DE2157738A1 - Verfahren zum behandeln von kationenaustauscherregeneraten und anderen salzhaltigen saeuren - Google Patents
Verfahren zum behandeln von kationenaustauscherregeneraten und anderen salzhaltigen saeurenInfo
- Publication number
- DE2157738A1 DE2157738A1 DE2157738A DE2157738A DE2157738A1 DE 2157738 A1 DE2157738 A1 DE 2157738A1 DE 2157738 A DE2157738 A DE 2157738A DE 2157738 A DE2157738 A DE 2157738A DE 2157738 A1 DE2157738 A1 DE 2157738A1
- Authority
- DE
- Germany
- Prior art keywords
- acid
- solvent
- acids
- salt
- exchanger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims description 117
- 238000000034 method Methods 0.000 title claims description 38
- 150000007513 acids Chemical class 0.000 title claims description 23
- 150000003839 salts Chemical class 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- 150000001768 cations Chemical class 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic alcohols Chemical class 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 description 26
- 230000008929 regeneration Effects 0.000 description 25
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 230000001172 regenerating effect Effects 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000005554 pickling Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 229940023913 cation exchange resins Drugs 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000012492 regenerant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000000061 acid fraction Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical class [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/01—Waste acid containing iron
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/01—Waste acid containing iron
- Y10S423/02—Sulfuric acid
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/09—Reaction techniques
- Y10S423/14—Ion exchange; chelation or liquid/liquid ion extraction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE788818D BE788818A (fr) | 1971-11-22 | Procede de traitement de produits de regeneration d'echangeurs de cations et d'autres acides contenant des sels | |
| DE2157738A DE2157738A1 (de) | 1971-11-22 | 1971-11-22 | Verfahren zum behandeln von kationenaustauscherregeneraten und anderen salzhaltigen saeuren |
| FR7224055A FR2160795B3 (US07655688-20100202-C00086.png) | 1971-11-22 | 1972-06-28 | |
| NL7209637A NL7209637A (US07655688-20100202-C00086.png) | 1971-11-22 | 1972-07-12 | |
| US282752A US3862298A (en) | 1971-11-22 | 1972-08-22 | Process for the treatment of a salt-containing acid solution |
| IT30118/72A IT968649B (it) | 1971-11-22 | 1972-10-05 | Procedimento per trattare rigenera ti di scambiatori di cationi ed altri acidi contenenti sali |
| GB5317472A GB1371589A (en) | 1971-11-22 | 1972-11-17 | Process for treating salt-containing acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2157738A DE2157738A1 (de) | 1971-11-22 | 1971-11-22 | Verfahren zum behandeln von kationenaustauscherregeneraten und anderen salzhaltigen saeuren |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2157738A1 true DE2157738A1 (de) | 1973-06-07 |
| DE2157738B2 DE2157738B2 (US07655688-20100202-C00086.png) | 1973-12-06 |
Family
ID=5825722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2157738A Pending DE2157738A1 (de) | 1971-11-22 | 1971-11-22 | Verfahren zum behandeln von kationenaustauscherregeneraten und anderen salzhaltigen saeuren |
Country Status (7)
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4018869A (en) * | 1973-06-06 | 1977-04-19 | Chemische Fabrik Budenheim Rudolf A. Oetker | Process for the extractive purification of phosphoric acid containing cationic impurities |
| US4049779A (en) * | 1975-12-24 | 1977-09-20 | Allied Chemical Corporation | Crystalline salt monomers for stable phosphate glasses |
| DE3065736D1 (en) * | 1979-01-25 | 1984-01-05 | Stamicarbon | Process for recovering a uranium-containing concentrate and purified phosphoric acid from wet-process phosphoric acid, and products thus obtained |
| NL8004221A (nl) * | 1980-07-23 | 1982-02-16 | Stamicarbon | Werkwijze voor het winnen van een uraniumbevattend concentraat en gezuiverd fosforzuur, alsmede uraniumbevattend concentraat en gezuiverd fosforzuur verkregen volgens deze werkwijze. |
| US4428915A (en) | 1982-10-25 | 1984-01-31 | Olin Corporation | Process for recovering phosphate values from precipitates formed during the neutralization of impure wet process phosphoric acid |
| US4608245A (en) * | 1985-10-17 | 1986-08-26 | Gaddy James L | Method of separation of sugars and concentrated sulfuric acid |
| HU198159B (en) * | 1987-03-23 | 1989-08-28 | Foevarosi Tavfuetoe Muevek | Process for regenerating ion-exchange resin and utilizing the regenerate in the agriculture |
| US4877594A (en) * | 1988-12-13 | 1989-10-31 | J. R. Simplot Co. | Purification of phosphoric acid |
| DE102007049757A1 (de) * | 2007-10-16 | 2009-04-23 | Chemische Fabrik Budenheim Kg | Eisen(III)orthophosphat für Li-Ionen-Akkumulatoren |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3463609A (en) * | 1967-05-04 | 1969-08-26 | Raymond W Garris | Phosphoric acid production |
| US3684438A (en) * | 1970-11-05 | 1972-08-15 | Fmc Corp | Purification of phosphoric acid |
-
0
- BE BE788818D patent/BE788818A/xx unknown
-
1971
- 1971-11-22 DE DE2157738A patent/DE2157738A1/de active Pending
-
1972
- 1972-06-28 FR FR7224055A patent/FR2160795B3/fr not_active Expired
- 1972-07-12 NL NL7209637A patent/NL7209637A/xx not_active Application Discontinuation
- 1972-08-22 US US282752A patent/US3862298A/en not_active Expired - Lifetime
- 1972-10-05 IT IT30118/72A patent/IT968649B/it active
- 1972-11-17 GB GB5317472A patent/GB1371589A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2160795B3 (US07655688-20100202-C00086.png) | 1975-08-29 |
| BE788818A (fr) | 1973-01-02 |
| FR2160795A1 (US07655688-20100202-C00086.png) | 1973-07-06 |
| DE2157738B2 (US07655688-20100202-C00086.png) | 1973-12-06 |
| GB1371589A (en) | 1974-10-23 |
| NL7209637A (US07655688-20100202-C00086.png) | 1973-05-24 |
| US3862298A (en) | 1975-01-21 |
| IT968649B (it) | 1974-03-20 |
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