CN101481161B - Method for producing rare-earth poly-ferric aluminum silicate sulfate from rare earth-containing sludge and iron-containing dust sludge - Google Patents
Method for producing rare-earth poly-ferric aluminum silicate sulfate from rare earth-containing sludge and iron-containing dust sludge Download PDFInfo
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- CN101481161B CN101481161B CN2009100091743A CN200910009174A CN101481161B CN 101481161 B CN101481161 B CN 101481161B CN 2009100091743 A CN2009100091743 A CN 2009100091743A CN 200910009174 A CN200910009174 A CN 200910009174A CN 101481161 B CN101481161 B CN 101481161B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 49
- 239000000428 dust Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims description 19
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052742 iron Inorganic materials 0.000 title claims description 7
- 239000010802 sludge Substances 0.000 title 2
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000009628 steelmaking Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000010801 sewage sludge Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 6
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 abstract description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 3
- 239000008394 flocculating agent Substances 0.000 abstract 3
- 229920002521 macromolecule Polymers 0.000 abstract 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum ion Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention belongs to the technical field of preparing macromolecule flocculating agent for sewage processing, and in particular relates to a method of producing poly-silicate rare-earth aluminum ferric sulfate by using mud containing rare earth and ferric dust, which comprises the steps of material mixing, acid hydrolysis and oxidization, hydrolysis and polymerization. The invention provides a novel technology of using main raw materials, such as sewage and mud containing rare earth and generated in pertrification catalyst production enterprises and mud containing ferric dust generated in metallurgy steel-smelting enterprises for preparing macromolecule flocculating agent. The invention simplifies the technical process for producing poly-silicate rare-earth aluminum ferric sulfate, shortens the production time, has good product stability and performance, provides a new way for utilizing the mud containing rare earth and ferric dust, increases resource integrated utilization rate, lowers the production cost of the poly-silicate rare-earth aluminum ferric sulfate flocculating agent and the cost for sewage processing, and has high economic benefit, environmental protection benefit and social benefit.
Description
One, technical field:
The invention belongs to sewage disposal polymeric flocculant preparing technical field, be specifically related to produce the method for poly-ferric aluminum silicate sulfate from rare earth with containing rare earth mud and ion dust mud contaning.
Two, background technology:
The existing raw material of producing polymeric aluminum sulfate silicate iron has water glass, ferric sulfate, Tai-Ace S 150, and production method is with behind the poly-silicic acid of water glass acidifying preparation, introduces iron again, aluminum ion is polymerized.This production method needs expensive industrial chemicals, and cost is higher.And ZL200510094967.1 " method for preparing poly-silicon iron aluminium sulphate with metallurgical slag ", though found a kind of approach of producing polymeric aluminum sulfate silicate iron production cost that reduces, effective concentration content is lower, poor stability.
Three, summary of the invention:
The objective of the invention is above-mentioned defective at the prior art existence, plan provides a kind of usefulness that is different from the prior art scheme to contain the method for rare earth mud and ion dust mud contaning production poly-ferric aluminum silicate sulfate from rare earth, make it technological process and condition is simple, the investment of production equipment expense is less, process cost is low, product performance are stable, and are superior in quality.
For realizing purpose of the present invention, the technical scheme of being taked is as follows:
Produce the method for poly-ferric aluminum silicate sulfate from rare earth with containing rare earth mud and ion dust mud contaning, it is characterized in that the ion dust mud contaning that it comprises that the sewage sludge that contains rare earth that produces with petrochemical industry Catalyst Production enterprise and metallurgical steel-making enterprise produce is a main raw material, be that it is made up of three step processes:
1. produce the main raw material and the chemical ingredients of poly-ferric aluminum silicate sulfate from rare earth:
The main raw material that the present invention relates to is the sewage sludge of petrochemical industry Catalyst Production enterprise generation and the ion dust mud contaning that metallurgical steel-making enterprise produces.The sewage sludge that petrochemical industry Catalyst Production enterprise produces is that petrochemical industry Catalyst Production enterprise is in producing the catalyst prod process, PH＜4 sewage that produce neutralize with NaOH, make sewage PH〉9 carry out sewage disposal with sewage treatment process again, the mud that in sewage treatment process, is produced, its chemical ingredients sees Table 1, and the SiO2 that contains in this mud, AL2O3, La2O3, CeO2 component are the raw material sources that this method is produced poly-ferric aluminum silicate sulfate from rare earth.Ion dust mud contaning, source and metallurgical steelmaking process, its chemical ingredients sees Table 2, and the Fe2O3 that contains in this dirt mud, FeO component are the raw material sources that this method is produced poly-ferric aluminum silicate sulfate from rare earth.
The main chemical compositions of the sewage sludge of table 1. production petrochemical industry catalyzer enterprise
The main chemical compositions of table 2. steel making dust slime
2. production process:
(1)。To contain rare earth mud, steel making dust slime by weight percentage 1: (1.7-2.2) thorough mixing is put into acid-resistant reacting kettle.
(2)。With mass percentage concentration (3-10%) H2SO4 slowly pour in the reactor to contain rare earth mud, steel making dust slime carries out acidolysis, rare earth mud, steel making dust slime: (3-10%) H2SO4 is by weight 1: (10-20) fully stir 1 hour, the question response system is cooled to room temperature, and acidolysis reaction finishes.
(3)。Reaction product is filtered removal throw out (being mainly gypsum and acid non-soluble substance), the H2O2 of filtrate (being mainly the mixing solutions of ferrous salt, trivalent iron salt, aluminium salt, lanthanum salt, cerium salt and silicate hydrate) with 27.5% makes that Fe2+ all is oxidized to Fe3+ in the solution, and its oxidation terminal point of the process of Oxidation of Fe 2+ is determined with the Tripotassium iron hexacyanide; Adjusting the solution pH value with 30%NaOH again is 2.0-2.5; Solution adjusted was placed heating in water bath 1-2 hour, maintain the temperature at about 80 ℃, make solution adjusted hydrolysis voluntarily, polymerization, dark red brown liquid product occurs, be the poly-ferric aluminum silicate sulfate from rare earth flocculation agent.
The present invention gel do not occur by the previous process steps products obtained therefrom in 2 months, product performance are more stable.
Compared with prior art the present invention has following unusual effect:
1, the sewage sludge of petrochemical industry Catalyst Production enterprise generation is that petrochemical industry Catalyst Production enterprise is in producing the catalyst prod process, PH＜4 sewage that produce neutralize with NaOH, make sewage PH〉9 carry out sewage disposal with sewage treatment process again, the mud that in sewage treatment process, is produced, make the SiO2 in the mud be converted into Na2SiO3, for acidifying, hydrolysis, polyreaction have been created condition.
2, the sewage sludge of petrochemical industry Catalyst Production enterprise generation is the mud that is produced in the sewage treatment process of petrochemical industry Catalyst Production enterprise in producing the catalyst prod process, the La2O3 that contains in this mud, CeO2s component play oxidation, katalysis in producing poly-ferric aluminum silicate sulfate from rare earth technology, shortened that time and the polymeric aluminum sulfate silicate ferrous acid that Fe2+ is converted into Fe3+ separated, hydrolysis, polymerization time.In addition, poly-ferric aluminum silicate sulfate from rare earth is because La2O3, CeO2 participate in polymeric aluminum sulfate silicate iron polymeric chemical reaction, changed the molecular structure of polymeric aluminum sulfate silicate ferric flocculant, formed than the also big poly-ferric aluminum silicate sulfate from rare earth complex molecule of polymeric aluminum sulfate silicate iron complex molecule volume, the wastewater treatment efficiency of this complex molecule will be considerably beyond the wastewater treatment efficiency of existing polymeric aluminum sulfate silicate iron complex molecule.
In a word, usefulness of the present invention contains the method for rare earth mud and ion dust mud contaning production poly-ferric aluminum silicate sulfate from rare earth, and the poly-ferric aluminum silicate sulfate from rare earth flocculation agent of being produced is suitable for handling high-concentration sewage, sanitary sewage, industrial sewage.This production method has been simplified technological process, has shortened the production time, and product stability is good, excellent property; Provide new approach for the utilization that contains rare earth mud and ion dust mud contaning simultaneously, improved the comprehensive utilization of resources rate, also reduce the production cost and the cost of sewage disposal of poly-ferric aluminum silicate sulfate from rare earth flocculation agent, had very high economic benefit, environmental benefit and social benefit.
Four, embodiment:
Example one:
(1). take by weighing 2kg and contain rare earth mud, 3.6kg steel making dust slime thorough mixing, will contain rare earth mud, steel making dust slime and put into acid-resistant reacting kettle in 1: 1.8 by weight percentage.
(2). with 52L mass percentage concentration 10%H2SO4 slowly pour in the reactor to contain rare earth mud, steel making dust slime carries out acidolysis, containing rare earth mud, steel making dust slime: 10%H2SO4 fully stirred 1 hour by weight 1: 10, the question response system is cooled to room temperature, and acidolysis reaction finishes.
(3). reaction product is filtered removal throw out (being mainly gypsum and acid non-soluble substance), the H2O2 of filtrate (being mainly the mixing solutions of ferrous salt, trivalent iron salt, aluminium salt, lanthanum salt, cerium salt and silicate hydrate) with 27.5% makes that Fe2+ all is oxidized to Fe3+ in the solution, its oxidation terminal point of the process of Oxidation of Fe 2+ is determined (drips of solution that takes a morsel is added on the Tripotassium iron hexacyanide solid, and the nondiscoloration explanation all is converted into Fe3+) with the Tripotassium iron hexacyanide; Adjusting the solution pH value with 30%NaOH again is 2.0-2.5; Solution adjusted was placed heating in water bath 1 hour, maintain the temperature at about 80 ℃, make solution adjusted hydrolysis voluntarily, polymerization, dark red brown liquid product appears, be the poly-ferric aluminum silicate sulfate from rare earth flocculation agent, product is preserved and gel do not occurred in two months, and product performance are more stable.
Example two:
(1). take by weighing 2kg and contain rare earth mud, 4kg steel making dust slime thorough mixing, will contain rare earth mud, steel making dust slime and put into acid-resistant reacting kettle in 1: 2 by weight percentage.
(2). with 99L mass percentage concentration 5%H2SO4 slowly pour in the reactor to contain rare earth mud, steel making dust slime carries out acidolysis, containing rare earth mud, steel making dust slime: 5%H2SO4 fully stirred 1 hour by weight 1: 17, the question response system is cooled to room temperature, and acidolysis reaction finishes.
(3). reaction product is filtered removal throw out (being mainly gypsum and acid non-soluble substance), the H2O2 of filtrate (being mainly the mixing solutions of ferrous salt, trivalent iron salt, aluminium salt, lanthanum salt, cerium salt and silicate hydrate) with 27.5% makes that Fe2+ all is oxidized to Fe3+ in the solution, its oxidation terminal point of the process of Oxidation of Fe 2+ is determined (drips of solution that takes a morsel is added on the Tripotassium iron hexacyanide solid, and the nondiscoloration explanation all is converted into Fe3+) with the Tripotassium iron hexacyanide; Adjusting the solution pH value with 30%NaOH again is 2.0-2.5; Solution adjusted was placed heating in water bath 1.5 hours, maintain the temperature at about 80 ℃, make solution adjusted hydrolysis voluntarily, polymerization, dark red brown liquid product appears, be the poly-ferric aluminum silicate sulfate from rare earth flocculation agent, product is preserved and gel do not occurred in two months, and product performance are more stable.
Claims (1)
1. produce the method for poly-ferric aluminum silicate sulfate from rare earth with containing rare earth mud and ion dust mud contaning for one kind, it is characterized in that the iron content steel making dust slime that it comprises that the sewage sludge that contains rare earth that produces with petrochemical industry Catalyst Production enterprise and metallurgical production enterprise produce is a raw material, be that it is made up of three step processes:
(1). will contain rare earth mud, steel making dust slime by weight 1: (1.7-2.2) thorough mixing is put into acid-resistant reacting kettle;
(2). with mass percentage concentration 3-10%H
2SO
4Slowly pour in the reactor to contain rare earth mud, steel making dust slime carries out acidolysis, contains rare earth mud, steel making dust slime: 3-10%H
2SO
4By weight 1: (10-20) fully stir 1 hour, the question response system is cooled to room temperature, and acidolysis reaction finishes;
(3). reaction product filter is removed throw out, and throw out is mainly gypsum and acid non-soluble substance, and filtrate is with 27.5% H
2O
2Make Fe in the solution
2+All be oxidized to Fe
3+, filtrate is mainly the mixing solutions of ferrous salt, trivalent iron salt, aluminium salt, lanthanum salt, cerium salt and silicate hydrate, Oxidation of Fe
2+Its oxidation terminal point of process determine with the Tripotassium iron hexacyanide; Adjusting the pH value of solution value with 30%NaOH again is 2.0-2.5; Solution adjusted was placed heating in water bath 1-2 hour, maintain the temperature at 80 ℃, make solution adjusted hydrolysis voluntarily, polymerization, dark red brown liquid product occurs, be the poly-ferric aluminum silicate sulfate from rare earth flocculation agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100091743A CN101481161B (en) | 2009-02-23 | 2009-02-23 | Method for producing rare-earth poly-ferric aluminum silicate sulfate from rare earth-containing sludge and iron-containing dust sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100091743A CN101481161B (en) | 2009-02-23 | 2009-02-23 | Method for producing rare-earth poly-ferric aluminum silicate sulfate from rare earth-containing sludge and iron-containing dust sludge |
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| Publication Number | Publication Date |
|---|---|
| CN101481161A CN101481161A (en) | 2009-07-15 |
| CN101481161B true CN101481161B (en) | 2010-12-01 |
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| CN2009100091743A Expired - Fee Related CN101481161B (en) | 2009-02-23 | 2009-02-23 | Method for producing rare-earth poly-ferric aluminum silicate sulfate from rare earth-containing sludge and iron-containing dust sludge |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173491B (en) * | 2011-03-18 | 2012-07-25 | 福建省长汀金龙稀土有限公司 | Process for comprehensively utilizing rare-earth ore leaching waste liquid and calcining waste heat in rare earth production |
| CN102583675A (en) * | 2012-03-02 | 2012-07-18 | 杨祺 | Method for producing poly-silicone sulfuric acid rare earth ferroaluminum with Byer process red mud and sludge containing rear earth |
| CN103030200A (en) * | 2013-01-09 | 2013-04-10 | 杨祺 | Method for producing poly-silicon rare earth chloride sulfate aluminum iron by using rare earth-containing sludge and electroplated and pickled acid-containing sewage |
| CN104556324A (en) * | 2013-10-18 | 2015-04-29 | 乔占印 | RE (rare earth)-PAFSS (poly-aluminum ferric sulfate silicate) and preparation method thereof |
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Effective date of registration: 20190111 Address after: 100875 No. 19 Xinjiekouwai Street, Haidian District, Beijing Normal University Patentee after: Yang Qi Address before: Room 321, West Building, 6 Beijing West Road, Taicang City, Jiangsu Province Patentee before: Jiangsu min operation and environmental protection science and technology limited company |
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