CN108516589A - A kind of method that manganous hydroxide is recycled in titanium pigment waste acid processing procedure - Google Patents
A kind of method that manganous hydroxide is recycled in titanium pigment waste acid processing procedure Download PDFInfo
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- CN108516589A CN108516589A CN201810478501.9A CN201810478501A CN108516589A CN 108516589 A CN108516589 A CN 108516589A CN 201810478501 A CN201810478501 A CN 201810478501A CN 108516589 A CN108516589 A CN 108516589A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 239000001038 titanium pigment Substances 0.000 title claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 19
- 239000002893 slag Substances 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 13
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 13
- 239000004571 lime Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 7
- -1 iron ion Chemical class 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 229910052925 anhydrite Inorganic materials 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention discloses a kind of method that manganous hydroxide is recycled in titanium pigment waste acid processing procedure, makes titanium white diluted acid and lime or carbide slag initial reaction first, removes ferrous ion therein, iron ion, calcium ion as possible, neutralizes acid therein；Then so that remaining ferrous ion is further aoxidized, formed and precipitate and detach；So that the Mn in filtrate is extracted in a manner of precipitating again, and is recycled；Finally the alkali in final filtrate is neutralized, qualified discharge.Compared with prior art, present invention process is simple, and raw material is easily purchased of low cost, and reaction process is thoroughly controllable, makes to have achieved the purpose that environmental protection without containing remaining manganese in waste residue or waste water.
Description
Technical field
The present invention relates to liquid waste disposal technique field, manganous hydroxide is recycled in specifically a kind of titanium pigment waste acid processing procedure
Method.
Background technology
At present in the spent acid of sulfuric acid method titanium pigment technique, containing a large amount of manganese, which is the raw material from titanium dioxide industry
The impurity introduced in titanium ore, titanium slag.Its content is 0.2% or so.Titanium white waste acid generally uses lime or carbide slag to neutralize, wherein
Manganese can by precipitation or ion in the form of be present in neutralize after residue or filtrate in, into environment, cause damages to environment,
Underground water can especially be polluted.
The Chinese invention patent of Publication No. CN102092790A disclose it is a kind of with manganese spar processing Waste Sulfuric Acid prepare hydrogen
The method of manganese oxide co-producing sodium sulfate, main technical schemes are：It takes full advantage of manganese spar and carrys out process for producing titanium dioxide and produced
Its contained manganese is leached out after first crushing manganese spar with hydrochloric acid by raw Waste Sulfuric Acid, then with leaching body fluid and production titanium dioxide
Generated Waste Sulfuric Acid is reacted, and finally carries out combined reaction with nitric acid.On the one hand turn waste into wealth, administered environmental pollution
Meanwhile Waste Sulfuric Acid is transformed into the manganese sulfate with very high economic value, and on the other hand, also coproduction while producing manganese sulfate
Manganous hydroxide and sodium sulphate.This method is handled to handle spent acid using the manganese spar rich in manganese element, instead further
Increase environmental pressure.
Invention content
The purpose of the present invention is overcoming the deficiencies of existing technologies, a kind of new side recycling manganese from titanium white waste acid is explored
Method is extracted manganese therein in the method for chemical oxidation, precipitation by controlling spent acid and lime or the N-process of carbide slag
Come, makes to have achieved the purpose that environmental protection without containing remaining manganese in waste residue or waste water.It is adopted the technical scheme that：
A kind of method that manganous hydroxide is recycled in titanium pigment waste acid processing procedure, comprises the following steps：
1）Titanium white waste acid is diluted to 10% concentration, concentration is added in 200-300g/L lime or carbide slag slurry, gradually adjusts
System pH6-9 is persistently aerated 4-8 hours, and keeps system pH6-9, filters, and in reaction process, system pH is no more than 9；Make
Titanium white diluted acid and lime or carbide slag initial reaction remove ferrous ion therein, iron ion, calcium ion, neutralize wherein as possible
Acid；
2）By step 1）The filtrate being obtained by filtration, the liquor natrii hypochloritis that mass concentration is added in 10%-15% are reduced to 4- to pH
5, concentration is added in 200-300g/L lime or carbide slag slurry or NaOH or KOH, adjusts to 7-8.5, and stablize 0.5 hour；
The liquor natrii hypochloritis that mass concentration is continuously added later in 10%-15% is reduced to 4-5 to pH, and concentration is added in 200-300g/L
Lime or carbide slag slurry or NaOH or KOH are adjusted to 7-8.5 ... repeatedly, until mass concentration is added 10%-15%'s
Liquor natrii hypochloritis pH no longer reduces stopping；Above-mentioned solution is filtered；Make the further oxygen of ferrous ion remaining in filtrate
Change, is formed and precipitate and detach；
3）To step 2）The NaOH or KOH solution of a concentration of 200-300g/L are added in the filtrate of gained, adjustment pH is 9.5-
11.5, and stablize 0.5 hour, clarification alkaline filtrate and the solid containing manganous hydroxide is obtained by filtration；Make the Mn in filtrate with heavy
The mode in shallow lake extracts, and is recycled；
4）To step 3）The dilute sulfuric acid of 10%-15% concentration is added in the filtrate of gained, pH to 6-9 is adjusted, to the alkali in final filtrate
It is neutralized, qualified discharge.
Compared with prior art, present invention process is simple, and raw material is easily purchased of low cost, and reaction process is thoroughly controllable, makes to give up
Without containing remaining manganese in slag or waste water, environmental protection is achieved the purpose that.
Specific implementation mode
1）Titanium white waste acid is diluted to 10% concentration, concentration is added in 200-300g/L lime or carbide slag slurry, gradually
Adjustment system pH6-9 is persistently aerated 4-8 hours, and keeps system pH6-9, filters, and in reaction process, system pH is no more than
9。
FeSO4+Ca(OH)2=Fe（OH）2↓+CaSO4↓；
12FeSO4+6H2O+3O2=4Fe2（SO4)3+4Fe (OH)3↓；
4Fe(OH)2+2H2O+O2=4Fe (OH)3；
Fe2（SO4）3+3Ca(OH)2=2Fe（OH）3↓+3CaSO4↓；
H2SO4+Ca(OH)2=2H2O+CaSO4↓。
The effect of the reaction step be titanium white diluted acid and lime or carbide slag initial reaction, remove Asia therein as possible
Iron ion, iron ion, calcium ion neutralize acid therein.
2）The filtrate that step a is obtained by filtration, the liquor natrii hypochloritis that mass concentration is added in 10%-15% are reduced to pH
4-5, be added concentration 200-300g/L lime or carbide slag slurry or NaOH KOH adjust to 7-8.5, and it is small to stablize 0.5
When.The liquor natrii hypochloritis that mass concentration is continuously added later in 10%-15% is reduced to 4-5 to pH, and concentration is added in 200-
300g/L lime or carbide slag slurry or NaOH KOH adjust to 7-8.5.Repeatedly, until mass concentration is added in 10%-
15% liquor natrii hypochloritis pH no longer reduces stopping.Above-mentioned solution is filtered.
6FeSO4+3NaClO+3H2O=2Fe2（SO4)3+2Fe(OH)3↓+3NaCl；
Fe2（SO4）3 +6H2O =2Fe(OH)3↓+3H2SO4；
FeSO4+Ca(OH)2=Fe（OH）2↓+CaSO4↓；
H2SO4+Ca(OH)2=2H2O+CaSO4↓。
Ferrous ion remaining in filtrate is further aoxidized, and forms precipitation, and is detached.
3）The NaOH or KOH solution of a concentration of 200-300g/L are added into the filtrate obtained by step b, adjustment pH is 9.5-
11.5, and stablize 0.5 hour, clarification alkaline filtrate and the solid containing manganous hydroxide is obtained by filtration.
MnSO4+2NaOH=Mn(OH)2↓+Na2SO4；
Mn2(SO4)3+6NaOH=2Mn(OH)3↓+3Na2SO4；
2Mn(OH)3==Mn(OH)2+MnO2+2H2O；
2Mn(OH)2+ O2==2MnO(OH)2。
Mn in filtrate is extracted in a manner of precipitating, and is recycled.
4）The dilute sulfuric acid of 10%-15% concentration is added to the filtrate obtained by step c, adjusts pH to 6-9.
Alkali in final filtrate is neutralized, qualified discharge.
Claims (4)
1. a kind of method for recycling manganous hydroxide in titanium pigment waste acid processing procedure, which is characterized in that comprise the following steps：
1）Titanium white waste acid is diluted to 10% concentration, concentration is added in 200-300g/L lime or carbide slag slurry, gradually adjusts
System pH6-9 is persistently aerated 4-8 hours, and keeps system pH6-9, filters, and in reaction process, system pH is no more than 9；Make
Titanium white diluted acid and lime or carbide slag initial reaction remove ferrous ion therein, iron ion, calcium ion, neutralize wherein as possible
Acid；
2）By step 1）The filtrate being obtained by filtration, the liquor natrii hypochloritis that mass concentration is added in 10%-15% are reduced to 4- to pH
5, concentration is added in 200-300g/L lime or carbide slag slurry or NaOH or KOH, adjusts to 7-8.5, and stablize 0.5 hour；
The liquor natrii hypochloritis that mass concentration is continuously added later in 10%-15% is reduced to 4-5 to pH, and concentration is added in 200-300g/L
Lime or carbide slag slurry or NaOH or KOH are adjusted to 7-8.5 ... repeatedly, until mass concentration is added 10%-15%'s
Liquor natrii hypochloritis pH no longer reduces stopping；Above-mentioned solution is filtered；Make the further oxygen of ferrous ion remaining in filtrate
Change, is formed and precipitate and detach；
3）To step 2）The NaOH or KOH solution of a concentration of 200-300g/L are added in the filtrate of gained, adjustment pH is 9.5-
11.5, and stablize 0.5 hour, clarification alkaline filtrate and the solid containing manganous hydroxide is obtained by filtration；Make the Mn in filtrate with heavy
The mode in shallow lake extracts, and is recycled；
4）To step 3）The dilute sulfuric acid of 10%-15% concentration is added in the filtrate of gained, pH to 6-9 is adjusted, to the alkali in final filtrate
It is neutralized, qualified discharge.
2. the method for recycling manganous hydroxide in a kind of titanium pigment waste acid processing procedure according to claim 1, feature exist
In the step 1）The chemical reaction of middle generation has：
FeSO4+Ca(OH)2=Fe（OH）2↓+CaSO4↓；
12FeSO4+6H2O+3O2=4Fe2（SO4)3+4Fe (OH)3↓；
4Fe(OH)2+2H2O+O2=4Fe (OH)3；
Fe2（SO4）3+3Ca(OH)2=2Fe（OH）3↓+3CaSO4↓；
H2SO4+Ca(OH)2=2H2O+CaSO4↓。
3. the method for recycling manganese in a kind of titanium pigment waste acid processing procedure according to claim 1, which is characterized in that described
Step 2）The chemical reaction of middle generation has：
6FeSO4+3NaClO+3H2O=2Fe2（SO4)3+2Fe(OH)3↓+3NaCl；
Fe2（SO4）3 +6H2O =2Fe(OH)3↓+3H2SO4；
FeSO4+Ca(OH)2=Fe（OH）2↓+CaSO4↓；
H2SO4+Ca(OH)2=2H2O+CaSO4↓。
4. the method for recycling manganese in a kind of titanium pigment waste acid processing procedure according to claim 1, which is characterized in that described
Step 3）The chemical reaction of middle generation has：
MnSO4+2NaOH=Mn(OH)2↓+Na2SO4；
Mn2(SO4)3+6NaOH=2Mn(OH)3↓+3Na2SO4；
2Mn(OH)3==Mn(OH)2+MnO2+2H2O；
2Mn(OH)2+ O2==2MnO(OH)2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810478501.9A CN108516589B (en) | 2018-05-18 | 2018-05-18 | Method for recycling manganese hydroxide in titanium dioxide waste acid treatment process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810478501.9A CN108516589B (en) | 2018-05-18 | 2018-05-18 | Method for recycling manganese hydroxide in titanium dioxide waste acid treatment process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108516589A true CN108516589A (en) | 2018-09-11 |
| CN108516589B CN108516589B (en) | 2020-10-02 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112386962A (en) * | 2020-11-26 | 2021-02-23 | 河南佰利联新材料有限公司 | Method for increasing sedimentation velocity of thickening tank |
| CN115536073A (en) * | 2022-09-27 | 2022-12-30 | 龙佰禄丰钛业有限公司 | Titanium white chlorination dust collection slag iron resource recovery process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557144A (en) * | 2011-12-29 | 2012-07-11 | 渤海大学 | Method for preparing MnO2 powder with manganese-containing titanium white waste salt |
| CN103395843A (en) * | 2013-07-31 | 2013-11-20 | 攀枝花市立宇矿业有限公司 | Method for preparing manganese dioxide from titanium dioxide waste acid |
| CN106396227A (en) * | 2016-09-08 | 2017-02-15 | 哈尔滨理工大学 | Recycling method for waste acid generated during preparation of graphite oxide through liquid-phase chemical method |
-
2018
- 2018-05-18 CN CN201810478501.9A patent/CN108516589B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557144A (en) * | 2011-12-29 | 2012-07-11 | 渤海大学 | Method for preparing MnO2 powder with manganese-containing titanium white waste salt |
| CN103395843A (en) * | 2013-07-31 | 2013-11-20 | 攀枝花市立宇矿业有限公司 | Method for preparing manganese dioxide from titanium dioxide waste acid |
| CN106396227A (en) * | 2016-09-08 | 2017-02-15 | 哈尔滨理工大学 | Recycling method for waste acid generated during preparation of graphite oxide through liquid-phase chemical method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112386962A (en) * | 2020-11-26 | 2021-02-23 | 河南佰利联新材料有限公司 | Method for increasing sedimentation velocity of thickening tank |
| CN115536073A (en) * | 2022-09-27 | 2022-12-30 | 龙佰禄丰钛业有限公司 | Titanium white chlorination dust collection slag iron resource recovery process |
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Address after: 265716 Dao'en Economic Park, Heping North Road, Longkou Economic Development Zone, Longkou City, Yantai City, Shandong Province Patentee after: Shandong Dao'en Titanium Industry Co.,Ltd. Country or region after: China Address before: 265700 North End of Heping Road, Longkou City, Yantai City, Shandong Province Patentee before: SHANDONG DAWN TITANIUM INDUSTRY Co.,Ltd. Country or region before: China |
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