distiller grain sorbing material and application thereof can realize losing poor changing waste into resources utilization, can reach the purpose of the treatment of wastes with processes of wastes against one another to heavy metal containing wastewater treatment.
Description of drawings
Fig. 1 is the SEM electron-microscope scanning image that adopts the spirit distiller grain sorbing material of the present invention's preparation (outer surface structure * 1000 times);
Fig. 2 is the SEM electron-microscope scanning image that adopts the spirit distiller grain sorbing material of the present invention's preparation (outer surface structure * 5000 times);
Fig. 3 is the SEM electron-microscope scanning image that adopts the spirit distiller grain sorbing material of the present invention's preparation (section structure * 5000 times);
Through ESEM outer surface and the section of losing poor sorbing material are directly observed, found to lose the surperficial rough and uneven in surface of poor sorbing material, surface area is bigger, has loose architectural feature, shows that it helps Adsorption of Heavy Metal Ions;
Fig. 4 is the infared spectrum that adopts the spirit distiller grain sorbing material of the present invention's preparation;
Losing poor infrared spectrogram resolves: because it is complicated to lose poor composition, sample all has tangible absorption in whole wave-number range, make some peak fail to show, and some not too sensitive absworption peaks are covered.
Can know 3427 cm by Fig. 4
-1The absworption peak at place is stronger and wide, and existence-OH is described, this stretching vibration is to be caused by free in the moisture content of silanol base (Si-OH), other hydroxyl and the absorption of losing poor surface and association-OH vibration; 2921 cm
-1The absworption peak at place is in the methoxyl group-the asymmetric stretching vibration peak of CH3; 1641 cm
-1The peak from C=O in the ketone group and the stretching vibration of acid amides I; 1515 cm
-1It is the skeleton stretching vibration of acid amides II and phenyl ring; 1383 cm
-1The absworption peak at place is-the symmetric curvature vibration peak of CH3; 1101 cm-1 place absworption peaks mainly are-flexural vibrations of OH and the stretching vibration of C-O-C, also possibly be SiO
2The contribution of antisymmetric stretching vibration.
Results of IR shows that losing poor sorbing material contains groups such as abundant hydroxyl, amide groups, is favourable to the absorption heavy metal.
The specific embodiment
Embodiment given below intends so that the present invention is described further; But can not be interpreted as it is restriction to protection domain of the present invention; The technical staff in this field to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
It is poor to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 60 mesh sieves, screenings and be that preliminary treatment is lost is poor; (unit can be kilogram with 5 weight portions; The back with) dry vinasse to join 50 weight portion mass percentage concentration be in a kind of solution in 5% hydrochloric acid, sodium hydroxide alkali and the sodium carbonate; The water washing of filtration after soaking 2 hours under 60 ℃ the temperature, 2～5 times of weight promptly gets the spirit distiller grain sorbing material after the grinding.
Embodiment 2:
It is poor to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 80 mesh sieves, screenings and be that preliminary treatment is lost is poor; It is in a kind of solution in 10% sulfuric acid, potassium hydroxide and the sodium chloride that the poor 200 weight portion mass percentage concentration that join are lost in the preliminary treatment of 15 weight portions; Filtration after soaking 4 hours under 100 ℃ the temperature, the water washing of 2～5 times of weight, 40 ℃ of dryings promptly get the spirit distiller grain sorbing material after the grinding.
Embodiment 3:
It is poor to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 100 mesh sieves, screenings and be that preliminary treatment is lost is poor; The mass percentage concentration that the dry vinasse of 30 weight portions are joined 300 weight portions is in a kind of solution in 20% nitric acid, ammoniacal liquor and the zinc chloride; Filtration after soaking 5 hours under 120 ℃ the temperature, the water washing of 2～5 times of weight, 50 ℃ of dryings promptly get the spirit distiller grain sorbing material after the grinding.
Embodiment 4:
Contain Pb
2+The adsorption treatment of effluent containing heavy metal ions.Adsorption treatment process: by solid-to-liquid ratio is that 0.5:100 (weight ratio) is in the heavy metal ion solution of 80mg/L with spirit distiller grain sorbing material adding initial concentration, uses HNO
3Transfer to pH5 with NaOH, 25 ℃ of constant temperature adsorption treatment were filtered after 1～24 hour, with the solubility of heavy metal in the solution before and after the atomic absorption spectrophotometer absorption, thereby calculated adsorption rate.Sorbing material is to Pb
2+Adsorption rate is all more than 95%, and advantages of good adsorption effect is to Pb
2+The absorption accords with Langmuir Adsorption Model of ion.
Embodiment 5:
Contain Cu
2+The adsorption treatment of effluent containing heavy metal ions.Adsorption treatment process: by solid-to-liquid ratio is that 1.0:100 (weight ratio) is in the heavy metal ion solution of 100 mg/L with spirit distiller grain sorbing material adding initial concentration, uses HNO
3Transfer to pH6 with NaOH, 30 ℃ of constant temperature adsorption treatment were filtered after 1～24 hour, with the solubility of heavy metal in the solution before and after the atomic absorption spectrophotometer absorption, thereby calculated adsorption rate.Sorbing material is to Cu
2+Adsorption rate is all more than 85%.
Embodiment 6:
Contain Cr
3+The adsorption treatment of effluent containing heavy metal ions.Adsorption treatment process: by solid-to-liquid ratio is that 1.5:100 (weight ratio) is in the heavy metal ion solution of 120mg/L with spirit distiller grain sorbing material adding initial concentration, uses HNO
3Transfer to pH5 with NaOH, 30 ℃ of constant temperature adsorption treatment were filtered after 1～24 hour, with the solubility of heavy metal in the solution before and after the atomic absorption spectrophotometer absorption, thereby calculated adsorption rate.Sorbing material is to Cr
3+Adsorption rate is all more than 80%.
Embodiment 7:
Contain Zn
2+The adsorption treatment of effluent containing heavy metal ions.Adsorption treatment process: by solid-to-liquid ratio is that 1.2:100 (weight ratio) is in the heavy metal ion solution of 100mg/L with spirit distiller grain sorbing material adding initial concentration, uses HNO
3Transfer to pH7 with NaOH, 35 ℃ of constant temperature adsorption treatment were filtered after 1～24 hour, with the solubility of heavy metal in the solution before and after the atomic absorption spectrophotometer absorption, thereby calculated adsorption rate.Sorbing material is to Zn
2+Adsorption rate is all more than 85%.
Embodiment 8:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 60 mesh sieves, screenings and be that preliminary treatment is lost is poor; (unit can be kilogram with 1 weight portion; The back with) preliminary treatment to lose the poor weight percent concentration that joins 10 weight portions be in 1% the aqueous acid; After soaking 1 hour under 50～150 ℃ the temperature, filter, solids uses the moisture of 2 times of solids weight to wash for 2～6 times to pH to be 6～8 again, under 40～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Embodiment 9:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 100 mesh sieves, screenings and be that preliminary treatment is lost is poor; (unit can be kilogram with 30 weight portions; The back with) preliminary treatment to lose the poor weight percent concentration that joins 300 weight portions be in 20% the aqueous acid; After soaking 6 hours under 50～150 ℃ the temperature, filter, solids uses the moisture of 5 times of solids weight to wash for 2～6 times to pH to be 6～8 again, under 40～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Embodiment 10:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 80 mesh sieves, screenings and be that preliminary treatment is lost is poor; (unit can be kilogram with 15 weight portions; The back with) preliminary treatment to lose the poor weight percent concentration that joins 155 weight portions be in 10% the aqueous acid; After soaking 3 hours under 50～150 ℃ the temperature, filter, solids uses the moisture of 4 times of solids weight to wash for 2～6 times to pH to be 6～8 again, under 40～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Embodiment 11:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; (unit can be kilogram with 1～30 weight portion; The back with) preliminary treatment to lose the poor weight percent concentration that joins 10～300 weight portions be in 1～20% the aqueous acid; After soaking 1～6 hour under 50～150 ℃ the temperature, filter, solids use again the moisture of 2～5 times of solids weight wash for 2～6 times to pH be 6～8, under 40～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Embodiment 12-18:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; It is in 1～20% the aqueous acid that the poor weight percent concentration that joins 1～300 weight portion is lost in the preliminary treatment of 1～30 weight portion; The water washing of after soaking 0.1～6 hour under 50～150 ℃ the temperature, filter, solids being used 2～5 times of solids weight again is to neutral; Under 30～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Each embodiment component and weight portion see the following form 1:
Table 1:
In the foregoing description 12-18: the weight percent concentration of aqueous acid can be the concentration of any point in 1～20%.
In the foregoing description 8-18: described acid can be hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
Embodiment 19-22:
Acid in the foregoing description 8-11 is replaced with alkali respectively, and other omits with embodiment 8-11.
Embodiment 23-29:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; The preliminary treatment of 1～30 weight portion is lost in the aqueous solution that the poor weight percent concentration that joins 1～300 weight portion is 1～20% alkali; The water washing of after soaking 0.1～6 hour under 50～150 ℃ the temperature, filter, solids being used 2～5 times of solids weight again is to neutral; Under 30～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Each embodiment component and weight portion see the following form 2:
Table 2:
In the foregoing description 23-29: the weight percent concentration of the aqueous solution of alkali can be the concentration of any point in 1～20%.
In the foregoing description 19-29: described alkali can be NaOH, potassium hydroxide or ammoniacal liquor.
Embodiment 30-33:
Acid in the foregoing description 8-11 is replaced with salt respectively, and other omits with embodiment 8-11.
Embodiment 34-40:
A kind of preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is poor to comprise the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; The preliminary treatment of 1～30 weight portion is lost in the aqueous solution that the poor weight percent concentration that joins 1～300 weight portion is 1～20% salt; The water washing of after soaking 0.1～6 hour under 50～150 ℃ the temperature, filter, solids being used 2～5 times of solids weight again is to neutral; Under 30～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
Each embodiment component and weight portion see the following form 3:
Table 3:
In the foregoing description 34-40: the weight percent concentration of the aqueous solution of salt can be the concentration of any point in 1～20%.
In the foregoing description 30-40: described salt can be one or both the mixture in sodium chloride, zinc chloride, the sodium carbonate.
When the spirit distiller grain sorbing material that makes in the foregoing description is used for the heavy metal ion adsorbed processing of the aqueous solution; Adsorption treatment process can for: to be 0.1～2.0:100 (weight ratio) add initial concentration with the spirit distiller grain sorbing material by solid-to-liquid ratio is in the heavy metal ion solution of 1 mg/L～200 mg/L, uses HNO
3And/or NaOH accent solution after 1～24 hour, filters 20～60 ℃ of constant temperature adsorption treatment to pH2～7; The solubility of heavy metal in the solution of absorption front and back be can measure with atomic absorption spectrophotometer, thereby its adsorbance and adsorption rate calculated.
In the foregoing description 8-40: the said spirit distiller grain sorbing material that makes can be used for the heavy metal ion (Pb of the aqueous solution
2+, Cd
2+, Hg
2+, Cr
3+, Cr
6+, Ag
+, Cu
2+, Zn
2+Deng) adsorption treatment, respond well.
In the foregoing description: each material component that is adopted is the commercially available prod.
In the foregoing description: in the percentage that is adopted, do not indicate especially, be weight (quality) percentage; Said weight portion can all be gram or kilogram.
In the foregoing description: the technological parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The not concrete same prior art of narrating of technology contents in content of the present invention and the foregoing description.
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (10)
1. preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material; It is characterized in that comprising the following steps: to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose poor; After air dry, pulverize, cross 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; It is in 1～20% the aqueous acid that the poor weight percent concentration that joins 1～300 weight portion is lost in the preliminary treatment of 1～30 weight portion; The water washing of after soaking 0.1～6 hour under 50～150 ℃ the temperature, filter, solids being used 2～5 times of solids weight again is to neutral; Under 30～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
2. by the said preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material of claim 1, it is characterized in that: it is poor to select for use the accessory substance of Production of Luzhou-flavor Liquor to lose, and after air dry, pulverizes, and crosses 20～100 mesh sieves, screenings and be that preliminary treatment is lost is poor; It is in 1～20% the aqueous acid that the poor weight percent concentration that joins 10～300 weight portions is lost in the preliminary treatment of 1～30 weight portion; After soaking 1～6 hour under 50～150 ℃ the temperature, filter, solids use again the moisture of 2～5 times of solids weight wash for 2～6 times to pH be 6～8; Under 40～60 ℃ of temperature dry 12～48 hours again, promptly make the spirit distiller grain sorbing material after the grinding.
3. by claim 1 or the 2 said preparation methods that are used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is characterized in that: described acid is hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
4. by claim 1 or the 2 said preparation methods that are used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is characterized in that: described acid replaces with alkali.
5. by the said preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material of claim 4, it is characterized in that: described alkali is NaOH, potassium hydroxide or ammoniacal liquor.
6. by claim 1 or the 2 said preparation methods that are used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is characterized in that: described acid replaces with salt.
7. by the said preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material of claim 6, it is characterized in that: described salt is one or both the mixture in sodium chloride, zinc chloride, the sodium carbonate.
8. by claim 1 or the 2 said preparation methods that are used for heavy metal ion adsorbed spirit distiller grain sorbing material, it is characterized in that: described spirit distiller grain sorbing material is used for the adsorption treatment of the heavy metal ion of the aqueous solution.
9. by the said preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material of claim 4, it is characterized in that: described spirit distiller grain sorbing material is used for the adsorption treatment of the heavy metal ion of the aqueous solution.
10. by the said preparation method who is used for heavy metal ion adsorbed spirit distiller grain sorbing material of claim 6, it is characterized in that: described spirit distiller grain sorbing material is used for the adsorption treatment of the heavy metal ion of the aqueous solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104645945A (en) * | 2015-02-15 | 2015-05-27 | 中国地质大学（武汉） | Wheat straw bio-based ion exchange type adsorbing material and preparation method thereof |
| CN107282016A (en) * | 2017-08-09 | 2017-10-24 | 陕西科技大学 | A kind of anion adsorbent prepared with vinasse and its preparation method and application |
| GB2581365A (en) * | 2019-02-14 | 2020-08-19 | Sem Energy Ltd | A method for remediating contaminated water and apparatus for the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104645945A (en) * | 2015-02-15 | 2015-05-27 | 中国地质大学（武汉） | Wheat straw bio-based ion exchange type adsorbing material and preparation method thereof |
| CN107282016A (en) * | 2017-08-09 | 2017-10-24 | 陕西科技大学 | A kind of anion adsorbent prepared with vinasse and its preparation method and application |
| GB2581365A (en) * | 2019-02-14 | 2020-08-19 | Sem Energy Ltd | A method for remediating contaminated water and apparatus for the same |
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