CN104894302B - Graphene oxide/ferrum nano-composite tanning agent and preparation method thereof - Google Patents
Graphene oxide/ferrum nano-composite tanning agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
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Abstract
The invention discloses a kind of graphene oxide/ferrum nano-composite tanning agent, is made up according to mass parts of following material：40～50 parts of stannic oxide/graphene nano lamella dispersion liquid, 30～40 parts of iron sulfate, 10～20 parts of agent solution of alkalization, 0.5～1 part of dispersant；The invention also discloses a kind of preparation method of graphene oxide/ferrum nano-composite tanning agent, tanning agent of the present invention can serve as tanning agent, when graphene oxide/ferrum nano-composite tanning agent is according to 6% that solid consumption is tare weight, the shrinkage temperature of its tan leather has reached 118 DEG C, the absorbance of iron tannage agent has reached 96%, tan leather is washed 10 its shrinkage temperatures and is not almost reduced, 20 shrinkage temperatures of washing reduce 4%, anti-aging test shows the stable performance of tan leather, the problems such as embrittlement of the tanbark without conventional iron tanning agent during storage is hardened, tan leather has good flexibility, elasticity and fullness.
Description
Technical field
The invention belongs to the preparing technical field of leather retanning agent, and in particular to a kind of nano combined tan of graphene oxide/ferrum
Agent and preparation method thereof.
Background technology
Leather retanning agent is a kind of chemical substance that rawhide can be made to be changed into leather, and can be used as leather retanning agent in theory has chrome tanning
Agent, zirconium tanning agent, titanium tannage agent, aluminium tanningagent, iron tannage agent, vegetable tanning agent, aldehyde tanning agent etc., it is comprehensive actually due to chrome tanning agent tan leather
Close performance preferably, only chrome tanning agent has obtained widely applying, and current chrome tanning leather accounts for 90% or so (Wang Weis of leather yield
Outstanding person, Liao Xuepin, Shi Bi. the extraction and its application in tanning of tea polyphenols in green tea pair tea. Chinese leather, 2014,43 (1):
11-14；Chattopadhyay B,Aich A,Mukhopadhyay S K.Chromium in the Tanning
Industry:An Odyssey from Cradle to Grave[J].Journal of the society of leather
technologists and chemists,2012,96(4):133-140).A large amount of uses of chrome tanning agent are generated and are difficult in a large number
The pollutant containing chromium administered, at present both at home and abroad the use of chrome tanning agent is proposed restriction (Li Dongling, Dan Zhihua, Yang Meng, etc.
Plant aldehyde combination tannage rigid matrix resistance to ag(e)ing research. Chinese leather, 2014,43 (13):27-30).Therefore, at present research and
Exploitation chrome-free tanning agent etc. becomes the focus of research, becomes research again with little iron tannage agent of affluent resources and pollution etc.
Object, it is desirable to use improve the performance of iron tannage agent to replace chrome tanning agent.Iron tannage agent exist subject matter be tan leather not
Resistance to storage, iron tannage leather can discharge acidic materials during storage makes leather glue fibril hydrolyze, be destroyed, become fragile；Iron tannage
Trivalent iron salt in leather is reduced to ferrous irons by collagen etc. in collagen fiber system, and ferrous irons are again by the oxygen in air afterwards
Be oxidized to ferric iron, so change causes collagen fiber embrittlement to be hardened and cannot use repeatedly, the resistance to water of iron tannage leather also compared with
Difference, it is hard, flat thin etc. that ferrum tan leather compares plate.Fewer for the improvement of iron tannage agent at present, main cause is that iron tannage agent is present
These problems be relatively difficult to solve (Karthikeyan R., Ramesh R., Venba R., Ramamoorthy U., Babu
N.K.C.,Ramasami T.The renaissance of Fe(III)as Self-tanning Agent.JSLTC,2011,
95(4):171-176).We have found there is higher stablize with the nano-composite tanning agent that iron sulfate is formed by GO under study for action
Property, tan leather stable performance, with the ability as tanning agent.
The content of the invention
To solve existing technical problem, the embodiment of the present invention provides a kind of graphene oxide/ferrum nano combined tan
Agent and preparation method thereof, gained tanning agent is by the compound of ferrum with coordinate bond, covalent bond etc. and stannic oxide/graphene nano lamella shape
Into nano-composite tanning agent, simultaneous oxidation Graphene is a kind of reducing agent in itself so that ferric iron and two occur in iron tannage leather again
In the change procedure repeatedly of valency ferrum, reducing agent is undertaken by graphite oxide, therefore reduces the oxidation to leather collagen fiber also
Former destruction.Formed with collagen by the active group in graphene oxide/ferrum nano-composite tanning agent during tan leather
Multiple spot chemical bonds and nanometer size effect reach the purpose of tan leather, have compared with the tanning effect of simple iron tannage agent
It is significant to improve, it is particular in that the stability and durability that improve ferrum tan leather.
To reach above-mentioned purpose, what the technical scheme of the embodiment of the present invention was realized in：
The embodiment of the present invention provides a kind of graphene oxide/ferrum nano-composite tanning agent, by following material according to mass parts system
Into：
40～50 parts of stannic oxide/graphene nano lamella dispersion liquid, 30～40 parts of iron sulfate, alkalization agent solution 10～20 part, point
0.5～1 part of powder.
In such scheme, in the stannic oxide/graphene nano lamella dispersion liquid containing graphene oxide layer mass fraction it is
1%～1.2%, the size of the graphene oxide layer is 5～30 nanometers.
In such scheme, the alkalization agent solution is that 15 parts of sodium bicarbonate are dissolved in 25 parts of deionized waters or 12 parts of carbonic acid
Sodium is dissolved in the solution that 20 parts of deionized waters are formed.
In such scheme, the dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, the imidazoline polyoxy
The weight ratio of vinyl Ether and penetrating agent JFC is 0.6～1.0:1～1.3.
The embodiment of the present invention also provides a kind of preparation method of graphene oxide/ferrum nano-composite tanning agent, the preparation method
For：40～50 parts of stannic oxide/graphene nano lamella dispersion liquid is taken according to mass parts and 30～40 parts of iron sulfate is stirred in reactor
Even regulation pH be 2.0～3.0, be heated to 85～95 DEG C, add to alkalize 5～8 parts of agent solution, insulation reaction 1～2 hour,
Then 70～80 DEG C are cooled to, under agitation slow residue basifier, insulation reaction 3～4 hours cools to 25～30 DEG C, adjusts
The pH value of section solution is 3.5～4.0, adds 0.5～1 part of dispersant, ultrasound wave to disperse 1～1.5 hour, and products therefrom is oxygen
Graphite alkene/ferrum nano-composite tanning agent, the wherein content of ferrum are 20%～25% according to iron sulfate mass fraction, graphene oxide
Mass fraction is 0.4～0.6%.
In such scheme, in the stannic oxide/graphene nano lamella dispersion liquid containing graphene oxide layer mass fraction it is
1%～1.2%, the size of the graphene oxide layer is 5～30 nanometers.
In such scheme, described alkalization agent solution is dissolved in 25 parts of deionized waters or 12 parts of carbon for 15 parts of sodium bicarbonate
Sour sodium is dissolved in the solution that 20 parts of deionized waters are formed.
In such scheme, the dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, the imidazoline polyoxy
The weight ratio of vinyl Ether and penetrating agent JFC is 0.6～1.0:1～1.3.
Compared with prior art, beneficial effects of the present invention：
The present invention is by the carboxyl of stannic oxide/graphene nano lamella, matching somebody with somebody of being formed between hydroxyl and epoxy radicals and ferric iron
Position, Covalent bonding together define nano-complex, in tannery by regulate and control solution pH value with increase iron tannage agent and its
Composite tanning agent with cumulative power, the coordination compound of the multinuclear ferrum for promoting to be formed with the participation of GO nano materials, while also improving oxidation
The dispersion effect of graphene nano lamella.Active group of the tanning effect on GO lamellas and the activity on materials with hide glue fibril
Group forms the nano-scale that polyacetylene compound tanning effect and stannic oxide/graphene nano lamella are matched somebody with somebody in chemical bonding effect, multinuclear ferrum
Effect.
The nano-composite tanning agent of gained of the invention is by multinuclear bodied ferric sulfate and activity on stannic oxide/graphene nano lamella
Multiple spot chemical bonds and stannic oxide/graphene nano dimensional effect that group is formed with collagen reach the purpose of tan leather.When
Graphene oxide/ferrum nano-composite tanning agent is reached according to the shrinkage temperature of its tan leather during 6% that solid consumption is tare weight
118 DEG C, the absorbance of aluminium tanningagent has reached 96%, and tan leather is washed 20 its shrinkage temperatures and reduces 4%, tan leather
Flexibility, elasticity and fullness etc. are close to chrome tanning leather.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
The embodiment of the present invention provides a kind of graphene oxide/ferrum nano-composite tanning agent, by following material according to mass parts system
Into：
40～50 parts of stannic oxide/graphene nano lamella dispersion liquid, 30～40 parts of aluminum sulfate, alkalization agent solution 10～20 part, point
Powder 0.6～1.0:1.0～1.3 parts.
The preparation method of the stannic oxide/graphene nano lamella dispersion liquid is：3～5 parts of graphite powder is slowly added to into 80
During～100 parts of mass fractions are 98% concentrated sulphuric acid, 0～5 DEG C of the temperature of control system is slowly added to 10～15 parts after stirring
Potassium permanganate react 3～4 hours, be then warmed up to 30～40 DEG C again and continue reaction 2～2.5 hours, be slow added into 150～
180 parts of deionized waters, are warming up to 80～90 DEG C and react 1～2 hour；Then 30 DEG C～35 Deca, 35～40 parts of quality point are cooled to
The hydrogenperoxide steam generator of number 30%, reacts 1～1.5 hour, and ultrasound wave dispersion prepares stannic oxide/graphene nano piece in 1～1.5 hour
Layer dispersion liquid, contains graphene oxide layer 1%～1.2% in stannic oxide/graphene nano lamella dispersion liquid；Due to the oxidation
The preparation process of graphene nano lamella dispersion liquid is complex, therefore typically once prepares more consumption, in case preparing
Taken in journey on demand.
Described alkalization agent solution is that 15 parts of sodium bicarbonate are dissolved in 25 parts of deionized waters or 12 parts of sodium carbonate are molten for solution
In the solution that 20 parts of deionized waters are formed.
The dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, the imidazoline polyoxyethylene ether and is oozed
The weight ratio of agent JFC is 0.5～0.8 thoroughly:1～1.3.
The embodiment of the present invention also provides a kind of preparation method of graphene oxide/ferrum nano-composite tanning agent, the preparation method
For：40～50 parts of stannic oxide/graphene nano lamella dispersion liquid is taken according to mass parts and 30～40 parts of iron sulfate is stirred in reactor
Even regulation pH is 2.0～3.0, is heated to 85～95 DEG C, addition 5～8 parts of agent solution of alkalization, insulation reaction 1～2 hour, so
After cool to 70～80 DEG C, be added slowly with stirring remaining basifier, insulation reaction 3～4 hours cools to 25～30 DEG C,
The pH value for adjusting solution is 3.5～4.0, adds 0.5～1 part of dispersant, ultrasound wave to disperse 1～1.5 hour, and products therefrom is
Graphene oxide/ferrum nano-composite tanning agent, the mass fraction for controlling iron sulfate are 20%～25%, control graphene oxide quality
Fraction is 1～1.2%.
The tanning agent of the present invention has the advantages that in tanning consumption is few, absorbance is high, chromium from waste chromium compound residual quantity is low,
And production technology is unique, technical process is easily operated, with good application prospect.
The carboxyl passed through in graphene oxide structure of the invention, hydroxyl and epoxy radicals etc. are from iron sulfate under different pH environment
Effect, it is the coordinate bond formed between active group on iron sulfate and graphene oxide is formed, covalently bonded nano combined
Beyond the region of objective existence, has been also carried out iron sulfate polyreaction, and what is made defines graphene oxide/ferrum nano-composite tanning agent, while and oxidation
The degree of scatter of graphene nano lamella increases.Active group of the tanning effect on stannic oxide/graphene nano lamella
Chemical bonding effect, the tanning effect of bodied ferric sulfate and graphene oxide can be formed with the active group on materials with hide glue fibril
The nanometer size effect of nanoscale twins.
Using graphene oxide/ferrum nano-composite tanning agent consumption during graphene oxide/ferrum nano-composite tanning agent tan leather
(with iron sulfate calculate) as tare weight 6%, graphene oxide (solid consumption) consumption be tare weight 0.20% when, tan leather can be made
Shrinkage temperature reaches 121 DEG C, and the absorbance of aluminium tanningagent has reached 96%.
Embodiment one：
Step one：The preparation of stannic oxide/graphene nano lamella dispersion liquid：
3 parts of graphite powder is slowly added to into 80 parts of mass fractions in 98% concentrated sulphuric acid, 0 DEG C of the temperature of control system,
The potassium permanganate that 10 parts are slowly added to after stirring reacts 3 hours, is then warmed up to 30 DEG C again and continues reaction 2 hours, then delays
Slowly 150 parts of deionized waters are added, 80 DEG C is warming up to and is reacted 1 hour；Then 30 DEG C of Deca, 35 parts of mass fractions 30% are cooled to
Hydrogenperoxide steam generator, reacts 1 hour, and ultrasound wave dispersion prepares stannic oxide/graphene nano lamella dispersion liquid, control oxidation stone for 1 hour
Contain graphene oxide layer 1% in black alkene nanoscale twins dispersion liquid.
Step 2：The preparation of alkalization agent solution：
Alkalization agent solution is the solution that 15 parts of sodium bicarbonate are dissolved in that 20 parts of deionized waters are formed.
Step 3：The preparation of dispersant：
Dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, and the weight ratio of the material is 0.5:1.
Step 4：The preparation method of graphene oxide/ferrum nano-composite tanning agent：
40 parts of stannic oxide/graphene nano lamella dispersion liquid is taken according to mass parts and 30 parts of iron sulfate is stirred in reactor
Even section pH is 2.0, is heated to 85 DEG C, adds 5 parts of agent solution of alkalization, insulation reaction 1 hour then to cool to 70 DEG C, stirring
Mix down and be slowly added to remaining alkalization agent solution, insulation reaction 3 hours cools to 25 DEG C, and the pH value for adjusting solution is 3.5, is added
0.5 part of dispersant, ultrasound wave disperse 1 hour, and products therefrom is graphene oxide/ferrum nano-composite tanning agent, controls iron sulfate
Mass fraction be 20% and graphene oxide mass fraction be 0.4%.
Embodiment two：
Step one：The preparation method of stannic oxide/graphene nano lamella dispersion liquid：
5 parts of graphite powder is slowly added to into 100 parts of mass fractions in 98% concentrated sulphuric acid, 5 DEG C of the temperature of control system,
The potassium permanganate that 15 parts are slowly added to after stirring reacts 4 hours, is then warmed up to 40 DEG C again and continues reaction 2.5 hours, then
180 parts of deionized waters are slowly added to, 90 DEG C are warming up to and are reacted 2 hours；Then 35 DEG C of Deca, 40 parts of mass fractions 30% are cooled to
Hydrogenperoxide steam generator, react 1.5 hours, ultrasound wave dispersion prepare within 1.5 hours stannic oxide/graphene nano lamella dispersion liquid, control
Contain graphene oxide layer 1.1% in stannic oxide/graphene nano lamella dispersion liquid.
Step 2：The preparation of alkalization agent solution：
Alkalization agent solution is the solution that 8 parts of sodium carbonate are dissolved in that 20 parts of deionized waters are formed.
Step 3：The preparation of dispersant：
Dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, and the weight ratio of the material is 0.8:1.3.
Step 4：The preparation method of graphene oxide/ferrum nano-composite tanning agent：
50 parts of stannic oxide/graphene nano lamella dispersion liquid is taken according to mass parts and 40 parts of iron sulfate is stirred in reactor
Even section pH is 3.0, is heated to 95 DEG C, adds 8 parts of agent solution of alkalization, insulation reaction 2 hours then to cool to 80 DEG C, stirring
Mix down and be slowly added to remaining alkalization agent solution, insulation reaction 4 hours cools to 30 DEG C, and the pH value for adjusting solution is 4.0, adds 1
The dispersant of part, ultrasound wave disperse 1.5 hours, and products therefrom is graphene oxide/ferrum nano-composite tanning agent, controls iron sulfate
Mass fraction is 25% and graphene oxide mass fraction is 0.6%.
Embodiment three：
Step one：The preparation method of stannic oxide/graphene nano lamella dispersion liquid：
4 parts of graphite powder is slowly added to into 90 parts of mass fractions in 98% concentrated sulphuric acid, 3 DEG C of the temperature of control system,
The potassium permanganate that 12 parts are slowly added to after stirring reacts 3.5 hours, is then warmed up to 35 DEG C again and continues reaction 2 hours, then
170 parts of deionized waters are slowly added to, 85 DEG C are warming up to and are reacted 1.5 hours；Then 30 DEG C of Deca, 35 parts of mass fractions are cooled to
30% hydrogenperoxide steam generator, reacts 1.5 hours, and ultrasound wave dispersion prepares stannic oxide/graphene nano lamella dispersion liquid for 1.5 hours,
Contain graphene oxide layer 1.2% in control stannic oxide/graphene nano lamella dispersion liquid.
Step 2：The preparation of alkalization agent solution：
Alkalization agent solution is the solution that 10 parts of sodium bicarbonate are dissolved in that 20 parts of deionized waters are formed.
Step 3：The preparation of dispersant：
Dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, and the weight ratio of the material is 0.6:1.2.
Step 4：The preparation method of graphene oxide/ferrum nano-composite tanning agent：
45 parts of stannic oxide/graphene nano lamella dispersion liquid is taken according to mass parts and 28 parts of iron sulfate is stirred in reactor
Even section pH is 2.5, is heated to 90 DEG C, is added to 6.5 parts of the agent solution that alkalizes, and then insulation reaction 1.5 hours cools to 75
DEG C, remaining basifier is added slowly with stirring, insulation reaction 3.5 hours cools to 30 DEG C, and the pH value for adjusting solution is 3.5,
1 part of dispersant, ultrasound wave is added to disperse 1 hour, products therefrom is graphene oxide/ferrum nano-composite tanning agent, controls iron sulfate
Mass fraction be 23% and graphene oxide mass fraction be 0.5%.
Claims (4)
1. the preparation method of a kind of graphene oxide/ferrum nano-composite tanning agent, it is characterised in that the preparation method is：According to matter
Amount part takes 40 ~ 50 parts of stannic oxide/graphene nano lamella dispersion liquid and 30 ~ 40 parts of iron sulfate stirs in reactor and adjusts pH
For 2.0 ~ 3.0,85 ~ 95 DEG C are heated to, add 5 ~ 8 parts of agent solution of alkalization, insulation reaction 1 ~ 2 hour then to cool to 70 ~ 80
DEG C, remaining alkalization agent solution is added slowly with stirring, the alkalization agent solution total amount is 10 ~ 20 parts, and insulation reaction 3 ~ 4 is little
When, 25 ~ 30 DEG C are cooled to, the pH value for adjusting solution is 3.5 ~ 4.0, adds 0.5 ~ 1 part of dispersant, ultrasound wave dispersion 1 ~ 1.5
Hour, products therefrom be graphene oxide/ferrum nano-composite tanning agent, wherein the content of ferrum according to iron sulfate mass fraction be 20% ~
25%, graphene oxide mass fraction is 0.4 ~ 0.6%.
2. the preparation method of graphene oxide according to claim 1/ferrum nano-composite tanning agent, it is characterised in that：It is described
It is 1% ~ 1.2% to contain graphene oxide layer mass fraction in stannic oxide/graphene nano lamella dispersion liquid, the graphene oxide
The size of lamella is 5 ~ 30 nanometers.
3. the preparation method of graphene oxide according to claim 1/ferrum nano-composite tanning agent, it is characterised in that：It is described
Alkalization agent solution be dissolved in 25 parts of deionized waters for 15 parts of sodium bicarbonate or 12 parts of sodium carbonate are dissolved in 20 parts of deionized waters and are formed
Solution.
4. the preparation method of graphene oxide according to claim 1/ferrum nano-composite tanning agent, it is characterised in that：It is described
Dispersant is made up of imidazoline polyoxyethylene ether and penetrating agent JFC, the weight of the imidazoline polyoxyethylene ether and penetrating agent JFC
Than for 0.6 ~ 1.0:1~1.3.
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| CN105624341A (en) * | 2016-01-29 | 2016-06-01 | 佛山市聚成生化技术研发有限公司 | Full grain leather tanning method based on iron tanning agent |
| CN105779668B (en) * | 2016-03-29 | 2017-10-20 | 陕西科技大学 | Zirconium tanning agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof |
| CN105755185B (en) * | 2016-03-29 | 2017-10-24 | 陕西科技大学 | Titanium tannage agent/stannic oxide/graphene nano composite tanning agent and preparation method thereof |
| CN105648124B (en) * | 2016-03-29 | 2017-10-20 | 陕西科技大学 | Zinc salt/stannic oxide/graphene nano composite tanning agent and preparation method thereof |
| CN108085434B (en) * | 2017-12-29 | 2020-11-17 | 温州大学 | Organic tanning agent for leather and preparation method thereof |
| CN108950102B (en) * | 2018-07-26 | 2020-11-17 | 陕西科技大学 | Iron (III) heterocyclic organic acid complex tanning agent and preparation method thereof |
| CN111084975B (en) * | 2019-12-25 | 2021-11-02 | 陕西科技大学 | Leather-based pressure sensor for recording walking track, preparation method and application |
| CN110957058B (en) * | 2019-12-25 | 2022-09-16 | 陕西科技大学 | Conductive leather and preparation method thereof |
| CN113736929B (en) * | 2021-10-15 | 2022-05-17 | 齐鲁工业大学 | Method for preparing high-physical-property leather by in-situ reduction of graphene oxide |
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| CN1474876A (en) * | 2000-11-13 | 2004-02-11 | 罗迪亚消费特殊有限公司 | Tannages and tanning material |
| US20080229511A1 (en) * | 2007-03-23 | 2008-09-25 | Council Of Scientific & Industrial Research | Process for the Preparation of Synthetic Tanning Agent for Improved Leather Characteristics |
| CN102321771B (en) * | 2011-08-22 | 2015-03-11 | 温州大学 | Chrome-free metal composite tanning agent and preparation method thereof |
| EP2574682B1 (en) * | 2011-09-30 | 2013-10-30 | Kemira Oyj | Environmentally friendly composition, suitable for leather tanning, comprising zeolite |
| CN104232808B (en) * | 2014-09-23 | 2016-06-29 | 陕西科技大学 | graphene oxide and trivalent chromium complex tanning agent and preparation method thereof |
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Inventor after: Lv Shenghua Inventor after: Jia Chunmao Inventor after: Deng Lijuan Inventor after: He Yaya Inventor after: Zhu Linlin Inventor before: Lv Shenghua Inventor before: Li Ying Inventor before: Deng Lijuan Inventor before: He Yaya Inventor before: Zhu Linlin |
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Effective date of registration: 20201210 Address after: 241080 No.23 Sanshan street, Sanshan Economic Development Zone, Wuhu City, Anhui Province Patentee after: Wu Junxi Address before: 710021 Shaanxi city of Xi'an province Weiyang University City Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
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Effective date of registration: 20210416 Address after: 362200 Building 1, No.150, Wenhua Road, Hongshan Comprehensive District, Qingyang street, Jinjiang City, Quanzhou City, Fujian Province Patentee after: CHINA LEATHER AND FOOTWEAR INDUSTRY RESEARCH INSTITUTE (JINJIANG) Co.,Ltd. Address before: 241080 No.23 Sanshan street, Sanshan Economic Development Zone, Wuhu City, Anhui Province Patentee before: Wu Junxi |
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