CN109529953A - A kind of collagen TiO2Composite catalyst and preparation method thereof - Google Patents
A kind of collagen TiO2Composite catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109529953A CN109529953A CN201811523152.4A CN201811523152A CN109529953A CN 109529953 A CN109529953 A CN 109529953A CN 201811523152 A CN201811523152 A CN 201811523152A CN 109529953 A CN109529953 A CN 109529953A
- Authority
- CN
- China
- Prior art keywords
- collagen
- tio
- composite catalyst
- acetum
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 102000008186 Collagen Human genes 0.000 title claims abstract description 69
- 108010035532 Collagen Proteins 0.000 title claims abstract description 69
- 229920001436 collagen Polymers 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005238 degreasing Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 12
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 12
- 239000000287 crude extract Substances 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 9
- 238000000502 dialysis Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 230000007071 enzymatic hydrolysis Effects 0.000 claims abstract description 7
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000010865 sewage Substances 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 102000057297 Pepsin A Human genes 0.000 claims description 8
- 108090000284 Pepsin A Proteins 0.000 claims description 8
- 229940111202 pepsin Drugs 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 238000004108 freeze drying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019581 fat taste sensations Nutrition 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of collagen TiO2Composite catalyst and preparation method thereof.The collagen TiO2Composite catalyst is one kind using collagen as carrier, supports the nano-particle composite catalyst that Nano titanium dioxide active constituent obtains.Preparation method, comprising: clean pigskin degreasing will be handled, foreign protein is removed after the completion of degreasing；The pigskin enzymatic hydrolysis of foreign protein will have been removed, has been filtered after enzymatic hydrolysis；Filtrate is saltoutd, centrifugation obtains collagen crude extract after saltouing；By collagen crude extract successively with acetum dialysis, ultrapure water dialysis, freeze-drying obtains collagen sterling later；Nano titanium dioxide sample is prepared using butyl titanate and diluted acid as raw material；Collagen sterling is dissolved, addition Nano titanium dioxide sample in acetum, impregnated after ultrasonic disperse, then successively dried, is broken, calcining, is broken rear up to collagen TiO2Composite catalyst.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of collagen TiO2Composite catalyst and its preparation side
Method.
Background technique
China's animal husbandry development is rapid, and national pork annual output, meat products and byproduct processing total value rise year by year, still
Due to pigskin crinosity fattiness, often waste is taken as to carry out discard processing in many places, can only be cooked in few places
It is eaten later, causes the significant wastage of resource, also polluted environment to a certain extent.Therefore, modern material is utilized
It is a good research topic that processing technology, which makes full use of its acquisition, not only can protect society to avoid the waste of resource
Environment can also improve use value, increase social benefit.
There is a large amount of collagen in pigskin, collagen therein can be extracted, it is pretty such as to can refer to discipline
Et al. the extraction process delivered at " extraction of Collagen Protein From Pig Skin and Structural Identification ", then, the collagen egg that will be extracted
It is white to be filmed, collagen film can be obtained.But natural collagen protein is as the generally existing water resistant of functional biological materials
Property it is poor, thermal stability is poor, mechanical strength is low, it is easy enzymatic hydrolysis and it is easy to pollute the defects of, significantly limit its usability.The application hair
Bright people attempts to be added for the first time, and there is the nano material of photocatalytic activity to carry out hydridization therewith, be prepared into good photocatalytic activity
Composite catalyst, this composite catalyst is with a wide range of applications in sewage treatment field, can effectively accelerate sewage
Treatment progress, so as to improve environmental problem.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of collagen TiO2Composite catalyst and its preparation side
Method.The technical solution of the present invention is as follows:
First aspect, the present invention provide a kind of collagen TiO2Composite catalyst, the collagen TiO2It is compound to urge
Agent is one kind using collagen as carrier, supports the Nanocomposites catalysis that Nano titanium dioxide active constituent obtains
Agent.
The second aspect, the present invention provide above-mentioned collagen TiO2The preparation method of composite catalyst, comprising:
(1) clean pigskin degreasing will be handled, foreign protein is removed after the completion of degreasing；
(2) pigskin for having removed foreign protein is adjusted pH value with acetum in 0~4 DEG C is 2.0~2.5, and constant temperature impregnates
8~10h is stirred, the isometric acetum and pepsin is continuously added later and is digested, filtered after enzymatic hydrolysis, is protected
Reserved filtrate；
(3) sodium chloride solution is added in filtrate to saltout, centrifugation obtains collagen crude extract after saltouing；
(4) dissolve collagen crude extract with the acetum of pH2.7, then successively with the acetum dialysis 3 of pH3.0~
4d, ultrapure water 1~2d of dialysis, are lyophilized later, obtain collagen sterling；
(5) TiO 2 sol is prepared using butyl titanate and diluted acid as raw material, TiO 2 sol is successively dried, is broken
Broken, calcining obtains Nano titanium dioxide sample after being crushed；
(6) collagen sterling is dissolved in the acetum of 0.5mol/L, Nano titanium dioxide sample, dioxy is added
The ratio for changing titanium and collagen is 1:(1~8), it mixes, dipping 18 after ultrasonic disperse~for 24 hours, then successively dry, be crushed, forge
Up to collagen TiO after burning, being broken2Composite catalyst.
Further, in the step (1) degreasing process control parameter are as follows: in pigskin be added mass concentration be 0.5
System is simultaneously utilized ultrasonic degreasing by~1.0% neopelex solution, and wherein solid-liquid ratio is 1:(2.0~3.0),
Skimming temp is 20~25 DEG C, and ultrasonic power is 80~100W, and degreasing time is 2~2.5h.
Further, the control parameter of foreign protein technique is removed in the step (1) are as follows: degreasing pigskin is immersed in quality
In the sodium chloride solution that concentration is 1~5%, solid-liquid ratio is 1:(3~8), soaking time is 2~4h.
Further, in the step (2) enzymolysis process control parameter are as follows: acetic acid additional amount is with pigskin and vinegar after impregnating
Acid solution solid-liquid ratio is 1:(10~20) meter, pepsin additional amount is the 1~1.2% of original pigskin dry weight, hydrolysis temperature 0
~4 DEG C, enzymolysis time is 16~18h.
Further, the control parameter for technique of saltouing in the step (3) are as follows: concentration of sodium chloride solution be 1.0~
1.5mol/L, time of saltouing are 6~12h.
Further, centrifugal rotational speed is 8000~12000r/min in the step (3), and centrifugation time is 10~15min.
Further, titania gel is prepared in the step (5) specifically comprises the processes of: at room temperature by butyl titanate
It is slowly added into dehydrated alcohol and stirs evenly, add dilute acid for adjusting pH to 2~3, then obtained in 40~50 DEG C of ultrasonic disperses
To TiO 2 sol.
Further, the diluted acid is acetum or dust technology.
Further, calcine technology in the step (5) and the step (6) are as follows: temperature is 300~600 DEG C, and the time is
2~4h.
In terms of third, the present invention provides above-mentioned collagen TiO2Application of the composite catalyst in sewage treatment.
The beneficial effects of the present invention are: the present invention by collagen and nano-TiO2The collagen that hydridization is prepared
Nano-TiO2Composite catalyst photocatalytic activity with higher, activity are significantly higher than pure TiO2Nanoparticle.In addition, incite somebody to action this
The composite catalyst of invention is used for the processing of sewage treatment, especially organic dyestuff, shows very excellent degradation capability.
Detailed description of the invention
Fig. 1 is the TEM figure of nano-particle composite catalyst prepared by the embodiment of the present invention 1.
Specific embodiment
In the description of the present invention, it should be noted that the person that is not specified actual conditions in embodiment, according to normal conditions or
The condition that manufacturer suggests carries out.Reagents or instruments used without specified manufacturer is that can be obtained by commercially available purchase
Conventional products.
The present invention is described in further details with specific embodiment with reference to the accompanying drawing, described is to solution of the invention
It releases rather than limits.
Embodiment 1
The present embodiment provides a kind of collagen TiO2The preparation method of composite catalyst, comprising:
(1) by pigskin cleaning, unhairing, strike off external fat after, be rinsed with physiological saline, then be cut into small pieces, with steaming
Distilled water is cleaned；Then with 0.75% neopelex solution by solid-liquid ratio be that 1:2.5 impregnates pigskin, and in 25 DEG C and
Ultrasonic power is degreasing 2h under conditions of 100W；Next degreasing pigskin is immersed in the sodium chloride solution that mass concentration is 1%
In, solid-liquid ratio 1:5, the soaking and stirring time is 2h to remove foreigh protein removing；
(2) by the pigskin for having removed foreign protein in the acetum that 4 DEG C are 2.2 with pH according to solid-liquid ratio be 1:15 soaking and stirring
8h, continuously adds the acetum later and pepsin is digested, the control parameter of enzymolysis process are as follows: a rear acetic acid is molten
The additional amount of liquid after impregnating pigskin and acetum solid-liquid ratio for 1:15 in terms of, pepsin additional amount is original pigskin dry weight
1%, hydrolysis temperature is 4 DEG C, enzymolysis time 18h；It is filtered after enzymatic hydrolysis, retains filtrate；
(3) sodium chloride solution that concentration is 1.2mol/L is added in filtrate to saltout 6h, white flock precipitate occurs, saltouts
After centrifugation obtain collagen crude extract；Wherein centrifugal rotational speed is 10000r/min, centrifugation time 10min；
(4) dissolve collagen crude extract with the acetum of pH2.7, then successively with the acetum dialysis 3d of pH3.0,
Ultrapure water dialysis 1d, is lyophilized later, obtains collagen sterling；
(5) TiO 2 sol is prepared using butyl titanate and diluted acid as raw material, specifically comprises the processes of: at room temperature by metatitanic acid four
Butyl ester, which is slowly added into, stirs 30min in the dehydrated alcohol of 5 times of volumes of butyl titanate, adds dust technology [V (concentrated nitric acid)
: V (distilled water)=1: 49] pH to 2.5 is adjusted, it is vigorously stirred after 40min in 45 DEG C of ultrasonic disperse 30min, obtains titanium dioxide
Colloidal sol；By TiO 2 sol successively in 80 DEG C of drying, it is broken, in 500 DEG C of calcining 2h, cooling, be crushed after obtain nanoscale two
Titanium oxide sample；
(6) collagen sterling is dissolved in the acetum of 0.5mol/L, Nano titanium dioxide sample, dioxy is added
The ratio for changing titanium and collagen is 1:1, mixes, impregnates for 24 hours after ultrasonic disperse 60min, then successively dried in 80 DEG C, is broken,
Up to collagen TiO after 500 DEG C of calcining 2h, broken2Composite catalyst, collagen TiO2Composite catalyst is a kind of
Using collagen as carrier, the nano-particle composite catalyst that Nano titanium dioxide active constituent obtains is supported, TEM result is such as
Shown in Fig. 1, it can be seen from the figure that prepared composite catalyst partial size is smaller, particle size range is 5~22nm, and with C
The doping TiO of atom2Forbidden bandwidth is got higher, and has been widened its response range to visible light, has even more been improved its photocatalytic activity.
In addition, by lattice fringe spacing it is found that d=0.235nm and d=0.350nm correspond respectively to sample (001) crystal face and
(101) crystal face, and the surface of (001) crystal face can be higher, shows excellent photocatalytic activity, therefore the result compound is urged with this
The highlight catalytic active that agent is shown is consistent.
Embodiment 2
The present embodiment provides a kind of collagen TiO2The preparation method of composite catalyst, comprising:
(1) by pigskin cleaning, unhairing, strike off external fat after, be rinsed with physiological saline, then be cut into small pieces, with steaming
Distilled water is cleaned；Then with 0.75% neopelex solution by solid-liquid ratio be that 1:3.0 impregnates pigskin, and in 25 DEG C and
Ultrasonic power is degreasing 2h under conditions of 100W；Next degreasing pigskin is immersed in the sodium chloride solution that mass concentration is 1%
In, solid-liquid ratio 1:8, the soaking and stirring time is 2h to remove foreigh protein removing；
(2) by the pigskin for having removed foreign protein in the acetum that 4 DEG C are 2.2 with pH according to solid-liquid ratio be 1:10 soaking and stirring
8h, continuously adds the acetum later and pepsin is digested, the control parameter of enzymolysis process are as follows: a rear acetic acid is molten
The additional amount of liquid after impregnating pigskin and acetum solid-liquid ratio for 1:15 in terms of, pepsin additional amount is original pigskin dry weight
1.2%, hydrolysis temperature is 0 DEG C, enzymolysis time 18h；It is filtered after enzymatic hydrolysis, retains filtrate；
(3) sodium chloride solution that concentration is 1.5mol/L is added in filtrate to saltout 6h, white flock precipitate occurs, saltouts
After centrifugation obtain collagen crude extract；Wherein centrifugal rotational speed is 10000r/min, centrifugation time 10min；
(4) dissolve collagen crude extract with the acetum of pH2.7, then successively with the acetum dialysis 3d of pH3.0,
Ultrapure water dialysis 2d, is lyophilized later, obtains collagen sterling；
(5) TiO 2 sol is prepared using butyl titanate and diluted acid as raw material, specifically comprises the processes of: at room temperature by metatitanic acid four
Butyl ester, which is slowly added into, stirs 30min in the dehydrated alcohol of 5 times of volumes of butyl titanate, adds dust technology [V (concentrated nitric acid)
: V (distilled water)=1: 49] pH to 2.5 is adjusted, it is vigorously stirred after 40min in 45 DEG C of ultrasonic disperse 30min, obtains titanium dioxide
Colloidal sol；By TiO 2 sol successively in 80 DEG C of drying, it is broken, in 500 DEG C of calcining 2h, cooling, be crushed after obtain nanoscale two
Titanium oxide sample；
(6) collagen sterling is dissolved in the acetum of 0.5mol/L, Nano titanium dioxide sample, dioxy is added
The ratio for changing titanium and collagen is 1:3, mixes, impregnates for 24 hours after ultrasonic disperse 60min, then successively dried in 80 DEG C, is broken,
Up to collagen TiO after 500 DEG C of calcining 2h, broken2Composite catalyst, collagen TiO2Composite catalyst is a kind of
Using collagen as carrier, the nano-particle composite catalyst that Nano titanium dioxide active constituent obtains is supported.
Embodiment 3
The nanoscale composite catalyst that the sanitary sewage (elements such as main carbon containing, nitrogen, phosphorus) of acquisition is prepared with embodiment 1
Handled (it takes 50mL sanitary sewage that 25mg composite catalyst is added, stirs 30min in the dark and make up to adsorption equilibrium, then
With irradiating 80min under high-pressure sodium lamp after ultrasonic disperse 30min), its COD value before and after the processing is measured with permanganimetric method, COD is gone
Except rate is calculated by formula [1], specific degradation effect is shown in Table 1.
COD removal rate=(COD value after COD value-processing before handling)/COD value × 100% [1] before handling
Embodiment 4
The methyl orange solution of 20mg/L is handled with nanoscale composite catalyst prepared by embodiment 2 and (takes 50mL
25mg composite catalyst is added in the methyl orange solution of 20mg/L, stirs 30min in the dark and makes up to adsorption equilibrium, then ultrasound point
80min is irradiated under high-pressure sodium lamp after dissipating 30min), its absorbance before and after the processing is measured with ultra-violet and visible spectrophotometer
Value, degradation effect are calculated by formula 2, and specific degradation effect is shown in Table 1.
Degradation rate=(OD value after OD value-processing before handling)/OD value × 100% [2] before handling
1 catalytic effect of table
| Sewage species | Before processing | After processing | Degradation effect |
| Sanitary sewage (COD) | 163.1mg/L | 82.7mg/L | 49.3% |
| Methyl orange (OD) | 0.750 | 0.136 | 81.9% |
To sum up, in the specific embodiment of the invention, by collagen and nano-TiO2The collagen that hydridization is prepared is received
Rice TiO2They are used for sanitary sewage and methyl orange dye wastewater treatment by composite catalyst photocatalytic activity with higher
When, show very excellent degradation capability.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of collagen TiO2Composite catalyst, which is characterized in that the collagen TiO2Composite catalyst be it is a kind of with
Collagen is carrier, supports the nano-particle composite catalyst that Nano titanium dioxide active constituent obtains.
2. a kind of collagen TiO described in claim 12The preparation method of composite catalyst characterized by comprising
(1) clean pigskin degreasing will be handled, foreign protein is removed after the completion of degreasing；
(2) pigskin for having removed foreign protein is adjusted pH value with acetum in 0~4 DEG C is 2.0~2.5, and constant temperature soaking and stirring 8
~10h continuously adds the isometric acetum and pepsin later and is digested, filtered after enzymatic hydrolysis, retains filter
Liquid；
(3) sodium chloride solution is added in filtrate to saltout, centrifugation obtains collagen crude extract after saltouing；
(4) dissolve collagen crude extract with the acetum of pH2.7, then successively with the acetum of pH3.0 dialyse 3~4d,
Ultrapure water 1~2d of dialysis, is lyophilized later, obtains collagen sterling；
(5) TiO 2 sol is prepared using butyl titanate and diluted acid as raw material, TiO 2 sol is successively dried, is crushed,
Calcining obtains Nano titanium dioxide sample after being crushed；
(6) collagen sterling is dissolved in the acetum of 0.5mol/L, Nano titanium dioxide sample, titanium dioxide is added
It is 1:(1~8 with the ratio of collagen), it mixes, dipping 18 after ultrasonic disperse~for 24 hours, then successively dry, is broken, is calcining, broken
Up to collagen TiO after broken2Composite catalyst.
3. a kind of collagen TiO according to claim 22The preparation method of composite catalyst, which is characterized in that described
The control parameter of degreasing process in step (1) are as follows: the detergent alkylate sulphur that mass concentration is 0.5~1.0% is added in pigskin
System is simultaneously utilized ultrasonic degreasing by acid sodium solution, and wherein solid-liquid ratio is 1:(2.0~3.0), skimming temp is 20~25 DEG C, is surpassed
Acoustical power is 80~100W, and degreasing time is 2~2.5h.
4. a kind of collagen TiO according to claim 22The preparation method of composite catalyst, which is characterized in that described
The control parameter of removal foreign protein technique in step (1) are as follows: degreasing pigskin is immersed in the sodium chloride that mass concentration is 1~5%
In solution, solid-liquid ratio is 1:(3~8), soaking time is 2~4h.
5. a kind of collagen TiO according to claim 22The preparation method of composite catalyst, which is characterized in that described
The control parameter of enzymolysis process in step (2) are as follows: acetic acid additional amount with pigskin after impregnating and acetum solid-liquid ratio for 1:(10~
20) count, pepsin additional amount be original pigskin dry weight 1~1.2%, hydrolysis temperature be 0~4 DEG C, enzymolysis time be 16~
18h。
6. a kind of collagen TiO according to claim 22The preparation method of composite catalyst, which is characterized in that described
The control parameter for technique of saltouing in step (3) are as follows: concentration of sodium chloride solution is 1.0~1.5mol/L, and the time of saltouing is 6~12h.
7. a kind of collagen TiO according to claim 2 or 62The preparation method of composite catalyst, which is characterized in that institute
Stating centrifugal rotational speed in step (3) is 8000~12000r/min, and centrifugation time is 10~15min.
8. a kind of collagen TiO according to claim 22The preparation method of composite catalyst, which is characterized in that described
Step prepares titania gel in (5) specifically comprises the processes of: butyl titanate is slowly added into dehydrated alcohol at room temperature
It stirs evenly, adds dilute acid for adjusting pH to 2~3, then obtain TiO 2 sol in 40~50 DEG C of ultrasonic disperses.
9. a kind of collagen TiO according to claim 82The preparation method of composite catalyst, which is characterized in that described
Diluted acid is acetum or dust technology.
10. a kind of collagen TiO described in claim 12Application of the composite catalyst in sewage treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811523152.4A CN109529953A (en) | 2018-12-13 | 2018-12-13 | A kind of collagen TiO2Composite catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811523152.4A CN109529953A (en) | 2018-12-13 | 2018-12-13 | A kind of collagen TiO2Composite catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109529953A true CN109529953A (en) | 2019-03-29 |
Family
ID=65854484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811523152.4A Pending CN109529953A (en) | 2018-12-13 | 2018-12-13 | A kind of collagen TiO2Composite catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109529953A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000030368A (en) * | 2000-02-25 | 2000-06-05 | 김영규 | Manufactural method of activated carbon as a bactericidal photo-catalyst. |
| US6265341B1 (en) * | 1996-09-20 | 2001-07-24 | Teruo Komatsu | Highly functional base material and a method of manufacturing the same |
| CN1695797A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing photocatalyst of titanium dioxide carried by active carbon |
| CN101244383A (en) * | 2008-03-13 | 2008-08-20 | 同济大学 | Process for producing absorbent charcoal loading titanium dioxide photocatalyst |
| CN102205253A (en) * | 2011-04-18 | 2011-10-05 | 四川大学 | Supported photocatalyst with high activity under visible light and preparation method thereof |
| CN103447019A (en) * | 2013-09-23 | 2013-12-18 | 四川大学 | Supported TiO2 photocatalytic material with high visible-light activity and method for preparing same |
| WO2016209064A1 (en) * | 2015-06-25 | 2016-12-29 | 고려대학교 산학협력단 | Three-dimensional mesh structure, impeller having three-dimensional mesh structure, and method for producing same |
| CN107586818A (en) * | 2017-09-11 | 2018-01-16 | 浙江海洋大学 | A kind of extracting method of Japanese croaker collagen and application |
-
2018
- 2018-12-13 CN CN201811523152.4A patent/CN109529953A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265341B1 (en) * | 1996-09-20 | 2001-07-24 | Teruo Komatsu | Highly functional base material and a method of manufacturing the same |
| KR20000030368A (en) * | 2000-02-25 | 2000-06-05 | 김영규 | Manufactural method of activated carbon as a bactericidal photo-catalyst. |
| CN1695797A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing photocatalyst of titanium dioxide carried by active carbon |
| CN101244383A (en) * | 2008-03-13 | 2008-08-20 | 同济大学 | Process for producing absorbent charcoal loading titanium dioxide photocatalyst |
| CN102205253A (en) * | 2011-04-18 | 2011-10-05 | 四川大学 | Supported photocatalyst with high activity under visible light and preparation method thereof |
| CN103447019A (en) * | 2013-09-23 | 2013-12-18 | 四川大学 | Supported TiO2 photocatalytic material with high visible-light activity and method for preparing same |
| WO2016209064A1 (en) * | 2015-06-25 | 2016-12-29 | 고려대학교 산학협력단 | Three-dimensional mesh structure, impeller having three-dimensional mesh structure, and method for producing same |
| CN107586818A (en) * | 2017-09-11 | 2018-01-16 | 浙江海洋大学 | A kind of extracting method of Japanese croaker collagen and application |
Non-Patent Citations (5)
| Title |
|---|
| DAN LUO ET AL.: "Biomimetic organization of a ruthenium-doped collagen-based carbon scaffold for hydrogen evolution", 《JOURNAL OR MATERIALS CHEMISTRY A》 * |
| 于玮等: "猪皮胶原蛋白提取过程中酶解条件优化及其结构鉴定", 《西南大学学报》 * |
| 张于弛: "活性炭负载TiO2的制备及其光催化性能的研究", 《化学工程与装备》 * |
| 陈丽清等: "猪皮超声波乳化脱脂工艺的研究", 《食品工业科技》 * |
| 陈芳艳等: "TiO2/AC复合光催化剂的研究进展", 《工业用水与废水》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102181385B (en) | Formaldehyde biodegradation agent and preparation method thereof | |
| CN101810355B (en) | Eel bone collagen drinking liquor and production method thereof | |
| CN107586818A (en) | A kind of extracting method of Japanese croaker collagen and application | |
| CN105344328B (en) | A kind of preparation method of cotton fiber carried titanium dioxide composite material film | |
| CN102764650B (en) | Modified titanium dioxide/ bamboo charcoal composite material and preparation method thereof | |
| CN102086464B (en) | Method for preparing chitin | |
| CN110272485B (en) | Method for extracting silver carp skin collagen by ultrasonic acid pretreatment assisted acid enzyme method | |
| CN106390971B (en) | A kind of production method of charcoal based titanium dioxide catalysis material | |
| CN101586139A (en) | Method of extracting scale collagen polypeptide by microwave-assisted enzyme | |
| CN103255662A (en) | Preparation method of nanometer fibril enteromorpha cellulose | |
| CN106866816A (en) | The acid-enzyme binding-method of collagen is extracted from pigskin | |
| CN105343928A (en) | Technology for preparing collagen sponge | |
| CN108675383A (en) | The method for preventing bacterium algae in water body | |
| CN102850466B (en) | A kind of method of Os Bovis grunniens chondroitin sulfate | |
| CN106957374A (en) | A kind of method that fucoidin and algin are extracted from algae | |
| CN105536714A (en) | Heavy metal cellulose adsorbent and preparation method thereof | |
| CN107022033B (en) | A kind of method of high-performance flash purification bacteria cellulose | |
| Olsen et al. | Some characteristics of the carbon compounds released by Daphnia | |
| CN109265758B (en) | temperature/pH dual-response type chitin nanofiber hydrogel and preparation method thereof | |
| CN109529953A (en) | A kind of collagen TiO2Composite catalyst and preparation method thereof | |
| CN106348360A (en) | Wastewater cleaning agent based on photocatalysis | |
| CN105349600B (en) | A kind of fishy-removing-method of gadus protein enzymatic hydrolyzate | |
| CN106032546A (en) | Method for extracting medical material-based collagen from fish scales | |
| CN103801277A (en) | Titanium dioxide nanoribbon photocatalyst and preparation and applications thereof | |
| CN104017073A (en) | Method for preparing collagen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190329 |