CN105327691A - Preparation method for leather collagen/sodium alginate porous gel bead heavy-metal adsorbent - Google Patents
Preparation method for leather collagen/sodium alginate porous gel bead heavy-metal adsorbent Download PDFInfo
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Abstract
The invention discloses a preparation method for a leather collagen/sodium alginate porous gel bead heavy-metal adsorbent. The preparation method comprises washing waste leather with water for removing impurities, crushing and sieving; immersing the waste leather powder in a NaOH solution, and stirring at 50-70 DEG C for 5-10 h, so as to obtain a leather collagen solution; getting a pore forming agent according to a weight proportion, adding water and performing ultrasonic dissolving, adding into the leather collagen solution, stirring for 0.5 h, adding sodium alginate, and stirring for 4-10 h, so as to prepare a leather collage/sodium alginate blended sol; and gradually dropwise adding the leather collage/sodium alginate blended sol into an acidic solution by using a syringe at a flow velocity of 60 mL/h, uniformly stirring, filtering, washing to neutral by using ultrapure water, and drying for 10-12 h, so as to obtain the adsorbent. The adsorbent is simple in preparation process and low in cost, can be regenerated and reused for multiple times, can be degraded after being discarded, and possesses good popularization application prospect.
Description
Technical field
The present invention relates to the composition containing collagen-based materials, particularly a kind of with leather leftover bits for the method for sorbing material prepared by raw material.
Background technology
Heavy metal wastewater thereby is mainly derived from mining, ore dressing, smelting, plating, chemical industry, machinery etc.The heavy metal kind of heavy metal wastewater thereby is very complicated, and pollutant sources is also diversified, after the heavy metal wastewater thereby that these industries produce enters natural water body, can not be decomposed by the microorganisms, the constantly enrichment by precipitation, absorption and food chain, destroys ecological environment, finally jeopardizes human health.
The improvement of heavy metal and radionuclide contamination both at home and abroad so far is still improved and thoroughly not, far can not stop heavy metal wastewater thereby and radionuclide to the pollution of environment.This destroys because which kind of method process heavy metal and radioactive wastewater adopt all to make heavy metal wherein and radionuclide decompose, and can only shift its position existed or change its physics and chemistry form.Such as after chemical precipitation process, the heavy metal in waste water and radionuclide change insoluble chemical compound into from the ionic condition of dissolving and precipitate, so proceed in mud from water.Therefore, if only note the process of waste water itself, and ignore recycling and the harmless treatment of process afterproduct, let alone to run off in environment, will secondary pollution be manufactured.
Absorption method reclaims the most effectual way of micro heavy and radionuclide in waste water, and have wide accommodation, good, the recyclable useful heavy metal for the treatment of effect and radionuclide and the advantage such as sorbing material is reusable.Existing sorbing material comprises active carbon, mineral matter, inorganic salts, synthetic resin etc.Domestic and international widely used adsorbent is activated carbon, although active carbon can adsorb many chemical substances, the adsorption capacity of heavy metal ion and radionuclide is little, generally only has 30 ~ 40mg/g, and regeneration difficulty.The adsorption capacity of ion exchange resin is higher, but only has adsorption capacity to some specific ion, and regeneration difficulty, and price is high.The low price of natural zeolite and clay, but the adsorption capacity of heavy metal ion and radionuclide is lower, is generally less than 10mg/g.And clay mineral materials process heavy metal and radionuclide waste water exists Separation of Solid and Liquid difficulty, adsorbent can not reuse, easily cause secondary pollution etc.
For this reason; many researchers are devoted to the research and development of novel absorption material; very active for the absorption research of heavy metal ion and radionuclide to natural biomass in recent years; the absorption that the natural biomass such as microorganism, shitosan and agricultural solid residue are used for Heavy Metals in Waters ion and radionuclide has much research report; but the adsorption capacity of these materials is not strong; and without definite shape, industrially apply and still have a lot of defect.
China is leather big producing country, and current China produces pigskin more than 8,000 ten thousand per year, and more than 4,000 ten thousand, sheepskin, more than 2,000 ten thousand, ox-hide, accounts for 14% of Gross World Product, more than 18% and 50% respectively.According to incompletely statistics, 1t wet salted hide can only produce the resultant Leather of 200kg, produces the leftover bits solid waste more than 600kg simultaneously, exceedes 60% of the quality of raw hide.If Leather Solid Waste can not get effective process, then both occupy place, pollute environment again, especially to the significant wastage of resource.
Therefore, heavy metal absorbent is prepared to leather leftover bits cheap and easy to get hydrolysis is rear and sodium alginate is blended, not only solve the problem such as the severe contamination of environment and the significant wastage of resource, and relative to again being prepared by its modification to the method for heavy-metal adsorption material after extraction materials with hide glue fibril, simplify operation, improve adsorbance, reduce cost, be more conducive to industrial applications.
Summary of the invention
The object of the invention is the preparation method that a kind of collagen/sodium alginate porous gel ball heavy metal absorbent is provided for the deficiencies in the prior art, be characterized in that will discard leather ion, pulverizing, sieves with discarded leather leftover bits for raw material; The collagen solution of hydrolysis preparation adds sodium alginate, the obtained blended colloidal sol of collagen/sodium alginate; CaCl is instilled with syringe
2in acid solution, obtain collagen/sodium alginate porous gel ball heavy metal absorbent.For the recycling of leather leftover bits and the exploitation of novel heavy metal absorbent provide technological service.
Technical scheme of the present invention is: the preparation method of a kind of collagen/sodium alginate porous gel ball heavy metal absorbent, in turn includes the following steps:
The preparation of A, waste leather powder: will discard leather ion, soaks 24 ~ 48h with ultra-pure water, after 40 ~ 60 DEG C of drying 12 ~ 24h, pulverizes with miniature high-speed pulverizer, crosses 40 mesh sieves;
B, prepare collagen colloidal sol: by 10 ~ 100 parts, waste leather powder, be soaked in 10 ~ 100 part of 0.5% ~ 4% (w/w) NaOH solution, in 50 ~ 70 DEG C, after stirring 5 ~ 10h with the speed of 100r/min ~ 300r/min, obtain collagen solution;
C, the blended colloidal sol of collagen/sodium alginate processed: get pore-foaming agent 3 ~ 10 parts and to add water by weight ratio 3 ~ 10 parts of ultrasonic dissolutions, join in collagen solution, after stirring 0.5h with the speed of 100r/min ~ 300r/min, add sodium alginate 10 ~ 100 parts, 300r/min stirs 4 ~ 10h, the obtained blended colloidal sol of collagen/sodium alginate;
D, prepare collagen/sodium alginate porous gel ball heavy metal absorbent: with syringe with the flow velocity of 60mL/h, blended for collagen/sodium alginate colloidal sol step is added dropwise in 10 ~ 100 parts of 2% ~ 6%CaCl2 acid solutions, 100r/min at the uniform velocity stirs 5 ~ 12h, neutrality is washed till with ultra-pure water after filtration, in 40 ~ 60 DEG C of drying 10 ~ 12h, namely obtain collagen/sodium alginate porous gel ball heavy metal absorbent.
Preferred collagen/each component of sodium alginate porous gel ball heavy metal absorbent is by weight ratio: 10 ~ 100 parts, waste leather powder, sodium alginate 10 ~ 100 parts, 0.5% ~ 4% (w/w) NaOH solution 10 ~ 100 parts, pore-foaming agent 3 ~ 10 parts, 2% ~ 6%CaCl
2acid solution 10 ~ 100 parts.
Described waste leather powder is pigskin, ox-hide, sheepskin leather processing leftover bits one or more any combination after crushed.Preferred pore-foaming agent is one or more any combination in calcium carbonate, sodium carbonate, potash; Described CaCl
2acid solution is CaCl
2aqueous solution acid for adjusting pH to 3 ~ 5.
The present invention has the following advantages: discard leather leftover bits wide material sources, easily obtain, containing a large amount of collagen, biodegradable, many kinds of metal ions can be adsorbed simultaneously, for Adsorption of Heavy Metals process water pollutions, not only solve the problems such as the significant wastage of serious environmental pollution and resource, the recycling of more discarded leather develops new way.
Discarded leather leftover bits are hydrolyzed into collagen solution and sodium alginate blended, be namely convenient to collagen to extrude balling-up, its size, shape control by blended collosol concentration, syringe aperture and flow velocity.And sodium alginate itself is containing measuring active group greatly, adds pore-foaming agent, makes absorption not occur over just microsphere surface, also occur in the micropore under top layer, add adsorption area, significantly improve adsorbance.
Collagen/sodium alginate porous gel ball forming is even, and after absorption, morphology volume is without significant change, solves the flow velocity problem after Dynamic Adsorption expansion in commercial Application.Collagen/sodium alginate porous gel ball good thermal stability, has very high mechanical strength, wear-resistant, be convenient to adsorb saturated after desorption and regeneration.
The present invention not only solves the problem such as the severe contamination of environment and the significant wastage of resource, and relative to preparing the method for heavy-metal adsorption material after extraction materials with hide glue fibril again to its modification, simplify operation, improve adsorbance, reduce cost, be more conducive to industrial applications.
Detailed description of the invention: the present invention is described in further details below in conjunction with specific embodiment.
Embodiment 1: will discard ox-hide ion, and soak 48h with ultra-pure water, after 60 DEG C of dry 24h, pulverizes with miniature high-speed pulverizer, crosses 40 mesh sieves; By 10 parts, waste leather powder, be soaked in 10 part of 4% (w/w) NaOH solution, in 70 DEG C, after stirring 10h with the speed of 300r/min, obtain collagen solution; Get 10 parts, calcium carbonate to add water by weight ratio 10 parts of ultrasonic dissolutions, join in collagen solution, after stirring 0.5h with the speed of 300r/min, add sodium alginate 10 parts, 300r/min stirs 10h, obtains the blended colloidal sol of collagen/sodium alginate; With syringe with the flow velocity of 60mL/h, blended for collagen/sodium alginate colloidal sol step is added dropwise to 10 parts of pH3,6%CaCl
2in acid solution, 100r/min at the uniform velocity stirs 12h, is washed till neutrality after filtration with ultra-pure water, in 60 DEG C of dry 12h, namely obtains collagen/sodium alginate porous gel ball heavy metal absorbent.
Embodiment 2: will discard pigskin ion, and soak 24h with ultra-pure water, after 40 DEG C of dry 12h, pulverizes with miniature high-speed pulverizer, crosses 40 mesh sieves; By 100 parts, waste leather powder, be soaked in 100 part of 0.5% (w/w) NaOH solution, in 50 DEG C, after stirring 5h with the speed of 100r/min, obtain collagen solution; Get 3 parts, sodium carbonate to add water by weight ratio 3 parts of ultrasonic dissolutions, join in collagen solution, after stirring 0.5h with the speed of 100r/min, add sodium alginate 100 parts, 300r/min stirs 4h, obtains the blended colloidal sol of collagen/sodium alginate; With syringe with the flow velocity of 60mL/h, blended for collagen/sodium alginate colloidal sol step is added dropwise to 100 parts of pH3,2%CaCl
2in acid solution, 100r/min at the uniform velocity stirs 5h, is washed till neutrality after filtration with ultra-pure water, in 40 DEG C of dry 10h, namely obtains collagen/sodium alginate porous gel ball heavy metal absorbent.
Embodiment 3: will discard sheepskin ion, and soak 30h with ultra-pure water, after 50 DEG C of dry 18h, pulverizes with miniature high-speed pulverizer, crosses 40 mesh sieves; By 50 parts, waste leather powder, be soaked in 50 part of 2% (w/w) NaOH solution, in 60 DEG C, after stirring 8h with the speed of 200r/min, obtain collagen solution; Get 5 parts, potash to add water by weight ratio 5 parts of ultrasonic dissolutions, join in collagen solution, after stirring 0.5h with the speed of 200r/min, add sodium alginate 50 parts, 300r/min stirs 8h, obtains the blended colloidal sol of collagen/sodium alginate; With syringe with the flow velocity of 60mL/h, blended for collagen/sodium alginate colloidal sol step is added dropwise to 50 parts of pH4,4%CaCl
2in acid solution, 100r/min at the uniform velocity stirs 8h, is washed till neutrality after filtration with ultra-pure water, in 50 DEG C of dry 8h, namely obtains collagen/sodium alginate porous gel ball heavy metal absorbent.
Embodiment 4: will discard sheepskin and pigskin ion, and soak 28h with ultra-pure water, after 55 DEG C of dry 16h, pulverizes with miniature high-speed pulverizer, crosses 40 mesh sieves; By 60 parts, waste leather powder, be soaked in 60 part of 3% (w/w) NaOH solution, in 55 DEG C, after stirring 9h with the speed of 180r/min, obtain collagen solution; Get 4 parts, potash, 4 parts, sodium carbonate adds water 8 parts of ultrasonic dissolutions by weight ratio, joins in collagen solution, after stirring 0.5h with the speed of 150r/min, add sodium alginate 60 parts, 300r/min stirs 6h, the obtained blended colloidal sol of collagen/sodium alginate; With syringe with the flow velocity of 60mL/h, blended for collagen/sodium alginate colloidal sol step is added dropwise to 60 parts of pH3.5,5%CaCl
2in acid solution, 100r/min at the uniform velocity stirs 7h, is washed till neutrality after filtration with ultra-pure water, in 50 DEG C of dry 11h, namely obtains collagen/sodium alginate porous gel ball heavy metal absorbent.
In sum; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (4)
1. a preparation method for collagen/sodium alginate porous gel ball heavy metal absorbent, in turn includes the following steps:
The preparation of A, waste leather powder: will discard leather ion, soaks 24 ~ 48h with ultra-pure water, after 40 ~ 60 DEG C of drying 12 ~ 24h, pulverizes with miniature high-speed pulverizer, crosses 40 mesh sieves;
B, prepare collagen colloidal sol: by 10 ~ 100 parts, waste leather powder, be soaked in 10 ~ 100 parts of 0.5% ~ 4%(w/w) in NaOH solution, in 50 ~ 70 DEG C, after stirring 5 ~ 10h with the speed of 100r/min ~ 300r/min, obtain collagen solution;
C, the blended colloidal sol of collagen/sodium alginate processed: get pore-foaming agent 3 ~ 10 parts and to add water by weight ratio 3 ~ 10 parts of ultrasonic dissolutions, join in collagen solution, after stirring 0.5h with the speed of 100r/min ~ 300r/min, add sodium alginate 10 ~ 100 parts, 300r/min stirs 4 ~ 10h, the obtained blended colloidal sol of collagen/sodium alginate;
D, prepare collagen/sodium alginate porous gel ball heavy metal absorbent: with syringe with the flow velocity of 60mL/h, blended for collagen/sodium alginate colloidal sol step is added dropwise in 10 ~ 100 parts of 2% ~ 6%CaCl2 acid solutions, 100r/min at the uniform velocity stirs 5 ~ 12h, neutrality is washed till with ultra-pure water after filtration, in 40 ~ 60 DEG C of drying 10 ~ 12h, namely obtain collagen/sodium alginate porous gel ball heavy metal absorbent.
2. the preparation method of collagen according to claim 1/sodium alginate porous gel ball heavy metal absorbent, it is characterized in that, described waste leather powder is pigskin, ox-hide, sheepskin leather processing leftover bits one or more any combination after crushed.
3. the preparation method of collagen according to claim 1/sodium alginate porous gel ball heavy metal absorbent, it is characterized in that, described pore-foaming agent is one or more any combination in calcium carbonate, sodium carbonate, potash.
4. the preparation method of collagen according to claim 1/sodium alginate porous gel ball heavy metal absorbent, it is characterized in that, described CaCl
2acid solution is CaCl
2aqueous solution acid for adjusting pH to 3 ~ 5.
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Cited By (7)
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| CN106540650A (en) * | 2016-10-20 | 2017-03-29 | 北京师范大学 | A kind of preparation method of waterworks sludge base dephosphorization granule adsorbent |
| CN108452785A (en) * | 2018-04-25 | 2018-08-28 | 西南科技大学 | Collagen polypeptide nanosphere is grafted the preparation method of hydrous titanium oxide sorbing material |
| CN108905983A (en) * | 2018-07-19 | 2018-11-30 | 浙江工业大学 | A kind of preparation method of the Beta-cyclodextrin-based material of sodium alginate-for handling intermetallic composite coating waste water |
| CN109364887A (en) * | 2018-09-13 | 2019-02-22 | 安庆师范大学 | A kind of preparation method of the porous Ca-alginate gel beads for heavy metal-polluted water process |
| CN110773134A (en) * | 2019-12-02 | 2020-02-11 | 烟台大学 | Montmorillonite-collagen composite hydrogel adsorption material and preparation method thereof |
| CN113976074A (en) * | 2021-11-23 | 2022-01-28 | 沈阳建筑大学 | Iron-manganese mud composite gel ball adsorption antimony removal material and preparation method thereof |
| CN115672293A (en) * | 2022-10-24 | 2023-02-03 | 中南大学 | Sodium alginate-loaded clay mineral gel microsphere, preparation method thereof and application of sodium alginate-loaded clay mineral gel microsphere as rare earth ion adsorption material |
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Cited By (8)
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| CN106540650A (en) * | 2016-10-20 | 2017-03-29 | 北京师范大学 | A kind of preparation method of waterworks sludge base dephosphorization granule adsorbent |
| CN108452785A (en) * | 2018-04-25 | 2018-08-28 | 西南科技大学 | Collagen polypeptide nanosphere is grafted the preparation method of hydrous titanium oxide sorbing material |
| CN108452785B (en) * | 2018-04-25 | 2020-07-28 | 西南科技大学 | Preparation method of collagen polypeptide nanosphere grafted hydrated titanium oxide adsorption material |
| CN108905983A (en) * | 2018-07-19 | 2018-11-30 | 浙江工业大学 | A kind of preparation method of the Beta-cyclodextrin-based material of sodium alginate-for handling intermetallic composite coating waste water |
| CN109364887A (en) * | 2018-09-13 | 2019-02-22 | 安庆师范大学 | A kind of preparation method of the porous Ca-alginate gel beads for heavy metal-polluted water process |
| CN110773134A (en) * | 2019-12-02 | 2020-02-11 | 烟台大学 | Montmorillonite-collagen composite hydrogel adsorption material and preparation method thereof |
| CN113976074A (en) * | 2021-11-23 | 2022-01-28 | 沈阳建筑大学 | Iron-manganese mud composite gel ball adsorption antimony removal material and preparation method thereof |
| CN115672293A (en) * | 2022-10-24 | 2023-02-03 | 中南大学 | Sodium alginate-loaded clay mineral gel microsphere, preparation method thereof and application of sodium alginate-loaded clay mineral gel microsphere as rare earth ion adsorption material |
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