CS260159B1 - Method of trihydrogenphosphoric acid neutralization and equipment for its realization - Google Patents
Method of trihydrogenphosphoric acid neutralization and equipment for its realization Download PDFInfo
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- CS260159B1 CS260159B1 CS85973A CS97385A CS260159B1 CS 260159 B1 CS260159 B1 CS 260159B1 CS 85973 A CS85973 A CS 85973A CS 97385 A CS97385 A CS 97385A CS 260159 B1 CS260159 B1 CS 260159B1
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- ammonia
- pipe
- diffuser
- circulation tank
- liquid
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 title claims abstract description 14
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 abstract 1
- 235000019837 monoammonium phosphate Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 239000013049 sediment Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Fertilizers (AREA)
Abstract
Neutralizácia trihydrogénfosforečnej kyseliny amoniakom sa prevádla cirkulovaným zmesným roztokom hydrogén- a/alebo dihydrogénfosforečnanom amónnym s prí davkom trihydrogénfosforečnej kyseliny pri pH 1 až 7,5 v difúzore kvapalinoprúdeho ejektora. Amoniak obsahuje vodnú páru v molárnom pomere 1 : 0,1 až 1 : 3. Zariadením pre uskutočnenie je kvapallnoprúdy ejektor, ktorého dýza je cirkulačnou rúrou a čerpadlom přepojená s cirkulačnou nádr žou, rúra procesných pár je na rúru výstupu inertov přepojená cez kondenzátor procesných pár a odvod procesných kondenzá- tov je rúrkovým prepojom procesovej vody spojený s cirkulačnou nádržou. Difúzor je spojený s rúrou vodnej páry a/alebo prepojovacou rúrou procesovej páry.Neutralization of trihydrogenphosphoric acid ammonia was circulated a mixed solution of hydrogen and / or with ammonium dihydrogen phosphate, e.g. trihydrogenphosphoric acid pH 1 to 7.5 in the liquid ejector diffuser. Ammonia contains water vapor in molar ratio of 1: 0.1 to 1: 3 for carrying out, the liquid stream is an ejector, the nozzle of which is a circulating tube and pump connected to the circulation tank the process pair oven is on the outlet pipe inerting through a process condenser pair and process condensate drain is a tubular interconnection of process water connected to the circulation tank. The diffuser is associated with a water steam pipe and / or interconnecting process steam.
Description
Vynález sa týká sposobu neutralizácie kyseliny trihydrogénfosforečnej amoniakom a zariadenia k jej uskutočneniu.The invention relates to a process for neutralizing ammonia trihydrogenphosphoric acid and to an apparatus for carrying out it.
Amónne soli trihydrogénfosforečnej kyseliny, popři dusičnane amónnom a močovině sú významnými anorganickými sofami. Majů široké uplatnenie při technológii výroby priemyselných hnojiv a to jak pevných, tak v roztoku ako kvapalné hnojivá číře i suspenzné. Technologická příprava sa zabezpečuje neutralizáciou trihydrogénfosforečnej kyseliny amoniakom, alebo amoniakálnou vodou, a to podlá sposobu uplatnenia připravovaných fosforečnanov, obvykle v reakčných nádobách opatřených miešadlom v jednom, alebo vo dvoch stupňoch s priamym vstupom plynného, alebo kvapalného amoniaku a vody pre reguláciu výstupnej koncentrácie. Sú známe riešenia pracujúce na principe sprchovacích kolón, kde do prúdu amoniakálnych pár sa nastrekuje kyselina trihydrogénfosforečná v dvojstupňovom zapojení, známe ako postup OTTO-v. Je známy postup priameho zmešovania kyseliny fosforečnej amoniaku vo vírivom reaktore s priamym rozstrekom ako tzv. postup GARDINIER-ov. Priemyselne našlo široké uplatnenie tzv. rúrkového T reaktora, ako zmešovacieho elementu s priamym vstrekom kyseliny a amoniaku do reakčnej zóny tvorenej rúrou, doplněného o separátor a účinný vypierač aerosolových exhalátov. Tieto systémy, alebo ich kombinácie sú predmetom v literatúre publikovaných práč, ako i US patentov 3 813 233; 3 775 534. Uvedené systémy, pri ich uplatnění v príprave kvapalných NP roztokov z komerčných tzv. extrakčných kyselin s obsahom znečisťujúcich příměsí, najma železa a hliníka poskytujú roztoky, v ktorých neutralizáciou vznikajú nerozpustné fosforečnany, 1'ahko sedimentujúce, čím znižujú užitnú hodnotu výrobkov v dósledku zanášania skladovacích nádrží, dopravných rúr, aplikačnej techniky, ktoré vlastnosti sú charakterizované tzv. fluiditou, ako percentuálneho zbytku sedimentu z celkového objemu za stanovený čas. Táto dosahuje hodnoty 3 % a vyššie. V dósledku toho je potřebný prídavok stabilizujúcich přísad, obvykle aktivovaného bentonitu, ako aj dalších látok, ktoré priebeh sedimentácie spomalujú.The ammonium salts of trihydrogenphosphoric acid, along with ammonium nitrate and urea, are important inorganic salts. They have a wide application in the technology of industrial fertilizer production, both solid and in solution, both liquid and suspension fertilizers. Technological preparation is ensured by neutralization of trihydrogenphosphoric acid with ammonia or ammonia water, according to the application of prepared phosphates, usually in reaction vessels equipped with a stirrer in one or two stages with direct inlet of gaseous or liquid ammonia and water to control the output concentration. There are known solutions based on the principle of shower columns, where the ammoniacal vapor stream is injected with trihydrogenphosphoric acid in a two-stage connection, known as the OTTO-v process. It is known to directly mix phosphoric acid ammonia in a direct spray vortex reactor as a so-called. GARDINIER procedure. Industry has found wide application of the so-called. of a tubular T reactor, as a mixing element with a direct injection of acid and ammonia into the reaction zone formed by the pipe, supplemented with a separator and an effective scrubber for aerosol exhalations. These systems, or combinations thereof, are the subject of published literature as well as U.S. Patents 3,813,233; Said systems, when used in the preparation of liquid NP solutions from commercial so-called " Extractive acids containing contaminants, especially iron and aluminum, provide solutions in which insoluble phosphates are formed which are easily sedimented, thereby reducing the utility value of the products due to clogging of storage tanks, conveyor tubes, application techniques, the characteristics of which are characterized by so-called " fluidity, as a percentage of the residual sediment from the total volume over a given time. It reaches 3% and higher. Consequently, the addition of stabilizing additives, usually activated bentonite, as well as other substances that slow down the sedimentation process is needed.
Ukázalo sa, že uvedený problém je možné riešit sposobom neutralizácie a zariadením podlá tohto vynálezu, podstatou ktorého je, že neutralizácia amoniakom sa uskutočňuje cirkulovaným zmesným roztokom hydrogén- a/alebo dihydrogénfosforečnanu amonného s prídavkom trihydrogénfosforečnej kyseliny pri pH 1 až 7,5 v difúzore kvapalinoprúdeho ejektoru. Amoniak obsahuje páru v molárnom pomere 1 : 0,1 až 1 : 3. Zariadenie pre uskutočnenie spósobu vyznačené tým, že dýza kvapalinoprúdeho ejektoru je cirkulačnou rúrou a čerpadlom přepojená s cirkulačnou nádržou, rúra procesných pár je na rúru výstupu inertov přepojená cez kondenzátor procesových pár, odvod procesných kondenzátov je rúrkovým prepojom procesovej vody spojený s cirkulačnou nádržou. Difúzor je spojený s rúrou vodnej páry a/alebo prepojovacou rúrou procesovej páry.It has been found that this problem can be solved by the neutralization method and the device according to the invention, which is characterized in that the neutralization with ammonia is carried out with a circulating mixed solution of hydrogen and / or dihydrogen phosphate with addition of trihydrogenphosphoric acid at pH 1 to 7.5. ejector. Ammonia contains steam in a molar ratio of 1: 0.1 to 1: 3. Apparatus for carrying out the method, characterized in that the liquid-jet ejector nozzle is connected to a circulation tank by a pump and a pump, the process vapor is connected to an inert outlet tube via a , the discharge of process condensates is connected to the circulation tank via a process water pipe connection. The diffuser is connected to a water vapor pipe and / or process steam interconnecting pipe.
Spósob a zariadenie podlá vynálezu vytvára reakčné podmienky v turbulentnom toku s pozvolným priebehom neutralizácie, čím sa získavajú roztoky, ktoré aj bez přídavku stabilizujúcich přísad sú dostatočne stabilně, pričom případný sediment je spSť 1'ahko dispergovatelný. Nevyžaduje sa zvláštnych doplňujúcich zariadení pre vypieranie aerosolových exhalácií aj v případe, keď neutralizácia prebieha jednostupňove a pri vyšších koncentráciach cirkulujúceho roztoku.The method and apparatus of the present invention create reaction conditions in a turbulent flow with a gradual neutralization process, thereby obtaining solutions which, even without the addition of stabilizing additives, are sufficiently stable, with the possible sediment being readily dispersible. No special additional devices for scrubbing aerosol exhalations are required even if the neutralization is carried out in one step and at higher circulating solution concentrations.
Na pripojenom obrázku je znázorněné schematické usporiadanie jednotlivých prvkov podlá vynálezu.The attached figure shows a schematic arrangement of the individual elements according to the invention.
Cirkulačně nádrž 1 je cirkulačnou rúrou 11 a čerpadlom 6, chladičom roztoku 18 přepojená s dýzou 3 kvapalinoprúdeho c-, jektora 2. Difúzor 4 kvapalinoprúdeho ejektora 2 je napojený na rúru 13 vstupu amoniaku, rúru 21 vodnej páry a prepojovaciu rúru 20 procesovej páry. Cirkulačně nádrž 1 je opatřená výstupnou rúrou 12 roztoku. Procesové páry odchádzajú z cirkulačnej nádrže 1 rúrou 8 procesných pár cez kondenzátor 5 procesných pár. Neskondenzovaný podiel odchádza rúrou 18 výstupu inertov. Procesná voda vstupuje rúrou 7 přívodu procesnej vody a je přepojená odvodom 17 procesných kondenzátov z kondenzátora 5 procesných pár rúrkovým prepojom 9. Cirkulačně rúra 11 je přepojená s rúrou 10 kyseliny trihydrogénfosforečnej. Chladič roztoku 18 a kondenzátor 5 sú napojené na přívod chladiacej vody 14 a odvod chladiacej vody 15.The circulation tank 1 is a circulation tube 11 and a pump 6, a solution cooler 18 connected to a liquid flow nozzle 3, a jector 2. The liquid flow ejector diffuser 4 is connected to the ammonia inlet tube 13, the water vapor tube 21 and the process steam connection tube 20. The circulation tank 1 is provided with a solution outlet pipe 12. The process vapors leave the circulation tank 1 through a process vapor tube 8 via a process vapor condenser 5. The non-condensed portion exits through the inert gas outlet pipe 18. The process water enters the process water supply pipe 7 and is connected by a process condensate drain 17 from the process pair condenser 5 via a pipe connection 9. The circulation pipe 11 is connected to the phosphoric acid phosphoric pipe 10. The solution cooler 18 and the condenser 5 are connected to the cooling water inlet 14 and the cooling water outlet 15.
V případe přípravy vysokokoncentrovaných presýtených roztokov s prídavkom aditívnych přísad, tieto móžu vstupovat rúrou 19 do cirkulačnej rúry 11. V případe nutnosti zvlášť vysokých požiadaviek ekologického znečistenia, rúra 16 výstupu inertov móže byť napojená na asanačný absorbér běžných konštrukčných typov.In the case of the preparation of highly concentrated supersaturated solutions with the addition of additives, these can enter through the pipe 19 into the circulation pipe 11. In the case of particularly high ecological contamination requirements, the inert outlet pipe 16 can be connected to a sanitation absorber of conventional design types.
PřikladlEXAMPLE
Kvapalinoprúdnym ejektorom cirkulovalo 114 m3/hod. roztoku hydrogén- a dihydrogénfosforečnanu amónneho. Počiatočná hodnota pH sa pohybovala v rozmedzí hodnot 1 až 1,2 a teplota 63 až 64 °C. Súčasne sa do cirkulačnej nádrže nastrekovala procesná voda v množstve 1,5 až 2,5 m3/h. v závislosti od mernej hmotnosti roztoku a do cirkulovaného roztoku 1 až 1,8 m3/h. extrakčná trihydrogénfosforečná kyselina. Do difúzora kvapalinoprúdeho ejektore sa přidávala zmes amoniakálnych pár a vodnej páry v molárnom pomere 1 : 2, ktorý sa po5 stupně upravil na molárny poměr 1 : 0,15. Teplota roztoku sa udržovala na hodnotě 63 až 67 °C. Postupné sa zvyšovalo pH až do dosiahnutia hodnoty 7,4. Získal sa roztok s měrnou hmotnosťou 1210 kg . cm-3 s obsahom 7,9 % hmot. N a 19,4 % hmot. citrorozpustného P2O5. Použitá kyselina obsahovala 54,2 % hmot. P2O5; 1,83 % hmot. R2O3;The liquid ejector circulated 114 m 3 / h. solution of ammonium hydrogen and dihydrogen phosphate. The initial pH ranged from 1 to 1.2 and the temperature was 63 to 64 ° C. At the same time, process water of 1.5 to 2.5 m 3 / h was injected into the circulation tank. depending on the specific gravity of the solution and into the circulating solution 1 to 1.8 m 3 / h. Extraction trihydrogenphosphoric acid. A 1: 2 molar ratio mixture of ammonia vapor and water vapor was added to the liquid ejector diffuser, which was adjusted to a molar ratio of 1: 0.15 after 5 degrees. The temperature of the solution was maintained at 63-67 ° C. The pH was gradually increased until it reached 7.4. A solution with a specific gravity of 1210 kg was obtained. cm -3 containing 7.9 wt. N and 19.4 wt. citric soluble P2O5. The acid used contained 54.2 wt. P2O5; 1.83 wt. R2O3;
2,9 % hmot. H2SO4; 0,11 % hmot. oxidovateíných příměsí a 1,34 % hmot. sedimentujúcich častíc.2.9 wt. H2SO4; 0.11% wt. % of oxidizable admixtures and 1.34 wt. sedimenting particles.
P r í k 1 a d 2Example 1 a d 2
Do cirkulovaného roztoku s počiatočným pH 1,5 kvapalinoprúdeho ejektora, ako v příklade 1 sa nastrekovala extrakčná kyselina trihydrogénfosforečná zloženia 53,3 % hmot. P2O5; 1,8 % hmot. R2O3; 3,6 % hmot. H2SO4; 0,12 % hmot. oxidovateíných příměsí, 1,04 % hmot. sedimentu, procesná voda a do difúzora kvapalinoprúdeho ejektora sa privádzala zmes plynného amoniaku a vodnej páry s molárnym pomerom 1 : 1,9 až 1 : 2,9. Cirkulovaný roztok sa udržoval v teplotnom intervale 66 až 87 =C. pH sa postupné zvyšovalo až na hodnotu 6,7. Prídavok procesnej vody sa reguloval podía hodnoty mernej hmotnosti, ktorá dosiahla 1 390 kilogramov . cm-3, pri zložení roztoku 35,6 pere. hmot. P2O5; 13,1 % hmot. N. Dalším prídavkom procesnej vody sa upravila měrná hmotnost roztoku na hodnotu 1 262 kg . . cm3. Získaný roztok so zložením 9,1 % hmot. N; 23,9 % hmot. P2O5; pH 6,6 mal fluiditu 1,05 %.In a circulating solution with an initial pH of 1.5 liquid ejector, as in Example 1, 53.3% by weight of trihydrogenphosphoric acid was injected. P2O5; 1.8 wt. R2O3; 3.6 wt. H2SO4; 0.12% wt. % of oxidizable impurities, 1.04 wt. sediment, process water, and a mixture of ammonia gas and water vapor with a molar ratio of 1: 1.9 to 1: 2.9 were fed to the liquid ejector diffuser. Circulating solution is maintained in the temperature range of 66-87 C. pH = it is gradually increased up to 6.7. The addition of process water was controlled by a specific gravity value of 1,390 kilograms. cm -3 , when the solution is 35.6 pens. wt. P2O5; 13.1 wt. N. The addition of the process water brought the solution to a specific gravity of 1262 kg. . cm 3 . The solution obtained was 9.1% by weight. N; 23.9 wt. P2O5; The pH of 6.6 had a fluidity of 1.05%.
Příklad 3Example 3
Do cirkulovaného roztoku s počiatočným pH 1,2 kvapalinoprúdeho ejektora, ako v příklade 1 sa nastrekovala trihydrogénfosforečná extrakčná kyselina zloženia 53,6 % hmot. P2O5; 1,49 % hmot. R2O3; 2,9 % hmot. H2SO4; 0,55 % hmot. sedimentu; 0,01 % hmot. oxidovateíných látok, procesný kondenzát a do difúzora kvapalinoprúdeho ejektora sa přidávala zmes pár amoniaku a vodnej páry v molárnom pomere 1 : 3.Trihydrogenphosphoric extraction acid of composition 53.6% by weight was injected into a circulating solution with an initial pH of 1.2 liquid ejector, as in Example 1. P2O5; 1.49% wt. R2O3; 2.9 wt. H2SO4; 0.55 wt. sediment; 0.01 wt. a mixture of ammonia vapor and water vapor in a molar ratio of 1: 3 was added to the liquid ejector diffuser.
Cirkulovaný roztok sa udržoval pri teplote 70 až 90 °C. pH sa postupné zvyšovalo až na hodnotu 6,7 a mernú hmotnost 1 322 kg . . cm'3. Roztok so zložením 10,4 % hmot. N; 27,6 % hmot. P2O5 sa kontinuálně odvádzal z cirkulačnej nádrže a po přídavku procesného kondenzátu sa upravil na konečné zloženie 9,1 °/o hmot. N; 24,2 % hmot. P2O5. Fluidita připravovaného roztoku bola 2,4 °/o.The circulated solution was maintained at 70-90 ° C. The pH gradually increased up to 6.7 and a specific gravity of 1322 kg. . cm ' 3 . 10.4% by weight solution. N; 27.6 wt. P2O5 was continuously withdrawn from the circulation tank and after addition of process condensate was adjusted to a final composition of 9.1% w / w. N; 24.2 wt. P2O5. The fluidity of the prepared solution was 2.4%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS85973A CS260159B1 (en) | 1985-02-12 | 1985-02-12 | Method of trihydrogenphosphoric acid neutralization and equipment for its realization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS85973A CS260159B1 (en) | 1985-02-12 | 1985-02-12 | Method of trihydrogenphosphoric acid neutralization and equipment for its realization |
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| Publication Number | Publication Date |
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| CS97385A1 CS97385A1 (en) | 1988-05-16 |
| CS260159B1 true CS260159B1 (en) | 1988-12-15 |
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