CN104944497A - Method for treating high-concentration ammonia nitrogen in coal chemical industry wastewater - Google Patents
Method for treating high-concentration ammonia nitrogen in coal chemical industry wastewater Download PDFInfo
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Abstract
The invention relates to a method for treating high-concentration ammonia nitrogen in coal chemical industry wastewater, belonging to the field of sewage treatment. The method comprises the following steps: mixing an organic composite denitrifier modified magnesium-aluminum-iron hydrotalcite magnetic nano adsorbing material and an adhesive in a mass ratio of 1:5 to obtain a viscous liquid, coating the viscous liquid to the surface layer of an adsorbing bar, drying in the ventilation state, putting in an adsorption column, enabling the coal chemical industry wastewater penetrating fluid to flow through the adsorption column to adsorb 5000-10000 mg/L high-concentration ammonia nitrogen in the wastewater, aging the surface layer of the adsorbing material surface layer after reaching the saturated state so that the aged adsorbing material surface layer sheds layer by layer under the action of an external magnetic field and water flow scour, and finally, determining the ammonia nitrogen content in the wastewater. The method can renew the adsorbing material, does not need to regenerate the adsorbing material, and can not cause secondary pollution to the environment. The ammonia nitrogen concentration in the finally discharged wastewater is lower than 0.5 mg/L, and the removal rate is up to 99.99% above.
Description
Technical field
The present invention relates to a kind of process coal chemical industrial waste water middle and high concentration ammonia nitrogen method, belong to sewage treatment area.
Background technology
Coal chemical industrial waste water refers to based on high-concentration coal washes, containing poisonous and hazardous materials such as a large amount of phenol, oil, ammonia nitrogens, ammonia nitrogen in waste water is at 5000mg/L ~ 10000mg/L, great majority keep the state of balance with ammonium ion and free ammonia and exist, there is quantity discharged large, pollution range is wide, and discharging modes are complicated, pollute that species is various, pollution substance strong toxicity, recover the feature such as more difficult after pollutant emission.
In recent years, along with expanding economy, rapidly, various places chemical enterprise is gushed out like the mushrooms after rain in the heavy industry such as oil, chemical industry development, consequent air, water pollution problems are also day by day by people are paid attention to, and the high ammonia-nitrogen wastewater produced therefrom also becomes one of industry development restraining factors.
Ammonia nitrogen waste water enters water body, particularly flow to lake more slowly, bay, easily cause algae and other microorganism amount reproduction in water, form eutrophication pollution, difficulty is run except water treatment plants can be made, cause outside the peculiar smell of tap water, oxygen in water can be made time serious to decline, fish kill, lake even can be caused to be destroyed, ammonia nitrogen also makes to increase chlorine dosage in water disinfection and industrial circulating water sterilisation process, to some metal, particularly to copper, there is corrodibility, in order to reduce waste and the environmental pollution of water resources, improve Business Economic Benefit and society's effect, advanced treatment carried out to ammonia nitrogen waste water imperative.
The main method of current removal ammonia nitrogen has: break point chlorination method, blow-off method and vaporizing extract process, break point chlorination method is passed in waste water by chlorine to reach certain a bit, cl content of wandering about as a refugee in water at this time is minimum, and the concentration of ammonia is reduced to zero, but working cost is high, by product chloramines and chloro have an opportunity to cause secondary pollution problem, the such as publication number again that also there is secondary pollution problem is CN101428889, name is called that a kind of " treatment process removing ammonia nitrogen in waste water " disclosed method is first be filled with pressurized air in the ingress of wastewater inlet pipe, waste water mixing reactor is injected through high pressure spray nozzle, denitrfying agent is added again in mixing reactor, finally flow out in total for mixed waste water Venturi, the Tuo Chizhong that blows entering corridor type gallery structure carries out aeration stripping, the method is simple to operate, improve ammonia nitrogen removal frank, but or cannot solve ammonia nitrogen discharges the secondary pollution problem brought, blow-off method and vaporizing extract process refer to when in waste water, pH value is adjusted to alkalescence in addition, ion state ammonium is converted into molecular state ammonia, again waste gas is contacted with gas, ammonia nitrogen is made to transfer to gas phase from liquid phase, the method is usually used in high-concentration ammonia nitrogenous wastewater process, but it is low to there is processing efficiency when actually operating, and easily causes secondary pollution to environment.
Summary of the invention
The technical problem that the present invention mainly solves: there is ammonia emission in conjunction with blow-off method in high-concentration ammonia nitrogenous wastewater treating processes for organic composite denitrfying agent, cause secondary environmental pollution problem, provide a kind of organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite nano magnetic adsorptive material, absorption high-concentration ammonia nitrogen in waste water, and saturated after can aging sorbing material top layer, under externally-applied magnetic field and current scour effect, realize the renewal of sorbing material, without the need to regeneration.
In order to achieve the above object, the technical solution adopted in the present invention is:
(1) magnesium-aluminum-iron hydrotalcite preparation: take 5.8 ~ 10.2g magnesium nitrate respectively, 3.5 ~ 7.0g aluminum nitrate, 4.6 ~ 13.4g iron nitrate is dissolved in 350 ~ 480ml and contains in the ethanol solution of 4.2 ~ 8.4g urea; Stirred at ambient temperature 1h; Pour in hydrothermal reaction kettle and be heated to 150 DEG C, reaction 12 ~ 14h; The room temperature of cooling; With after ethanol and washed with de-ionized water two times at 100 DEG C dry 8h, obtain nano magnalium molten iron talcum;
(2) magnetize: be concentrated hydrochloric acid and the saturated potassium hydroxide solution immersion 6h of 36.5% successively by mass concentration by the nano magnalium molten iron talcum of above-mentioned preparation, be placed in retort furnace, dry at temperature is 110 DEG C, near magnetic field magnetisation;
(3) modification: the nano magnalium molten iron talc materials after pickling, alkali leaching and magnetization is immersed in 10 ~ 30g organic composite denitrfying agent, stirs 40 ~ 60min;
(4) dry: by modified nano magnalium molten iron talc materials washed with de-ionized water 3 times, dry under nitrogen protection condition;
(5) activate: at temperature is 800 DEG C ~ 900 DEG C, calcine 4 ~ 6h.
Described organic composite denitrfying agent is ethyl acetate, propylene glycol amine, fumaric acid form, by quality ratio, and 20% ~ 45% ethyl acetate, 20% ~ 55% propylene glycol amine, 15% ~ 45% fumaric acid.
Application method of the present invention is:
(1) by the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material prepared and tackiness agent in mass ratio 5:1 be made into viscous fluid, by viscous fluid Tu in plastic sheet top layer, coat-thickness is 3 ~ 6cm, by the plastic sheet of coated viscous fluid dry 10 ~ 20min under ventilation state, described tackiness agent counts 18 parts of polyvinyl alcohol, 22 parts of water glass, 5 parts of Graphenes, 35 parts of starch and 20 parts of water with parts by weight;
(2) plastic sheet of coated viscous fluid is placed in adsorption tower, every layer of mounting height is 10 ~ 50cm, and space height is 50 ~ 100cm, allow ammonia nitrogen concentration be the coal chemical industrial waste water permeate flow of 5000 ~ 10000mg/L through adsorption tower, flow rate control 5 ~ 15m
3/ h, absorption dwell time in the tower 40 ~ 60min, until the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material ammonia nitrogen absorption of plastic sheet surface reaches capacity, organic composite denitrfying agent aging magnesium-aluminum-iron hydrotalcite magnetic Nano material top layer;
(3) coal chemical industrial waste water penetrating fluid again current wash away with under externally-applied magnetic field effect, aging sorbing material top layer comes off layer by layer;
(4) ammonia-nitrogen content in last wastewater measurement water outlet.
Principle of the present invention: it is large that magnesium-aluminum-iron hydrotalcite material has specific surface area, belong to mesoporous material material, to ammonia nitrogen in waste water, there is absorption property through organic composite denitrfying agent is modified, the more important thing is, adding of organic composite denitrfying agent, can come off layer by layer voluntarily after sorbing material absorption ammonia nitrogen can be made to reach capacity, realize the renewal on sorbing material surface, again adsorb the ammonia nitrogen in high density in waste water, and the residue after coming off is separated with externally-applied magnetic field effect in current scour.
The invention has the beneficial effects as follows:
(1) produce without obnoxious flavour, can not secondary environmental pollution be caused;
(2) organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite nano magnetic adsorptive material is prepared, absorption high-concentration ammonia nitrogen in waste water, and saturated after can aging sorbing material top layer, under externally-applied magnetic field and current scour effect, realize the renewal of sorbing material, without the need to regeneration;
(3) after coming off, residue is little without moisture, volume, separable under externally-applied magnetic field, and ammonia nitrogen removal frank is high, cost is low.
Embodiment
The preparation of organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material:
(1) magnesium-aluminum-iron hydrotalcite preparation: take 5.8 ~ 10.2g magnesium nitrate respectively, 3.5 ~ 7.0g aluminum nitrate, 4.6 ~ 13.4g iron nitrate is dissolved in 350 ~ 480ml and contains in the ethanol solution of 4.2 ~ 8.4g urea; Stirred at ambient temperature 1h; Pour in hydrothermal reaction kettle and be heated to 150 DEG C, reaction 12 ~ 14h; The room temperature of cooling; With after ethanol and washed with de-ionized water two times at 100 DEG C dry 8h, obtain nano magnalium molten iron talcum;
(2) magnetize: be concentrated hydrochloric acid and the saturated potassium hydroxide solution immersion 6h of 36.5% successively by mass concentration by the nano magnalium molten iron talcum of above-mentioned preparation, be placed in retort furnace, dry at temperature is 110 DEG C, near magnetic field magnetisation;
(3) modification: the nano magnalium molten iron talc materials after pickling, alkali leaching and magnetization is immersed in 10 ~ 30g organic composite denitrfying agent, stirs 40 ~ 60min;
(4) dry: by modified nano magnalium molten iron talc materials washed with de-ionized water 3 times, dry under nitrogen protection condition;
(5) activate: at temperature is 800 DEG C ~ 900 DEG C, calcine 4 ~ 6h.
Described organic composite denitrfying agent is ethyl acetate, propylene glycol amine, fumaric acid form, by quality ratio, and 20% ~ 45% ethyl acetate, 20% ~ 55% propylene glycol amine, 15% ~ 45% fumaric acid.
Nano adsorption material removes the embody rule of high-concentration ammonia nitrogenous wastewater:
(1) by the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material prepared and tackiness agent in mass ratio 5:1 be made into viscous fluid, by viscous fluid Tu in plastic sheet top layer, coat-thickness is 3 ~ 6cm, by the plastic sheet of coated viscous fluid dry 10 ~ 20min under ventilation state, described tackiness agent counts 18 parts of polyvinyl alcohol, 22 parts of water glass, 5 parts of Graphenes, 35 parts of starch and 20 parts of water with parts by weight;
(2) plastic sheet of coated viscous fluid is placed in adsorption tower, every layer of mounting height is 10 ~ 50cm, and space height is 50 ~ 100cm, allow ammonia nitrogen concentration be the coal chemical industrial waste water permeate flow of 5000 ~ 10000mg/L through adsorption tower, flow rate control 5 ~ 15m
3/ h, absorption dwell time in the tower 40 ~ 60min, until the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material ammonia nitrogen absorption of plastic sheet surface reaches capacity, organic composite denitrfying agent aging magnesium-aluminum-iron hydrotalcite magnetic Nano material top layer;
(3) coal chemical industrial waste water penetrating fluid again current wash away with under externally-applied magnetic field effect, aging sorbing material top layer comes off layer by layer;
(4) ammonia-nitrogen content in last wastewater measurement water outlet.
Example 1
First take respectively 5.8g magnesium nitrate, 3.5g aluminum nitrate, 4.6g iron nitrate be dissolved in 350ml and contain in the ethanol solution of 4.2g urea; Stirred at ambient temperature 1h; Pour in hydrothermal reaction kettle and be heated to 150 DEG C, reaction 12h, the room temperature of cooling; With after ethanol and washed with de-ionized water two times at 100 DEG C dry 8h, obtain nano magnalium molten iron talcum; Be concentrated hydrochloric acid and the saturated potassium hydroxide solution immersion 6h of 36.5% more successively by mass concentration by the nano magnalium molten iron talcum of above-mentioned preparation, be placed in retort furnace, dry at temperature is 110 DEG C, near magnetic field magnetisation; Then the nano magnalium molten iron talc materials after pickling, alkali leaching and magnetization is immersed in 10g organic composite denitrfying agent, wherein comprise 2.5g ethyl acetate, 3.5g propylene glycol amine, 4g fumaric acid, stir 40min; By modified nano magnalium molten iron talc materials washed with de-ionized water 3 times, dry under nitrogen protection condition, at temperature is 800 DEG C, calcines 4h, organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material can be obtained; By the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material prepared and tackiness agent in mass ratio 5:1 be made into viscous fluid, by viscous fluid Tu in plastic sheet top layer, coat-thickness is 3cm, by the plastic sheet of coated viscous fluid dry 10min under ventilation state; The plastic sheet of coated viscous fluid is placed in adsorption tower, and every layer of mounting height is 10cm, and space height is 50cm, allow ammonia nitrogen concentration be the coal chemical industrial waste water permeate flow of 5000mg/L through adsorption tower, flow rate control 5m
3/ h, absorption dwell time in the tower 40min, until the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material ammonia nitrogen absorption on adsorbing bar surface reaches capacity, organic composite denitrfying agent aging magnesium-aluminum-iron hydrotalcite magnetic Nano material top layer; Coal chemical industrial waste water penetrating fluid again current wash away with under externally-applied magnetic field effect, aging sorbing material top layer comes off layer by layer, ammonia-nitrogen content 0.4mg/L in last wastewater measurement water outlet, and ammonia nitrogen removal frank is more than 99.99%.
Example 2
First take respectively 8.2g magnesium nitrate, 4.5g aluminum nitrate, 10.3g iron nitrate be dissolved in 400ml and contain in the ethanol solution of 5.4g urea; Stirred at ambient temperature 1h; Pour in hydrothermal reaction kettle and be heated to 150 DEG C, reaction 13h, the room temperature of cooling; With after ethanol and washed with de-ionized water two times at 100 DEG C dry 8h, obtain nano magnalium molten iron talcum; Be concentrated hydrochloric acid and the saturated potassium hydroxide solution immersion 6h of 36.5% more successively by mass concentration by the nano magnalium molten iron talcum of above-mentioned preparation, be placed in retort furnace, dry at temperature is 110 DEG C, near magnetic field magnetisation; Then the nano magnalium molten iron talc materials after pickling, alkali leaching and magnetization is immersed in 20g organic composite denitrfying agent, wherein comprise 6g ethyl acetate, 7g propylene glycol amine, 7g fumaric acid, stir 50min; By modified nano magnalium molten iron talc materials washed with de-ionized water 3 times, dry under nitrogen protection condition, 5h is calcined at temperature is 850 DEG C, organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material can be obtained, by the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material prepared and tackiness agent in mass ratio 5:1 be made into viscous fluid, by viscous fluid Tu in plastic sheet top layer, coat-thickness is 5cm, by the plastic sheet of coated viscous fluid dry 15min under ventilation state; The plastic sheet of coated viscous fluid is placed in adsorption tower, and every layer of mounting height is 30cm, and space height is 70cm, allow ammonia nitrogen concentration be the coal chemical industrial waste water permeate flow of 8000mg/L through adsorption tower, flow rate control 10m
3/ h, absorption dwell time in the tower 50min, until the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material ammonia nitrogen absorption of plastic sheet surface reaches capacity, organic composite denitrfying agent aging magnesium-aluminum-iron hydrotalcite magnetic Nano material top layer; Coal chemical industrial waste water penetrating fluid again current wash away with under externally-applied magnetic field effect, aging sorbing material top layer comes off layer by layer, ammonia-nitrogen content 0.3mg/L in last wastewater measurement water outlet, and ammonia nitrogen removal frank is more than 99.99%.
Example 3
First take respectively 10.2g magnesium nitrate, 7.0g aluminum nitrate, 13.4g iron nitrate be dissolved in 480ml and contain in the ethanol solution of 8.4g urea; Stirred at ambient temperature 1h; Pour in hydrothermal reaction kettle and be heated to 150 DEG C, reaction 14h, the room temperature of cooling; With after ethanol and washed with de-ionized water two times at 100 DEG C dry 8h, obtain nano magnalium molten iron talcum; Be concentrated hydrochloric acid and the saturated potassium hydroxide solution immersion 6h of 36.5% more successively by mass concentration by the nano magnalium molten iron talcum of above-mentioned preparation, be placed in retort furnace, dry at temperature is 110 DEG C, near magnetic field magnetisation; Then the nano magnalium molten iron talc materials after pickling, alkali leaching and magnetization is immersed in 30g organic composite denitrfying agent, wherein comprise 9g ethyl acetate, 12g propylene glycol amine, 12g fumaric acid, stir 60min; By modified nano magnalium molten iron talc materials washed with de-ionized water 3 times, dry under nitrogen protection condition, 6h is calcined at temperature is 900 DEG C, organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material can be obtained, by the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material prepared and tackiness agent in mass ratio 5:1 be made into viscous fluid, by viscous fluid Tu in plastic sheet top layer, coat-thickness is 6cm, by the plastic sheet of coated viscous fluid dry 20min under ventilation state; The plastic sheet of coated viscous fluid is placed in adsorption tower, and every layer of mounting height is 50cm, and space height is 100cm, allow ammonia nitrogen concentration be the coal chemical industrial waste water permeate flow of 10000mg/L through adsorption tower, flow rate control 15m
3/ h, absorption dwell time in the tower 60min, until the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material ammonia nitrogen absorption on adsorbing bar surface reaches capacity, organic composite denitrfying agent aging magnesium-aluminum-iron hydrotalcite magnetic Nano material top layer; Coal chemical industrial waste water penetrating fluid again current wash away with under externally-applied magnetic field effect, aging sorbing material top layer comes off layer by layer, ammonia-nitrogen content 0.2mg/L in last wastewater measurement water outlet, and ammonia nitrogen removal frank is more than 99.99%.
Claims (3)
1. process a coal chemical industrial waste water middle and high concentration ammonia nitrogen method, it is characterized in that organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material preparation process is:
(1) magnesium-aluminum-iron hydrotalcite preparation: take 5.8 ~ 10.2g magnesium nitrate respectively, 3.5 ~ 7.0g aluminum nitrate, 4.6 ~ 13.4g iron nitrate is dissolved in 350 ~ 480ml and contains in the ethanol solution of 4.2 ~ 8.4g urea; Stirred at ambient temperature 1h; Pour in hydrothermal reaction kettle and be heated to 150 DEG C, reaction 12 ~ 14h; The room temperature of cooling; With after ethanol and washed with de-ionized water 2 times at 100 DEG C dry 8h, obtain nano magnalium molten iron talcum;
(2) magnetize: be concentrated hydrochloric acid and the saturated potassium hydroxide solution immersion 6h of 36.5% successively by mass concentration by the nano magnalium molten iron talcum of above-mentioned preparation, be placed in retort furnace, dry at temperature is 110 DEG C, near magnetic field magnetisation;
(3) modification: the nano magnalium molten iron talc materials after pickling, alkali leaching and magnetization is immersed in 10 ~ 30g organic composite denitrfying agent, stirs 40 ~ 60min;
(4) dry: by modified nano magnalium molten iron talc materials washed with de-ionized water 3 times, dry under nitrogen protection condition;
(5) activate: at temperature is 800 DEG C ~ 900 DEG C, calcine 4 ~ 6h.
2. one processes coal chemical industrial waste water middle and high concentration ammonia nitrogen method according to claim 1, it is characterized in that described organic composite denitrfying agent is ethyl acetate, propylene glycol amine, fumaric acid form, by quality ratio, 20% ~ 45% ethyl acetate, 20% ~ 55% propylene glycol amine, 15% ~ 45% fumaric acid.
3. process a coal chemical industrial waste water middle and high concentration ammonia nitrogen method, it is characterized in that embody rule method is:
(1) by the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material prepared and tackiness agent in mass ratio 5:1 be made into viscous fluid, by viscous fluid Tu in plastic sheet top layer, coat-thickness is 3 ~ 6cm, by the plastic sheet of coated viscous fluid dry 10 ~ 20min under ventilation state, described tackiness agent counts 18 parts of polyvinyl alcohol, 22 parts of water glass, 5 parts of Graphenes, 35 parts of starch and 20 parts of water with parts by weight;
(2) plastic sheet of coated viscous fluid is placed in adsorption tower, every layer of mounting height is 10 ~ 50cm, and space height is 50 ~ 100cm, allow ammonia nitrogen concentration be the coal chemical industrial waste water permeate flow of 5000 ~ 10000mg/L through adsorption tower, flow rate control 5 ~ 15m
3/ h, absorption dwell time in the tower 40 ~ 60min, until the organic composite denitrfying agent modification magnesium-aluminum-iron hydrotalcite magnetic nano adsorption material ammonia nitrogen absorption of plastic sheet surface reaches capacity, organic composite denitrfying agent aging magnesium-aluminum-iron hydrotalcite magnetic Nano material top layer;
(3) coal chemical industrial waste water penetrating fluid again current wash away with under externally-applied magnetic field effect, aging sorbing material top layer comes off layer by layer;
(4) ammonia-nitrogen content in last wastewater measurement water outlet.
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Cited By (2)
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| CN106693925A (en) * | 2016-12-25 | 2017-05-24 | 常州亚环环保科技有限公司 | Preparation method of saturation self-falling-off ammonia-nitrogen wastewater adsorbent |
| CN108946858A (en) * | 2018-08-01 | 2018-12-07 | 江苏艾特克环境工程有限公司 | A kind of sewage denitrification and dephosphorization agent and preparation method thereof |
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| CN102502909A (en) * | 2011-11-01 | 2012-06-20 | 同济大学 | Method of using magnesium-aluminum-iron ternary hydrotalcite-like to remove perchlorate in water |
| CN102633345A (en) * | 2012-04-28 | 2012-08-15 | 常州亚环环保科技有限公司 | Method for treating high-concentration ammonia nitrogen in coal chemical wastewater |
| CN102633318A (en) * | 2012-04-28 | 2012-08-15 | 常州亚环环保科技有限公司 | Treatment method for high-concentration ammonia nitrogen in urine waste water |
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| JP2005211818A (en) * | 2004-01-30 | 2005-08-11 | Mitsubishi Chemicals Corp | Adsorbent |
| CN102502909A (en) * | 2011-11-01 | 2012-06-20 | 同济大学 | Method of using magnesium-aluminum-iron ternary hydrotalcite-like to remove perchlorate in water |
| CN102633345A (en) * | 2012-04-28 | 2012-08-15 | 常州亚环环保科技有限公司 | Method for treating high-concentration ammonia nitrogen in coal chemical wastewater |
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| CN108946858B (en) * | 2018-08-01 | 2021-08-20 | 江苏艾特克环境工程有限公司 | Sewage nitrogen and phosphorus removal agent and preparation method thereof |
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Effective date of registration: 20211228 Address after: Room 407-2-6, building C, Tian'an Digital City, 588 Changwu South Road, Wujin high tech Industrial Development Zone, Changzhou City, Jiangsu Province 213100 Patentee after: CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
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