CN103127916A - Preparation method of tourmaline/magnetic chitosan microsphere treatment agent - Google Patents
Preparation method of tourmaline/magnetic chitosan microsphere treatment agent Download PDFInfo
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- CN103127916A CN103127916A CN2013100968484A CN201310096848A CN103127916A CN 103127916 A CN103127916 A CN 103127916A CN 2013100968484 A CN2013100968484 A CN 2013100968484A CN 201310096848 A CN201310096848 A CN 201310096848A CN 103127916 A CN103127916 A CN 103127916A
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Abstract
The invention provides a preparation method of a tourmaline/magnetic chitosan microsphere treatment agent which is prepared by dissolving and uniformly mixing mixed powder of tourmaline and magnetic chitosan microspheres in sodium alginate and polyvinyl alcohol, and solidifying and balling. The magnetic chitosan microsphere is prepared by using superparamagnetic ferroferric oxide, 1 to 10 weight percent of chitosan acetic acid liquid, liquid paraffin, Span-80 and glutaraldehyde as reaction materials through an emulsion crosslinking method, wherein the mass ratio of the superparamagnetic ferroferric oxide to the chitosan acetic acid liquid is 1:(1-10), the volume ratio of the liquid paraffin to the Span-80 is (10-100):1, the volume ratio of the chitosan acetic acid liquid of superparamagnetic ferroferric oxide to mixed liquid of paraffin-Span-80 is 1:(1-10), and the volume ratio of the mixed liquid of superparaferroferric oxide, paraffin and Span-80 to glutaraldehyde is (5-50):1. According to the water treating agent, the removal rate of volatile phenol in water is between 80 and 90 percent, the removal rate of chromium in water is 93 percent; and the magnetic chitosan microsphere treating agent has the advantages of large adsorption capacity, high purification efficiency, low cost, regeneration, no toxicity, no pollution to environment and the like.
Description
The present invention is to be on 09 23rd, 2011 the applying date, and application number is 201110284933.4 divides an application.
Technical field
The present invention relates to the water treatment preparation, relate in particular to the preparation method of a kind of tourmaline good to volatile phenol removal effect in water/chitosan magnetic micro-sphere inorganic agent, belong to water treatment field.
Background technology
In recent years, the character of chitosan magnetic micro-sphere uniqueness and structure had caused people's extensive concern, especially obtained good achievement in the application study in water treatment.Chitosan magnetic can be with removing Cu in water
2+, Cr
2+, Hg
2+, Zn
2+, Pb
2+, Ca
2+, Ag
+Deng metal ion, also can be used for processing organic wastewater, and can reach very soon balance.Wong and G.Mckay etc.
[22-23]Once the shitosan treatment of dyeing and printing had been done very detailed research, result shows that shitosan is had very high affinity to permitting eurypalynous dyestuff, comprising disperse, directly, active, acid, sulfuration and Naphthol dyestuff, only basic-dyeable fibre is had lower affinity.Flood love is true etc.
[24]Process acid azo-colour waste water with the magnetic microsphere that shitosan parcel iron is made, result shows for certain density methyl orange solution, only needs 1 h just can remove more than 95%; And activated carbon needs 8 h could remove 88%.Han Deyan etc.
[25]Also did related experiment, reaction 1 h is more than 98% to the clearance of color degree of dyeing waste water.Document is also arranged
[27]Report is that flocculant can reclaim protein in food processing wastewater, starch etc. with shitosan.Chinese scholars is by a large amount of research, inquire into from different perspectives the using value of chitosan magnetic, utilize chitosan magnetic existing a lot of to the bibliographical information of metal ion, paper waste, dyeing waste water etc., but do not seen the Study on purification to volatile phenol in water, especially the discussion of the novel substance of crosslinked generation is very rare especially again with itself and other material.
Tourmaline because of its pyroelectricity and piezoelectricity well-known, used fully at industrial circle from mid-term in century 18th century to 20, yet its electrical properties and environment-friendly function are but paid attention to always always.1989, Kubo proposed first after deliberation the tourmaline particles surface and exists electrostatic field, and has predicted the application prospect of tourmaline at environmental area.Japanese scholars research also finds to contain tourmaline in the stratum river is difficult to contaminated, has opened up the application of tourmaline in field of environment protection.Correlative study shows, tourmaline has polarity preferably, and surface electrostatic is strong, to harmful ion in water (as Cu, As (III), F
OneDeng) stronger adsorptivity is arranged, can be used for purifying water body, be to administer the good environment mineral material that water pollutes.Up to the present, not yet see about utilizing shitosan and tourmaline to unite the relevant report that the preparation water purification agent is purified waste water.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of tourmaline/chitosan magnetic micro-sphere inorganic agent.
The objective of the invention is to be achieved through the following technical solutions:
A kind of tourmaline/chitosan magnetic micro-sphere inorganic agent is characterized in that: it is that mixed-powder with tourmaline and chitosan magnetic micro-sphere joins dissolving, mixing in sodium alginate and polyvinyl alcohol, then solidifies balling-up and makes; Described chitosan magnetic micro-sphere is preferably 2wt% take SPIO powder, 1～10wt%() shitosan acetic acid solution, atoleine, Span-80, glutaraldehyde solution are as reaction mass, make by emulsion-crosslinking method, wherein SPIO is that 1:1～10(preferred mass is than being 2:5 with the mass ratio of described shitosan acetic acid solution); Atoleine and Span-80 volume ratio 10～100:1(preferred volume ratio are 40:1); The volume ratio of the shitosan acetic acid solution of SPIO and paraffin-Span-80 mixed liquor is 1:1～10, be preferably 1:2; The mixed liquor of the shitosan acetic acid solution of above-mentioned SPIO and paraffin, Span-80 is with glutaraldehyde solution (preferred adopt analyze pure) volume ratio 5～50:1, be preferably 25:1.
In the preparation of tourmaline and chitosan magnetic micro-sphere, if balling-up very little, in use easily loose, balling-up too much, blocked up can affect the performance of active ingredient effect, so all can affect treatment effeciency.In order further to improve uniformity and the validity of balling-up, thereby improve water treatment agent of the present invention to the clearance of phenol, in the mixed-powder of above-mentioned tourmaline and chitosan magnetic micro-sphere, the mass ratio of tourmaline and chitosan magnetic micro-sphere is 1～10:1, is preferably 5:2, and the mass ratio of the mixed-powder of above-mentioned sodium alginate, polyvinyl alcohol and tourmaline and chitosan magnetic micro-sphere is that 1:1～10:1～12, preferred mass compare 1:6:7.
Preferably, SPIO powder of the present invention makes by following:
Take 5.56 g FeSO
47H
2O, 6.5 g FeCl
3Be dissolved in 50 mL in advance through N with 1.7 mL concentrated hydrochloric acids
2In degassed processing distilled water, then with in the above-mentioned NaOH solution that is added drop-wise to 250 mL 1.0mol/L.(100r/min) stirs 5min at a slow speed in 80 ℃ of water-baths, then stirs (2000r/min) at Quick mechanical, treats to occur in solution the precipitation of black, continues stirring until 30min.After question response finished, the standing room temperature that is cooled to was separated the black precipitate product by externally-applied magnetic field, cleaned 3 times with deionized water and absolute ethyl alcohol respectively, and drying is 12 hours in the vacuum drying chamber of 60 ℃, and is stand-by.
Shitosan acetic acid solution of the present invention is dissolved in shitosan in acetic acid solution (preferred employing is analyzed pure) and makes; It is 90% shitosan that described shitosan is preferably deacetylation, available from Shanghai Hu Feng biochemical reagents Co., Ltd, be the commercially available prod.
Preferably, tourmaline of the present invention originates in Chifeng Area, Inner Mongolia, is the commercially available prod.
The preparation method of preparation method's inorganic agent of above-mentioned tourmaline/chitosan magnetic micro-sphere, preparation as follows:
A. the pretreatment of tourmaline
Tourmaline was pulverized 100-400 mesh sieve (being preferably 200 orders), it is the zwitterion of 5～7 removal adhering on surface bands of NaOH solution (being preferably 5%) washing of 2-10% with mass concentration, with after the same number of times of washed with de-ionized water, be put in baking oven the inside oven dry again, stand-by;
B. the preparation of SPIO powder
Take 5.56 g FeSO
47H
2O, 6.5 g FeCl
3Be dissolved in 50 mL in advance through N with 1.7 mL concentrated hydrochloric acids
2In degassed processing distilled water, then with in the above-mentioned NaOH solution that is added drop-wise to 250 mL 1.0mol/L; With 100r/min low rate mixing 5min, then stirring with the 2000r/min Quick mechanical in 80 ℃ of water-baths, treating to occur in solution the precipitation of black, continuing stirring until 30min; After question response finished, the standing room temperature that is cooled to was separated the black precipitate product by externally-applied magnetic field, cleaned 3 times with deionized water and absolute ethyl alcohol respectively, and drying is 12 hours in the vacuum drying chamber of 60 ℃, and is stand-by;
C. the preparation of chitosan magnetic micro-sphere
taking the SPIO powder, to join mass concentration be that 1～10%(is preferably 2%) the shitosan acetic acid solution in, wherein the mass ratio of SPIO and shitosan acetic acid solution is that 1:1～1:10(is preferably 2:5), after mixing, be transferred in the mixed liquor of atoleine and Span-80, wherein atoleine and Span-80 volume ratio 10:1～100:1(preferred volume ratio are 40:1), adjust pH to 3.0～12.0(is preferably 9.0), preferred 200 r/min of 100～500 r/min() stir 30min, the volume ratio of the shitosan acetic acid solution of described SPIO and paraffin-Span-80 mixed liquor is that 1:1～1:10(is preferably 1:2), drip glutaraldehyde solution, the mixed liquor of the shitosan acetic acid solution of SPIO and paraffin, Span-80, and glutaraldehyde solution (preferred employing is analyzed pure) volume ratio 5:1～50:1(is preferably 25:1), at 20～80 ℃ (preferred 40 ℃) the lower stirring 60min that continues, make it abundant reaction, again filtration under diminished pressure, use benzinum, absolute ethyl alcohol extracting 1-10 time (preferred 3 times) successively, vacuum drying under 20-100 ℃ of (preferred 50 ℃) condition, and get final product,
D. the preparation of tourmaline/chitosan magnetic micro-sphere (MCD)
After above-mentioned chitosan magnetic micro-sphere is ground to form 100～400 orders (being preferably 140 orders) powder, then with tourmaline powder according to mass ratio 1:1～10:1(preferred mass than being 5:2) the abundant mixing of ratio, make mixed-powder; With sodium alginate, polyvinyl alcohol and mixed-powder according to 1:1:1～1:10:12(preferred mass than 1:6:7) ratio prepare microballoon; Preparation first with sodium alginate and polyvinyl alcohol heating for dissolving 15min, adds mixed-powder to stir during microballoon immediately, and the preferred time of cooling 5～60min(is 20min) after with constant flow pump with constant flow rate continuously with hanging drop to containing 1～10wt%CaCl
2Solidify in the saturated BAS of (preferred 2wt%).Leach bead after solidifying 5～40 h (preferred 20 h), dry standby after water is rinsed well.
The present invention has following beneficial effect:
Tourmaline of the present invention/chitosan magnetic micro-sphere inorganic agent to the volatile phenol clearance in drinking water source (as underground water, reservoir water etc.) can reach 80%～90%, the clearance of chromium can reach 93%, obvious processing effect, referring to specific embodiment part, simultaneously inorganic agent of the present invention have that adsorption capacity is large, purification efficiency is high, cost is low, the advantage such as renewable, nontoxic, environmentally safe.The preparation method of tourmaline of the present invention/chitosan magnetic micro-sphere inorganic agent is easy, repetitive operation is strong, with low cost, be fit to industrial-scale production.
The specific embodiment
Below by embodiment, the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
A kind of tourmaline/chitosan magnetic micro-sphere inorganic agent makes according to the following steps:
A. the pretreatment of tourmaline
Tourmaline was pulverized 200 mesh sieves, was the zwitterion that 5% NaOH solution washing is removed the adhering on surface bands for 5～7 times with mass concentration, then with after the same number of times of washed with de-ionized water, was put in baking oven the inside oven dry, stand-by;
B. the preparation of SPIO powder
Take 5.56 g FeSO
47H
2O, 6.5 g FeCl
3Be dissolved in 50 mL in advance through N with 1.7 mL concentrated hydrochloric acids
2In degassed processing distilled water, then with in the above-mentioned NaOH solution that is added drop-wise to 250 mL 1.0mol/L; (100r/min) stirs 5min at a slow speed in 80 ℃ of water-baths, then stirs (2000r/min) at Quick mechanical, treats to occur in solution the precipitation of black, continues stirring until 30min; After question response finished, the standing room temperature that is cooled to was separated the black precipitate product by externally-applied magnetic field, cleaned 3 times with deionized water and absolute ethyl alcohol respectively, and drying is 12 hours in the vacuum drying chamber of 60 ℃, and is stand-by.
C. the preparation of chitosan magnetic micro-sphere
It is that in 2% shitosan acetic acid solution, the mass ratio of described SPIO and shitosan acetic acid solution is 2:5 that the SPIO powder that takes about particle diameter 20nm joins mass concentration; After mixing, be transferred to the edible class of atoleine (analyzing pure) and Span-80() mixed liquor in, wherein atoleine and Span-80 volume ratio are 40:1, adjust pH to 9.0,200 r/min stir 30min, and wherein the consumption volume ratio of the shitosan acetic acid solution of SPIO and paraffin-Span-80 mixed liquor is 1:2; Drip glutaraldehyde solution, the mixed liquor of the shitosan acetic acid solution of SPIO and paraffin, Span-80, with glutaraldehyde solution (analyzing pure) volume ratio be 25:1, continue to stir 60min under 40 ℃, make it abundant reaction, then filtration under diminished pressure, benzinum, absolute ethyl alcohol extracting three times used successively, vacuum drying under 50 ℃ of conditions, and get final product;
D. the preparation of tourmaline/chitosan magnetic micro-sphere (MCD)
After above-mentioned chitosan magnetic micro-sphere is ground to form 140 order powder, then with the ratio abundant mixing of above-mentioned tourmaline powder according to 5:2, make mixed-powder; Sodium alginate, polyvinyl alcohol and mixed-powder are prepared microballoon according to the ratio of mass ratio 1:6:7; Preparation first with sodium alginate and polyvinyl alcohol heating for dissolving 15min, adds mixed-powder to stir during microballoon immediately, after cooling 20 min with constant flow pump with constant flow rate continuously with hanging drop to containing 2%CaCl
2Saturated BAS in solidify, leach bead after solidifying 20 h, dry standby after water is rinsed well.
Embodiment 2～4: undertaken by following each material and step, all the other are with embodiment 1.
The above-mentioned tourmaline that makes/chitosan magnetic micro-sphere inorganic agent is 78%～90% to the clearance of volatile phenol in source water.
Application Example 1
Tourmaline/chitosan magnetic micro-sphere (MCD) microballoon purifies water sample
1, the removal of volatile phenol in water is tested
Get the 50ml source water and (contain the water sample of volatile phenol 0.0043-0.0049mg/L) in the 250ml triangular flask, add the MCD microballoon that embodiment 1 makes, regulate experiment condition, standing after the vibration certain hour, filtration in the constant temperature oscillation case, with the phenol content of measuring in filtrate, can draw MCD to the clearance of volatile phenol by calculating.Experimental design is as shown in table 1, table 2.Each tests equal triplicate, gets its mean value.
(1), experiment of single factor
Table 1 single factor design
(2), quadratic regression political affairs religion rotation combination
Adopt on the basis of the above quadratic regression orthogonal rotational combination 3(1/2) design the factor of MCD bead to volatility phenol in water designed, get MCD dosage (x
1), pH (x
2) and reaction time (x
3) as three investigation factors, each factor is chosen five levels, sees Table 2.
Table 2 orthogonal test factor level coding schedule
2, the removal of Cr in water is tested
Get 50ml source water (containing Cr 0.045-0.056mg/L) in the 250ml triangular flask, the MCD microballoon that adds embodiment 1 to make, regulate experiment condition, standing after the vibration certain hour, filtration in the constant temperature oscillation case, with the volatile phenol in gas chromatography determination filtrate, with the Cr(VI in atomic absorption spectroscopy determination filtrate), can draw microballoon to the clearance of Cr (VI) by calculating.Experimental design is as shown in table 1, table 2.Each tests equal triplicate, gets its mean value.
Table 1 single factor design
Table 2 orthogonal test factor level coding schedule
(3) conclusion:
1, the removal of volatile phenol in water is tested
(1) experiment of single factor shows, the MCD bead can be used for removing the phenol compounds in water, there are certain impact in MCD dosage, pH, reaction time etc. on the removal of volatile phenol in water, be 10 at pH, when duration of oscillation is 1.5h, MCD dosage 2.5g, in water, the potential clearance of volatile phenol reaches 84.17%.
(2) on the experiment of single factor basis, use theory and the method for Fertilizer Test of Regression Design, determined optimum experimental condition by the DPS data handling system: the MCD dosage is 2.16g, processing time to be that 1.12h, pH value are 10.55, and in water, the clearance of volatile phenol reaches 90.72% with this understanding.
2, the removal of chromium in water is tested
(1) experiment of single factor shows, MCD is used for removing the chromium of source water, is that 3g, pH are 6, the reaction time, when being 90min, in source water, the clearance of chromium reached best at dosage.
(2) on the experiment of single factor basis, use theory and the method for Fertilizer Test of Regression Design, the optimum experimental condition of determining by the DPS data handling system: the microballoon dosage is that 2.444g, pH 4.6, reaction time are 80.4min, and in source water, the chromium clearance reaches 93.13% with this understanding.
(3) on the experiment of single factor basis, use theory and the method for Fertilizer Test of Regression Design, determined optimum experimental condition by the DPS data handling system: the reaction time is 80.4min, and the pH value is 4.6, and the microballoon dosage is 2.444g.With this understanding, know Cr(VI in source water by inference according to Mathematical Modeling) clearance can reach 93.93%.
Claims (1)
1. the preparation method of tourmaline/chitosan magnetic micro-sphere inorganic agent, according to the following steps:
A. the pretreatment of tourmaline
Tourmaline was pulverized 150 mesh sieves, was the zwitterion that 2.6% NaOH solution washing is removed the adhering on surface bands for 5～7 times with mass concentration, then with after the same number of times of washed with de-ionized water, was put in baking oven the inside oven dry, stand-by;
B. the preparation of SPIO powder
Take 5.56 g FeSO
47H
2O, 6.5 g FeCl
3Be dissolved in 50 mL in advance through N with 1.7 mL concentrated hydrochloric acids
2In degassed processing distilled water, then with in the above-mentioned NaOH solution that is added drop-wise to 250 mL 1.0mol/L; (100r/min) stirs 5min at a slow speed in 80 ℃ of water-baths, then stirs (2000r/min) at Quick mechanical, treats to occur in solution the precipitation of black, continues stirring until 30min; After question response finished, the standing room temperature that is cooled to was separated the black precipitate product by externally-applied magnetic field, cleaned 3 times with deionized water and absolute ethyl alcohol respectively, and drying is 12 hours in the vacuum drying chamber of 60 ℃, and is stand-by;
C. the preparation of chitosan magnetic micro-sphere
It is that in 3% shitosan acetic acid solution, the mass ratio of described SPIO and shitosan acetic acid solution is 1:2 that the SPIO powder that takes about particle diameter 20nm joins mass concentration; After mixing, be transferred to the edible class of atoleine (analyzing pure) and Span-80() mixed liquor in, wherein atoleine and Span-80 volume ratio are 15:1, adjust pH to 9.0,200 r/min stir 30min, and wherein the consumption volume ratio of the shitosan acetic acid solution of SPIO and paraffin-Span-80 mixed liquor is 1:1; Drip glutaraldehyde solution, the mixed liquor of the shitosan acetic acid solution of SPIO and paraffin, Span-80, with glutaraldehyde solution (analyzing pure) volume ratio be 26:1, continue to stir 60min under 40 ℃, make it abundant reaction, then filtration under diminished pressure, benzinum, absolute ethyl alcohol extracting three times used successively, vacuum drying under 50 ℃ of conditions, and get final product;
D. the preparation of tourmaline/chitosan magnetic micro-sphere (MCD)
After above-mentioned chitosan magnetic micro-sphere is ground to form 140 order powder, then with the ratio abundant mixing of above-mentioned tourmaline powder according to 1:2, make mixed-powder; Sodium alginate, polyvinyl alcohol and mixed-powder are prepared microballoon according to the ratio of mass ratio 1:5:10; Preparation first with sodium alginate and polyvinyl alcohol heating for dissolving 15min, adds mixed-powder to stir during microballoon immediately, after cooling 20 min with constant flow pump with constant flow rate continuously with hanging drop to containing 2%CaCl
2Saturated BAS in solidify, leach bead after solidifying 20 h, dry standby after water is rinsed well.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014321A (en) * | 2014-06-20 | 2014-09-03 | 厦门大学 | Chitosan/polyvinyl alcohol/ferroferric oxide composite magnetic particle as well as preparation and application thereof |
| CN108212105A (en) * | 2018-01-02 | 2018-06-29 | 天津市职业大学 | Application of the Tourmaline/chitosan composite material in landfill leachate treatment |
| CN108854988A (en) * | 2018-07-06 | 2018-11-23 | 武汉霖泉环保科技有限公司 | Chitosan magnetic adsorbent, preparation process and the application in heavy metal water process |
| CN111534644A (en) * | 2020-05-26 | 2020-08-14 | 广西大学 | Method for removing alkaline degradation pigments of sugar beet sugar-making dilute juice hexose |
| CN112915972A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | high-Cr (VI) adsorption amount core-shell structure high-molecular magnetic nanosphere and preparation method and application thereof |
| CN113929211A (en) * | 2021-10-18 | 2022-01-14 | 中国环境科学研究院 | Biological enhanced reactor denitrification process based on tourmaline carrier |
| CN116364377A (en) * | 2023-02-23 | 2023-06-30 | 南通冠优达磁业股份有限公司 | Superparamagnetism conductive fluid material and preparation method thereof |
| CN116637591A (en) * | 2023-05-26 | 2023-08-25 | 中国丝绸博物馆 | Adsorption material for enrichment of trace collagen of leather cultural relics and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104014321A (en) * | 2014-06-20 | 2014-09-03 | 厦门大学 | Chitosan/polyvinyl alcohol/ferroferric oxide composite magnetic particle as well as preparation and application thereof |
| CN108212105A (en) * | 2018-01-02 | 2018-06-29 | 天津市职业大学 | Application of the Tourmaline/chitosan composite material in landfill leachate treatment |
| CN108212105B (en) * | 2018-01-02 | 2021-01-12 | 天津市职业大学 | Application of tourmaline/chitosan composite material in landfill leachate treatment |
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| CN111534644A (en) * | 2020-05-26 | 2020-08-14 | 广西大学 | Method for removing alkaline degradation pigments of sugar beet sugar-making dilute juice hexose |
| CN112915972A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | high-Cr (VI) adsorption amount core-shell structure high-molecular magnetic nanosphere and preparation method and application thereof |
| CN113929211A (en) * | 2021-10-18 | 2022-01-14 | 中国环境科学研究院 | Biological enhanced reactor denitrification process based on tourmaline carrier |
| CN113929211B (en) * | 2021-10-18 | 2022-11-08 | 中国环境科学研究院 | Biologically enhanced reactor denitrification process based on tourmaline carrier |
| CN116364377A (en) * | 2023-02-23 | 2023-06-30 | 南通冠优达磁业股份有限公司 | Superparamagnetism conductive fluid material and preparation method thereof |
| CN116637591A (en) * | 2023-05-26 | 2023-08-25 | 中国丝绸博物馆 | Adsorption material for enrichment of trace collagen of leather cultural relics and preparation method and application thereof |
| CN116637591B (en) * | 2023-05-26 | 2024-04-05 | 中国丝绸博物馆 | Adsorption material for enrichment of trace collagen of leather cultural relics and preparation method and application thereof |
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| CN103127916B (en) | 2014-09-10 |
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