CN1410157A - Collagen fiber solidified tannin adsorptive material and its preparation method and its adsorption and separation of metallic ion - Google Patents
Collagen fiber solidified tannin adsorptive material and its preparation method and its adsorption and separation of metallic ion Download PDFInfo
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Abstract
An adsorbing collagen fibre-solidified tannin material for adsorbing and separating metallic ions (Pb, Cd, Hg, Cr and Cu) is prepared from animal skin through preparing collagen fibre membrane or granules, adding the said collagen fibres along with the aqueous solution of tannin to a reactor, reacting at 10-45 deg.c for 6-24 hr, laying aside for 12-24 hr, filtering, washing to remove excessive tannin, adding cross-linking agent, reacting at 20-70 deg.c for 2-8 hr, filtering, washing and drying at 60 deg.c for 12-24 hr. It has very high adsorption selectivity.
Description
One, technical field
The present invention relates to a kind of collagen fiber solidified tannin adsorptive material and preparation method thereof with to the absorption of metal ion with separate.
Two, background technology
Production processes such as chemical industry, metallurgy, oil will produce a large amount of waste water, and heavy metal ion such as the lead in the waste water, cadmium, mercury are serious environment pollution, and human body is had extremely strong toxic and side effect.Therefore, each state has all formulated strict wastewater discharge standard.The method of removing heavy metal ion at present mainly contains the precipitation method, ion-exchange and absorption method (Zhang Ping, Cai Shuihong, Luo Zanchun, Zhang Qiuhua, the research of shitosan adsorbing metal ions " hydrometallurgy " 1994,49 (1): 16-20; Liu Lizhong, Yu Shanxin, Xiao Lixin, the macromolecule loading schiff bases is to the characterization of adsorption " ion-exchange and absorption " 1995,11 (2) of metal ion: 122-127; Zhang Jianbo, Feng Jinmin, application and the development " Techniques and Equipment for Environmental Pollution Control " 2000 of ion exchange technique in wastewater treatment, 1 (1): 46-51), extraction (Zhang Yanjun, Xiao Jun, the progress of the supercritical liquid extraction technique of metal ion " physical and chemical inspection-chemical fascicle ", 2001,37 (12): 576-578) etc.The efficient of the precipitation method is low, and will introduce other impurity in precipitate metal ion; The selectivity of ion-exchange is relatively poor and exchange capacity is low; Extraction will use different solvents, will produce secondary pollution to environment, but also relate to the solvent recovery problem.In addition, with the exhaustion day by day of landing field mineral resources, separation and concentration metal element such as uranium etc. will be one of fields of various countries' focus development from seawater, and marine resources development will be the important content of various countries' strategy of sustainable development.From the angle of Technological Economy, adsorption method of separation should be the main method of separation and concentration metal ion, and the research and development of sorbing material are key technologies.The sorbing material of exploitation is of a great variety at present, and overview is got up and mainly had following defective: the one, and adsorption capacity is lower, and the 2nd, selectivity is not high, and the 3rd, the sorbing material price is higher.
Tannin has the ability of precipitate metal ion.Because the water-soluble problem of tannin, therefore use tannin seldom separately, but tannin is solidificated in (Chibata I, Tosa T, Mori T on some matrix, et al., Immobilized tannin-anovel adsorbent for protein and metal ion, Enzyme Microb.Technol., 1986,8:130-136), be called solidified tannin.These solidified tannins are many to be matrix with the cellulose, and its reactions steps is many, complex process, and tannin can not be solidificated on the matrix securely, comes off easily, and physical property is also very poor.
As everyone knows, the triple helix structure that collagenous fibres are made up of three peptide chains contains peptidyl, amino, carboxyl, hydroxyl etc. on its main chain and the side chain; And tannin is a polyphenol compound, and its ortho position phenolic hydroxyl group has extremely strong metal ion-chelant ability.Collagenous fibres can combine by hydrophobic bond and hydrogen bond with tannin, and this combination is reversible.If directly certainly exist the loss of tannin as sorbing material with tannin or tannin resin; And it is relatively poor that tannin is solidificated on the string intensity as sorbing material; If tannin is adsorbed on the collagenous fibres sorbing material as metal ion, because of collagenous fibres and tannin are by the hydrogen bond combination, the therefore problem that exists tannin to come off equally.
Three, summary of the invention
The objective of the invention is provides a kind of collagen fiber solidified tannin adsorptive material and preparation method thereof at the deficiencies in the prior art, be characterized in adopting the matrix of natural biodegradable collagenous fibres for the preparation sorbing material, the tannin that will have an extremely strong metal ion-chelant ability by chemical bond in conjunction with being fixed on the collagenous fibres, thereby prepared the sorbing material of high selectivity, high-adsorption-capacity.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1, the recipe ingredient of collagen fiber adsorption material is:
10～20 parts of collagenous fibres
5～10 parts of tannin
1～6 part of crosslinking agent
Wherein collagenous fibres are that membranoid substance or the average grain diameter of thickness 0.5-5mm are the shot-like particle of 10-100 μ m, and the shrinkage temperature of collagen fiber solidified tannin adsorptive material is 70-115 ℃.
Tannin is condensing class tannin (as acacia mearnsii skin tannin, larch tannin) or mixes class tannin (as Baybery tannin).
Crosslinking agent is formaldehyde, glutaraldehyde with at least a in the/Huo oxazolidine.
2, the preparation method of collagen fiber solidified tannin adsorptive material
(1) preparation of collagenous fibres
Choosing animal skins is raw material, cleans according to a conventional method, alkali treatment, splitting, dealkalize, demineralization thing and buffer solution processing, dehydration, dry collagenous fibres are thickness 0.5～5mm membranoid substance or obtain average grain diameter through grinding is 10-100 μ m granular rubber fibrillation.
(2) preparation of collagen fiber solidified tannin adsorptive material
With 10～20 parts of collagenous fibres and 5～10 parts of tannin (tannin is made into the 10-100g/L aqueous solution), adding has in the reactor of agitator, thermometer and reflux condenser, reacts 6-24 hour down in temperature 10-45 ℃, leaves standstill 12-24 hour; Remove by filter unreacted tannin; Add 1～6 part of crosslinking agent (being mixed with the 0.5-3.0% aqueous solution), temperature 20-70 ℃ of reaction 2-8 hour; Filter the unreacted crosslinking agent of flush away; At 50～70 ℃ of dry 12-24 of temperature hours, obtain collagen fiber solidified tannin adsorptive material; Recording shrinkage temperature with differential thermal analyzer (DSC) is 70-115 ℃.
Prepared collagen fiber solidified tannin adsorptive material combines by chemical bond tannin with collagenous fibres, thereby has eliminated the solubility problem of tannin resin or string solidified tannin and the problem of intensity difference; Collagen fiber solidified tannin adsorptive material has high selective adsorption capacity to metal ion.Can be widely used in chemical industry, metallurgy and the absorption of the lead during petroleum industry is wastewater produced, cadmium, mercury, chromium, copper etc. with separate.
The present invention has following advantage:
1, collagen fiber solidified tannin adsorptive material surpasses 99% to the adsorption rate of some metal ion, and adsorption capacity reaches 150mg/g (adsorbent).
2, its tannin of having solved other solidified tannin adsorptive material problem that comes off has higher mechanical strength and heat endurance.
3, it is extensive that collagen fiber solidified tannin prepares the raw material sources of this sorbing material, and technology is easy, complete biodegradable, environmentally safe.
Four, the specific embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
The preparation method of embodiment 1 collagen fiber solidified acacia mearnsii skin tannin adsorptive material
1, the fibriilar preparation of granular rubber
Choosing animal skins is raw material, cleans according to a conventional method, alkali treatment, splitting, dealkalize, demineralization thing and buffer solution is handled, dehydration, dry and grind the granular rubber fibrillation that obtains average grain diameter 90 μ m.
2, the preparation of collagen fiber solidified acacia mearnsii skin tannin adsorptive material
9g is mixed with the 20-40g/L aqueous solution with acacia mearnsii skin tannin; Taking by weighing 15g granular rubber fibrillation returns wet with distilled water; The collagenous fibres that return after wet are joined in the acacia mearnsii skin tanning solution,, left standstill 12 hours 25 ℃ of stirring reactions of temperature 24 hours; Filter,, get intermediate product A with the unreacted tannin of deionized water flush away; Oxazolidine 6g is prepared 1.5% aqueous solution; In A Fang Ru oxazolidine solution,, left standstill 12 hours 60 ℃ of stirring reactions of temperature 4 hours; Filter, wash the not oxazolidine of reaction with deionized water, and 60 ℃ of dryings of temperature 15 hours, obtain collagen fiber solidified acacia mearnsii skin tannin adsorptive material, recording shrinkage temperature with differential thermal analyzer (DSC) is 98 ℃.
Embodiment 2 collagen fiber solidified Baybery tannin adsorbed film preparation methods
1, the preparation of collagenous fibres film
Method by embodiment 1 is handled animal skins, but does not grind, and gets the collagenous fibres film
2, the preparation of collagen fiber solidified Baybery tannin absorption glue material:
Baybery tannin 9g is made into the 25g/L aqueous solution; Taking by weighing the membranaceous collagenous fibres of 15g returns wet with distilled water; The collagenous fibres that return after wet are joined in the Baybery tannin solution,, left standstill 12 hours 25 ℃ of stirring reactions of temperature 24 hours; Filter,, get intermediate product A with the unreacted tannin of distilled water flush away; Oxazolidine 4g is prepared 1.5% solution; In A Fang Ru oxazolidine solution,, left standstill 12 hours 60 ℃ of stirring reactions of temperature 4 hours; Filter, with distilled water flush away Wei reaction De oxazolidine, and at 65 ℃ of dry 12-24 hours, obtain collagen fiber solidified tannin adsorbed film material, recording shrinkage temperature with differential thermal analyzer (DSC) is 90 ℃.
The preparation method of embodiment 3 collagen fiber solidified acacia mearnsii skin tannin adsorptive materials
1, the fibriilar preparation of granular rubber
Prepare the granular rubber fibrillation by embodiment 1 method
2, the preparation of collagen fiber solidified acacia mearnsii skin tannin adsorptive material:
6g is made into the 20g/L aqueous solution with acacia mearnsii skin tannin; Taking by weighing the 10g collagenous fibres returns wet with distilled water; The collagenous fibres that return after wet are joined in the acacia mearnsii skin tanning solution,, left standstill 12 hours 25 ℃ of stirring reactions of temperature 24 hours; Filter,, get intermediate product A with the unreacted tannin of distilled water flush away; The aqueous solution with formaldehyde 6g preparation 3%; A is put into formalin,, left standstill 12 hours 60 ℃ of stirring reactions of temperature 6 hours; Filter, with the unreacted formaldehyde of distilled water flush away, and at 60 ℃ of dry 12-24 hours, obtain collagen fiber solidified tannin adsorptive material, recording shrinkage temperature with differential thermal analyzer (DSC) is 92 ℃.
The preparation method of embodiment 4 collagen fiber solidified acacia mearnsii skin tannin adsorptive materials
1, the preparation of membranaceous collagenous fibres
Choose goat skin, handle, comprise processing such as depilation, degreasing, splitting, obtain membranaceous collagenous fibres by the conventional method of leather industry.
2, the preparation of membranaceous collagen fiber solidified acacia mearnsii skin tannin
Take by weighing the membranaceous collagenous fibres of 100g, add the 100ml deionized water, normal temperature vibrated 1 hour down; Regulate pH to 6.6, vibrated again 1 hour; Take out membranaceous collagenous fibres drip-dry moisture content under field conditions (factors), about 12 hours; Put into the 100ml deionized water, add 15g acacia mearnsii skin tannin again, normal temperature vibrated 6 hours down, left standstill 12 hours; Waste liquid is removed in membranaceous collagenous fibres taking-up, add the 100ml deionized water,, add 0.25g formic acid again, vibrated 1.5 hours 40 ℃ of vibrations 1.5 hours; Fully wash drip-dry moisture content with deionized water; The concentration of putting into 100ml oxazolidine solution ， oxazolidine solution is 2%; In 60 ℃ of oscillating reactions of temperature 4 hours, left standstill 12 hours; Fully wash with deionized water, dry under the natural conditions; Membranaceous collagenous fibres are processed into the thickness that needs, promptly obtain membranaceous collagen fiber solidified tannin adsorptive material.Recording contraction people temperature with differential thermal analyzer (DSC) is 98 ℃.
Application example 1 collagen fiber solidified Baybery tannin sorbing material is to the absorption of lead, cadmium, mercury, chromium, copper
Preparation contains each 100ml of simulated wastewater of lead, cadmium, mercury, chromium, copper 20mg/L respectively, each vibrates at normal temperatures with the prepared collagen fiber solidified Baybery tannin sorbing material of 0.5g and adsorbed 8 hours, change calculations adsorption rate by concentration before and after the absorption, the results are shown in Table 1, illustrate that collagen fiber solidified tannin adsorptive material has high selective adsorption capacity to metal ion.
Application example 2 collagen fiber solidified acacia mearnsii skin tannin adsorption columns are to the absorption of copper (II) ion
Preparation cupric (II) solution, its concentration is 20.0mg/L.With collagen fiber solidified acacia mearnsii skin tannin adsorptive material dress post, packing layer diameter 11mm highly is 170mm.Solution is crossed adsorption column with the velocity flow of 2.75BV/hr (BV-bed volume), reaches leakage point when effluent volume is 30 bed volume.
Application example 3 collagen fiber solidified Baybery tannins are to the absorption of iron (II) ion
Preparation contains the ethanol water 100ml of iron (II) ion, concentration of alcohol 25% (V/V), iron concentration is 60mg/L, adsorbed 4 hours with the vibration under 25 ℃ of collagen fiber solidified Baybery tannin sorbing material, iron (II) ion concentration is 0.10mg/L in the solution of absorption back, and adsorption rate is 99.83%.
The adsorption rate metal ion initial concentration absorption back concentration adsorption rate of table 1 heavy metal ion
mg/L mg/L ％ Pb
2+ 20.00 0.26 98.7 Cd
2+ 20.00 0.82 95.9 Ag
+ 20.00 0.07 99.65 Cr
3+ 20.00 1.10 94.5 Cu
2+ 20.00 0.04 99.8
Claims (6)
1, collagen fiber solidified tannin adsorptive material is characterized in that the recipe ingredient (by weight) of this tannin adsorptive material is:
10～20 parts of collagenous fibres
5～10 parts of tannin
1～6 part of crosslinking agent
Wherein collagenous fibres are that membranoid substance or the average grain diameter of thickness 0.5-5mm are the shot-like particle of 10-100 μ m, and the shrinkage temperature of collagen fiber solidified tannin adsorptive material is 70-115 ℃.
2,, it is characterized in that collagen fiber solidified tannin is with the chemical bond combination according to the described collagen fiber solidified tannin adsorptive material of claim 1.
3,, it is characterized in that tannin is condensing class tannin or mixes the class tannin according to the described collagen fiber solidified tannin adsorptive material of claim 1.
4,, it is characterized in that crosslinking agent is formaldehyde, glutaraldehyde with at least a in the/Huo oxazolidine according to the described collagen fiber solidified tannin adsorptive material of claim 1.
5, according to the preparation method of the described collagen fiber solidified tannin adsorptive material of claim 1～4, it is characterized in that:
(1) preparation of collagenous fibres
Choosing animal skins is raw material, clean according to a conventional method, alkali treatment, splitting, dealkalize, demineralization thing and buffer solution processing, dehydration, dry that thickness be 0.5-5mm collagenous fibres films, or again through grinding to such an extent that average grain diameter is the granular rubber fibrillation of 10-100 μ m.
(2) preparation of collagen fiber solidified tannin adsorptive material
With 10～20 parts of collagenous fibres, 5～10 parts of tannin (being mixed with the 10-100g/L aqueous solution), add and have in the reactor of agitator, thermometer and reflux condenser, reacted 6-24 hour down in temperature 10-45 ℃, left standstill 12-24 hour, filter then, the unreacted tannin of flush away, add 1～6 part of crosslinking agent (being mixed with the 0.5-3.0% aqueous solution), temperature 20-70 ℃ of reaction 2-8 hour, filtration, the unreacted crosslinking agent of flush away, at 50～70 ℃ of dry 12-24 of temperature hours, obtain collagen fiber solidified tannin adsorptive material.
6, according to the purposes of the described collagen fiber solidified tannin adsorptive material of claim 1～5, the absorption that it is characterized in that lead, cadmium, mercury, chromium, copper during this solidified tannin adsorptive material can be used as column packing or membrane material is widely used in chemical industry, metallurgy and petroleum industry is wastewater produced with separate.
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- 2002-11-27 CN CNB021341745A patent/CN1164357C/en not_active Expired - Fee Related
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