CN102765890B - Method using titanium gypsum and acetylene sludge to prepare high-calcium sulphoaluminate or high-sulfur clinkers - Google Patents
Method using titanium gypsum and acetylene sludge to prepare high-calcium sulphoaluminate or high-sulfur clinkers Download PDFInfo
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- CN102765890B CN102765890B CN2012102748709A CN201210274870A CN102765890B CN 102765890 B CN102765890 B CN 102765890B CN 2012102748709 A CN2012102748709 A CN 2012102748709A CN 201210274870 A CN201210274870 A CN 201210274870A CN 102765890 B CN102765890 B CN 102765890B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
Abstract
A method using titanium gypsum and acetylene sludge to prepare high-calcium sulphoaluminate or high-sulfur clinkers includes the steps: (1) compounding; (2) homogenizing; and (3) calcining. According to the method using the titanium gypsum and the acetylene sludge to prepare the high-calcium sulphoaluminate or the high-sulfur clinkers, drying and grinding of wet sludge titanium gypsum and the acetylene sludge are omitted, energy consumption in drying and grinding is reduced, the firing temperature is low, firing energy consumption is low, production cost of the clinkers is low, and waste recycling benefits are good.
Description
Technical field
The present invention relates to a kind of useless method of profit of titanium gypsum, especially relate to a kind of method of making broad-spectrum high calcium sulfoaluminate clinker or high-sulfur grog with industrial residue titanium gypsum and carbide slag.
Background technology
The titanium gypsum is the industrial residue of sulfuric acid legal system titanium dioxide, contains heavy metal ion such as great amount of soluble zinc, lead, cadmium, the water ratio height, and viscosity is big, dry difficulty, outward appearance loess look is the clod shape when dry.At present, nearly 20,000,000 tons of China's titanium gypsum annual emissions, only the gully volume of cargo in storage has exceeded hundred million tons.Owing to contain the great amount of soluble heavy metal ion and be the loess look, in the record of production practice both at home and abroad and scientific research, document, only be confined to making cement retardant or plaster of Paris powder product are handled in its modification.But it as cement setting retarder, causes strength of cement to descend after each class methods modification is handled first, easily produces desciccation crack, second influences the cement color; Do building gypsum plaster and plastering, its drying and frying cost height, quality is also unstable, is not that the place difficulty is looked for and store up landfill disposal, and its antiseepage is handled also very difficult.Current, titanium gypsum mud is entered river, depression, culvert in large quantities, has caused serious environmental pollution.Along with the extensive output of titanium dioxide, titanium gypsum prevention and cure of pollution problem is outstanding day by day.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides that a kind of investment is little, cost is low, and technology is simple, the method for utilizing titanium gypsum and carbide slag high calcium sulplo-aluminate processed or high-sulfur grog of environmental protection and energy saving.
The technical solution adopted for the present invention to solve the technical problems is that a kind of method of utilizing titanium gypsum and carbide slag high calcium sulplo-aluminate processed or high-sulfur grog may further comprise the steps:
(1) batching: producing each raw material weight per-cent of high calcium sulfoaluminate clinker is: titanium gypsum 10-50%, carbide slag 20-70%, correction material 10-40%, and each material per-cent sum is 100%; Producing each raw material weight per-cent of high-sulfur grog is titanium gypsum 25-70%, carbide slag 20-50%, correction material 5-30%, and each material per-cent sum is 100%;
Described titanium gypsum be drain or press filtration after the hygrometric state industrial residue titanium gypsum of moisture 20-60wt%;
Described carbide slag refers to the waste residue behind the preparation of ethyne by carbide of chemical plant, and drying acetylene technology carbide slag is directly prepared burden, the carbide slag of wet method acetylene technology through drain or press filtration after prepare burden, when carbide slag was not enough, available Wingdale partly or entirely substituted;
Described correction material is silicon, aluminium, iron, magnesium, the fluorine matter correction material of powdery;
Wherein in the added material of correction material, replenish silicon, aluminium, ferro element, reach the requirement of clinker mineral moiety content; Mg supplementation, fluorine matter correction material are benchmark with the raw material gross weight, and Mg content is in MgO, and weight percent is 0.5-8.5%, and fluorine content is with CaF
2Meter, weight percent is 0.1-2.5%;
Described correction material is generally the high alumina cinder or coal dust, high-alumina clay, rhombspar, fluorite, alumina, red mud and other industrial residue that are easy to get; If correction material is block, granular, participate in the batching homogeneous again after then should grinding making dry powder; If correction material is flyash, chimney ash class subparticle, no matter dried hygrometric state then all can be participated in the batching homogeneous directly;
(2) homogeneous: adopt dried wet stock to roll over the mixing method homogeneous; When adopting calcined by rotary kiln, coal-fired by prior art powder process use; When adopting the vertical furnace calcining, the coal-fired homogeneous of after correction material is made dry powder, preparing burden; When adopting the calcining of tunnel furnace or annular kiln, the fire coal homogeneous of can partly or entirely after correction material is made dry powder, preparing burden; Coal-fired consumption is joined hot account form and is calculated by known, generally accounts for the 3%-20% of material quantity; The fire coal that does not mix homogeneous uses by the prior art mode;
(3) calcining: rotary kiln, vertical furnace, tunnel furnace or annular kiln are selected in calcining for use; When selecting rotary kiln for use, the material behind the homogeneous is directly sent into calcined by rotary kiln, or sends into the drying crusher oven dry fragmentation of kiln system earlier, and then sends into calcined by rotary kiln; When selecting vertical furnace for use, the material behind the homogeneous is calcined through being shaped to spherical or bar-shaped sending in the kiln; When selecting tunnel furnace or annular kiln for use, the material of homogeneous is sent in the kiln and is calcined through being shaped to brick shape or strip and block; Send into the material of calcining in the kiln, calcining generates the high-sulfur grog under 900 ℃-1350 ℃, non-reduced atmosphere, or calcining generates the high calcium sulfoaluminate clinker under 1100 ℃-1350 ℃, non-reduced atmosphere; Calcination time is with selecting for use the kiln difference and different, and when selecting rotary kiln, vertical furnace, tunnel furnace for use, calcination time was generally 20 minutes-120 minutes, and when selecting annular kiln for use, calcination time is 1-24 hour.
Gained high calcium sulfoaluminate clinker or high-sulfur grog can be used for producing material of construction such as cement, swelling agent, masonry mortar, aerating concrete.
The present invention with drain or press filtration after industrial residue titanium gypsum and the carbide slag of hygrometric state be main raw material, the silicon, aluminium, iron, magnesium, the fluorine matter correction material batching that are aided with powdery, be in order to solve titanium gypsum and carbide slag because of silicon, aluminium, iron, the magnesium chemical composition change of used titanium ore and the generation of carbide raw material difference, replenish and adjust required silicon, aluminium, irony content, and for solving the stability problem of firing temperature problem and generation mineral, replenish required magnesium and fluorine element content.Mineralogical composition according to chemical composition analysis and design requires to prepare burden in the known calculation formula calculating of cement industry each component ratio.
Adopt dried wet stock to roll over the mixing method homogeneous, be in order to save down oven dry and grinding energy consumption, alleviate environmental pollution, through drain naturally or press filtration after the titanium gypsum of hygrometric state of moisture 20-60% or carbide slag without oven dry and powder-grinding process, become the auxiliary correction material of dry powder attitude or the correction material of powdery to adopt the direct spreading of spreading mixing equipment to mix with grinding.
Beneficial effect of the present invention: it is superfine that (1) has taken into full account titanium gypsum mud granule, visco-plasticity is strong, physical property and the chemical ingredients characteristics of extremely difficult oven dry, utilize the zinc in the titanium gypsum, plumbous, the heavy metal element that cadmium etc. are harmful improves burn-ability, and utilize silicate minerals to the solid fixed characteristics of blow of heavy metal, simultaneously, can provide a large amount of calcareous industrial residue carbide slags and titanium gypsum to constitute main raw material, replenish required silicon, aluminium, the composition of irony deficiency, and Mg supplementation, fluorine element is to improve burn-ability and significantly to reduce the grog firing temperature and stable clinker mineral composition, allow the gained grog have high hydration activity, and technology is simple; That (2) can suit measures to local conditions selects for use rotary kiln, vertical furnace, tunnel furnace or annular kiln as Equipment for Heating Processing, and technology is flexible, investment is little, practical, and the environmental issue processing is simple, except the waste gas that gathers dust, pollution-free substantially; Saved oven dry and the powder-grinding process of hygroscopic state sewage sludge titanium gypsum and carbide slag, reduced oven dry and grinding energy consumption, and firing temperature has been low, it is low to burn till energy consumption, and the grog production cost is low, sharp useless handle profitable.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Among the application, the per-cent that does not indicate unit in addition all is weight percentage.
Embodiment 1
Present embodiment may further comprise the steps:
(1) batching: producing each raw material weight per-cent of high calcium sulfoaluminate clinker is: titanium gypsum 24%, carbide slag 47.4%, Wingdale 17.6%, correction material 11%;
Described titanium gypsum is the titanium gypsum that nature drains water ratio 43wt%; Carbide slag is the carbide slag of moisture 38wt% after the press filtration; The calcium oxide content of Wingdale is that 48wt%, content of magnesia are 3.9wt%; Wingdale is to remedy the deficiency of carbide slag for alternative part carbide slag; The consisting of of described correction material (per-cent is benchmark with total raw material weight): high alumina cinder 9.8%, fluorite 1.2%; Contain Al in the high alumina cinder
2O
341wt%;
Wingdale, high alumina cinder, fluorite are made dry powder with ball milling;
(2) homogeneous: Wingdale, cinder, fluorite ball milling are made behind the dry powder and titanium gypsum, carbide mud residue ingredient, mix the machine homogeneous through rolling over;
(3) calcining: the drying crusher oven dry that the material behind the homogeneous is sent into rotary kiln with conveyor is broken, adopts thin material to burn soon then, and firing temperature is controlled at 1300 ± 50 ℃; 30 minutes high-temperature calcination time.
The essential mineral of the high calcium sulfoaluminate clinker product that present embodiment makes consists of: 3CaO3Al
2O
3CaSO
416%, 3CaOSiO
240%, 2CaOSiO
229%, 4CaOAl
2O
3Fe
2O
37%, CaSO
46%; Other is 2% years old.
Measure time of coagulation according to GB/T1346-2001, measure intensity, 97 minutes average presetting periods of present embodiment high calcium sulfoaluminate clinker, final setting time 113 minutes, 1 day average ultimate compression strength 35.6MPa, anti-folding 6.7MPa according to GB/T17671-1999; 3 days average ultimate compression strength 47.3MPa, folding strength 7.5MPa; 28 days average ultimate compression strength 67.7MPa, folding strength 9.3MPa.
Embodiment 2
Present embodiment may further comprise the steps:
(1) batching: producing each raw material weight per-cent of high calcium sulfoaluminate clinker is: titanium gypsum 27%, carbide slag 61%, correction material 12%;
Described titanium gypsum is the titanium gypsum of water ratio 41wt% after the press filtration; Carbide slag is the drying acetylene carbide slag; The consisting of of described correction material (per-cent is benchmark with total raw material weight): bauxitic clay 4.5%, flyash 4.5%, fluorite mine tailing 1.5%, rhombspar 1.5%;
Correction material and fire coal are made dry powder in 12:11 ratio ball milling together;
(2) homogeneous: correction material and fire coal ball milling are together made behind the dry powder and titanium gypsum, carbide mud residue ingredient, mix the machine homogeneous through rolling over;
(3) calcining: be extruded into rod-like behind the raw material homogeneous, belt is sent into mechanical shaft kiln burning, and firing temperature is controlled at 1250 ℃ ± 50 ℃, does fire coal with hard coal; High temperature section calcination time 40 minutes.
The essential mineral of the high calcium sulfoaluminate clinker product that present embodiment makes consists of:
17%, C
3S38%, C
2S30%, C
4AF8%, CaSO
45%, other 2%.
Measure time of coagulation according to GB/T1346-2001, measure intensity, 88 minutes average presetting periods of present embodiment gained high calcium sulfoaluminate clinker, 1 day average ultimate compression strength 34.2MPa, folding strength 6.1MPa according to GB/T17671-1999; 3 days average ultimate compression strength 45.2MPa, folding strength 6.9MPa; 28 days average ultimate compression strength 64.3MPa, folding strength 8.9MPa.
Embodiment 3
Present embodiment may further comprise the steps:
(1) batching: producing each raw material weight per-cent of high calcium sulfoaluminate clinker is: titanium gypsum 31%, carbide slag 52%, correction material 17%;
Described titanium gypsum is for storing up the titanium gypsum of water ratio 27wt% in the open, and carbide slag is the carbide slag of water ratio 41wt% after the press filtration; The consisting of of described correction material (per-cent is benchmark with total raw material weight): the fluorite waste residue 3.5% of rough coal ash 7%, high-alumina clay 5%, discarded magnesia 1.5%, ball milling ore dressing;
Rough coal ash, high-alumina clay, discarded magnesia, hard coal are earlier with the powder process of 4R Raymond mill;
(2) homogeneous: after rough coal ash, high-alumina clay, discarded magnesia, the hard coal powder process, to mix the extrusion moulding of machine homogeneous be the perforated brick shape through rolling over titanium gypsum, carbide slag, fluorite waste residue, the seasoning of sign indicating number heap;
(3) calcining: homogeneous moulding, dried material are sent into the tunnel furnace calcining, and firing temperature is controlled at 1200 ± 100 ℃; Do fire coal with hard coal, high temperature section calcination time 50 minutes, getting brick shape grog is the high calcium sulfoaluminate clinker.
The essential mineral of the high calcium sulfoaluminate clinker product that present embodiment makes consists of:
20%, C
3S25%, C
2S33%, C
4AF10%, CaSO
410%, other 2%;
Measure time of coagulation according to GB/T1346-2001, measure intensity, 81 minutes high calcium sulfoaluminate clinker presetting periods of present embodiment according to GB/T17671-1999; 1 day average ultimate compression strength 31.2MPa, folding strength 5.9MPa; 3 days ultimate compression strength 43.1MPa, folding strength 6.7MPa; 28 days ultimate compression strength 57.4MPa, folding strength 8.9MPa.
Embodiment 4
Present embodiment may further comprise the steps:
(1) batching: producing each raw material weight per-cent of high-sulfur grog is: titanium gypsum 60%, carbide slag 28%, correction material 12%;
Described titanium gypsum is for storing up the titanium gypsum of average moisture content 26wt% in the open, and carbide slag is the carbide slag of the moisture 39wt% of press filtration;
The consisting of of described correction material (per-cent is benchmark with total raw material weight): the flyash of loss on ignition 7%-11% (containing burnt grain) 9%, Sodium Silicofluoride 1.7%, magnesium chloride 1.3%;
(2) homogeneous: the magnesium chloride of titanium gypsum, carbide slag, flyash (containing burnt grain), powdery Sodium Silicofluoride and dissolving is mixed the machine homogeneous through rolling over, and the brick press extrusion moulding is the brick shape, sends into the annular kiln calcining after the seasoning of sign indicating number heap;
(3) calcining: the material behind the homogeneous is sent into the drying crusher of annular kiln with conveyor, adopts thin material to burn soon, and firing temperature is controlled at 1050 ± 100 ℃; High temperature section calcination time 5 hours.
The high-sulfur grog product essential mineral that present embodiment makes consists of:
16%, C
2S25%, CaSO
455%, other 4%.
Measure time of coagulation according to GB/T1346-2001, measure intensity, 167 minutes present embodiment gained high-sulfur grog presetting periods, final setting time 213 minutes according to GB/T17671-1999; 1 day ultimate compression strength 21.1MPa, folding strength 2.8MPa; 3 days ultimate compression strength 25.7MPa, folding strength 4.2MPa; 28 days ultimate compression strength 31.3MPa, folding strength 6.7MPa; 7 days ultimate compression strength 72MPa of clean slurry.
Claims (7)
1. a method of utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog is characterized in that, may further comprise the steps:
(1) batching: producing each raw material weight per-cent of high calcium sulfoaluminate clinker is: titanium gypsum 10-50%, carbide slag 20-70%, correction material 10-40%, and each material per-cent sum is 100%; Producing each raw material weight per-cent of high-sulfur grog is titanium gypsum 25-70%, carbide slag 20-50%, correction material 5-30%, and each material per-cent sum is 100%;
Described titanium gypsum be drain or press filtration after the hygrometric state industrial residue titanium gypsum of moisture 20-60wt%;
Described carbide slag refers to the waste residue behind the preparation of ethyne by carbide of chemical plant, and drying acetylene technology carbide slag is directly prepared burden, the carbide slag of wet method acetylene technology through drain or press filtration after prepare burden;
Described correction material is silicon, aluminium, iron, magnesium, the fluorine matter correction material of powdery;
Wherein in the added material of correction material, replenish silicon, aluminium, ferro element, reach the requirement of clinker mineral moiety content; Mg supplementation, fluorine matter correction material are benchmark with the raw material gross weight, and Mg content is in MgO, and weight percent is 0.5-7.5%, and fluorine content is with CaF
2Meter, weight percent is 0.1-2.5%;
(2) homogeneous: adopt dried wet stock to roll over the mixing method homogeneous;
(3) calcining: the material behind the homogeneous or homogeneous aftershaping are the material of spherical, bar-shaped, brick shape, strip and block, calcining generates the high-sulfur grog under 900 ℃-1350 ℃, non-reduced atmosphere, or calcining generates the high calcium sulfoaluminate clinker under 1100 ℃-1350 ℃, non-reduced atmosphere.
2. the method for utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog according to claim 1 is characterized in that, partly or entirely substitutes carbide slag with Wingdale.
3. the method for utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog according to claim 1 and 2 is characterized in that, described correction material is at least a in high alumina cinder, coal dust, high-alumina clay, rhombspar, fluorite, alumina, the red mud.
4. the method for utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog according to claim 1 and 2 is characterized in that, participates in correction material flyash, chimney ash class subparticle directly the batching homogeneous.
5. the method for utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog according to claim 1 and 2 is characterized in that, in the step (2), and when adopting the vertical furnace calcining, the coal-fired homogeneous of after correction material is made dry powder, preparing burden; When adopting the calcining of tunnel furnace or annular kiln, the fire coal homogeneous of partly or entirely after correction material is made dry powder, preparing burden.
6. the method for utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog according to claim 1 and 2 is characterized in that, rotary kiln, vertical furnace, tunnel furnace or annular kiln are selected in calcining for use; When selecting rotary kiln for use, the material behind the homogeneous is directly sent into calcined by rotary kiln, or sends into the drying crusher oven dry fragmentation of kiln system earlier, and then sends into calcined by rotary kiln; When selecting vertical furnace for use, the material behind the homogeneous is calcined through being shaped to spherical or bar-shaped sending in the kiln; When selecting tunnel furnace or annular kiln for use, the material of homogeneous is sent in the kiln and is calcined through being shaped to brick shape or strip and block.
7. the method for utilizing titanium gypsum high calcium sulfoaluminate clinker processed or high-sulfur grog according to claim 1 and 2 is characterized in that, rotary kiln, vertical furnace, tunnel furnace or annular kiln are selected in calcining for use; When selecting rotary kiln, vertical furnace, tunnel furnace for use, calcination time is 20 minutes-120 minutes, when selecting annular kiln for use, and calcination time 1-24 hour.
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| CN103922622B (en) * | 2014-03-20 | 2015-11-04 | 山东大学 | A kind of technique utilizing aluminium ash to produce aluminosulfate cement |
| CN104496232A (en) * | 2014-12-29 | 2015-04-08 | 桂林理工大学 | Method for preparing Alite-barium calcium sulphoaluminate cement from red mud |
| CN105060749B (en) * | 2015-07-24 | 2017-11-07 | 湖南省小尹无忌环境能源科技开发有限公司 | The method that the extraordinary anhydrite binder materials of processing ardealite system is equipped with tunnel cave |
| CN105693122A (en) * | 2016-04-18 | 2016-06-22 | 廖引家 | Sulphoaluminate cement |
| CN106186763A (en) * | 2016-07-01 | 2016-12-07 | 卓达新材料科技集团威海股份有限公司 | A kind of pulverized fuel ash cement for building |
| CN107304108B (en) * | 2016-12-30 | 2019-11-05 | 江苏苏博特新材料股份有限公司 | The method for preparing concrete expansion clinker using low-grade limestone |
| CN108558245A (en) * | 2018-05-30 | 2018-09-21 | 盐城市诚信水泥机械制造有限公司 | A kind of sludge base cement mixture and preparation method thereof |
| CN113372029B (en) * | 2021-07-21 | 2022-12-02 | 攀钢冶金材料有限责任公司 | Low-carbon type super-sulfate cement, preparation method thereof and cement mortar |
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| CN100513341C (en) * | 2006-04-04 | 2009-07-15 | 马芸仙 | Method for producing cement and vitriol from high silicon ardealite |
| CN101468792B (en) * | 2007-12-28 | 2013-03-20 | 尹小林 | Novel technique for producing sulfur from industrial waste gypsum |
| CN101519282A (en) * | 2008-02-27 | 2009-09-02 | 尹小林 | Novel technology of vertical kiln for manufacturing cement clinker by utilizing dry acetylene sludge two-stage batching |
| CN101863629B (en) * | 2010-06-28 | 2012-04-11 | 长治市漳山建材有限公司 | Method for preparing sulphoaluminate cement clinker mainly from industrial solid waste |
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Application publication date: 20121107 Assignee: CHANGSHA ZICHEN TECHNOLOGY DEVELOPMENT CO., LTD. Assignor: Yin Xiaolin Contract record no.: 2015430000009 Denomination of invention: Method using titanium gypsum and acetylene sludge to prepare high-calcium sulphoaluminate or high-sulfur clinkers Granted publication date: 20131002 License type: Exclusive License Record date: 20150323 |
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Effective date of registration: 20161209 Address after: 410205 Hunan city high tech Development Zone Changsha Changsha Wenxuan Road No. 27 Lu Valley Yuyuan D3-101 building two floor Patentee after: CHANGSHA ZICHEN TECHNOLOGY DEVELOPMENT CO., LTD. Address before: 410013 Hunan province high tech Development Zone C2 group Binjiang fortune Silicon Valley building, room 5, building 510, room Patentee before: Yin Xiaolin |