CS234967B1 - Method of liquid zinc concentrate preparation - Google Patents
Method of liquid zinc concentrate preparation Download PDFInfo
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- CS234967B1 CS234967B1 CS403382A CS403382A CS234967B1 CS 234967 B1 CS234967 B1 CS 234967B1 CS 403382 A CS403382 A CS 403382A CS 403382 A CS403382 A CS 403382A CS 234967 B1 CS234967 B1 CS 234967B1
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- 239000011701 zinc Substances 0.000 title claims description 47
- 229910052725 zinc Inorganic materials 0.000 title claims description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 26
- 239000007788 liquid Substances 0.000 title claims description 11
- 239000012141 concentrate Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical class [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 235000009529 zinc sulphate Nutrition 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 hydrogen ions Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 235000014692 zinc oxide Nutrition 0.000 description 8
- 239000003929 acidic solution Substances 0.000 description 7
- 239000003337 fertilizer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 206010048259 Zinc deficiency Diseases 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000011785 micronutrient Substances 0.000 description 2
- 235000013369 micronutrients Nutrition 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 229930192334 Auxin Natural products 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 102000003846 Carbonic anhydrases Human genes 0.000 description 1
- 108090000209 Carbonic anhydrases Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- 244000025221 Humulus lupulus Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 239000002363 auxin Substances 0.000 description 1
- ZVCNBVJYXBEKTC-UHFFFAOYSA-L azanium;zinc;phosphate Chemical class [NH4+].[Zn+2].[O-]P([O-])([O-])=O ZVCNBVJYXBEKTC-UHFFFAOYSA-L 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003324 growth hormone secretagogue Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 231100000001 growth retardation Toxicity 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
Vynález sa .týku sposobu výroby kvapalnéhoi zinočnatého' koncentrátu z kyslých roztokov síranov, a/alebo dusičnanov a/alebo chloridoví zinočnatých.The invention relates to a process for the production of a liquid zinc concentrate from acidic solutions of sulphates, and / or nitrates and / or zinc chloride.
Zinok je jednou z tých důležitých mikroživín, ktoré prispievajú k harmonickému vývinu rastlín. Zúčastňuje sa. enzymatických procesov riadiacich metabolickú aktivitu v rastlinách a podporuje tvorbu rastových stim-ulátorov — auxínov.Zinc is one of those important micronutrients that contribute to the harmonious development of plants. Participating. enzymatic processes controlling metabolic activity in plants and promoting the formation of growth stimulators - auxins.
Zinok významné ovplyvňuje oxldačné procesy, transformáciu aminokyselin, spotřebu cukru a osikový metabolismus dusíka. Je podstatnou zložkou enzýmu karboanhydrázy, ktorá katalyzuje vratnú reakciu ^co^co^^o.Zinc significantly affects oxidation processes, amino acid transformation, sugar consumption and aspen nitrogen metabolism. It is an essential constituent of the carbonic anhydrase enzyme that catalyzes the reversible reaction.
Pvc výživu rastlín má velký význam synergický příjem fosforu (vo vorme ortofosfor ečnanov a. kondenzovaných fosforečmanov) za přítomnosti zinku. Resorbovateínosť (příjem) zinku je v značnéj miere funkciou půdně j reakcie. Na neutrálnych a alkalických půdách může důjsť k jeho retrogradácíi v důsledku vzniku fosforečmanov zinočnato-amónmych a zinočnatamov.Pvc plant nutrition is of great importance for the synergistic uptake of phosphorus (in the form of orthophosphates and condensed phosphates) in the presence of zinc. The resorbability of zinc is to a large extent a function of the soil reaction. On neutral and alkaline soils, it can be retrograded due to the formation of zinc-ammonium phosphates and zincnatamates.
Vzhladom k tomu, že dusičnany zvyšujú kyslosť půdy, je společná aplikácia zinku s dusíkatými hnojivami zvlášť výhodná najma z hfadiska jeho účinnosti. Výhodou zinku je, že sa zo systému nevyluhuje a pri jeho predávkovaní sa nepozorujú příznaky fytotoxicity.Since nitrates increase the acidity of the soil, the co-application of zinc with nitrogen fertilizers is particularly advantageous, particularly in terms of its effectiveness. The advantage of zinc is that it is not leached from the system and no symptoms of phytotoxicity are observed in its overdose.
Typickým vizuálnym symptómom nedostatku zinku je chloróza sprevádzaná spomalením rastu a žhnutím listov. V důsledku nedostatku zinku dochádza k zníženiu tvorby triptofánu (medziproduktu kyseliny beta-indolyloctovej) a v konečnom důsledku může dochádzať k rozkladu rastových stimulátorov a k zabrzdeniu tvorby organických kyselin a, glycidov.A typical visual symptom of zinc deficiency is chlorosis accompanied by growth retardation and leaf glowing. Due to the lack of zinc, the formation of triptophan (an intermediate of beta-indolylacetic acid) is reduced and ultimately decomposition of growth promoters and inhibition of the formation of organic acids and carbohydrates can occur.
Na zinok sú citlivé predovšetkým. tieto kultury: kukurica, fazula, chmel', vinič, sója, jabloně, čerešne, broskyne a pod. Na vyrovnáváme porúch vyvolaných ďeficienciou zinku sa odporúča aplikovat síran zinočnatý, chlorid zinečnatý, kysličník zinečnatý alebo uhličitan zinočnatý vo formě tuhej alebo' vo formo roztokov a suspenzií.They are particularly sensitive to zinc. the following cultures: maize, beans, hops, vine, soybeans, apples, cherries, peaches and the like. It is recommended to apply zinc sulphate, zinc chloride, zinc oxide or zinc carbonate in solid or in the form of solutions and suspensions to compensate for zinc deficiency disorders.
Z aspektu rýchlejšieho příjmu je zvlášť výhodná aplikácia kvapalných prípravkov na list, pričom je dokázatetné, že chelátové formy mikroživín sú pri foliárnej aplikácii’ asi 2,5-násobne rýchlejšie rastlinami přijímané než iónové formy solí.From the aspect of faster uptake, it is particularly advantageous to apply the liquid formulations to the leaf, and it has been shown that chelate forms of micronutrients are fed by plants approximately 2.5 times faster than ionic salt forms.
Ako chelátotvorné činidlá sa používajú predovšetkým syntetické chelátotvorné látky EDTA (sodná sof kyseliny etyléndiamínotetraoctovej) DTPA (sodná sof kyseliny dietyléntriamínopentaoctovejj, NTA (sof kyseliny nitriloitrioctovej), kondenzované fosforečnany, soli kyseliny citrónovej a i.The chelating agents used are in particular synthetic chelating agents EDTA (sodium salt of ethylenediaminotetraacetic acid) DTPA (sodium salt of diethylenetriaminopentaacetic acid), NTA (salt of nitriloitriacetic acid), condensed phosphates, salts of citric acid and others.
Z prírodných chelátotvorných látok sú významné lignosulfónany, polyflavonoidy a humáty.Of the natural chelating agents, lignosulfonates, polyflavonoids and humates are important.
Nosiče stopových prvkov s chelátotvornými vlastnosťami tvoria různé stabilně komplexně zlúčeminy. Sekvestračný (maskovací] účinok komplexu alebo' chelátu sa prejavuje pri aplikácii do půdy, pri ktorej no'sič zabraňuje retrogradácíi stopového prvku. Pri spoločnej aplikácii komplexnej formy stopového prvku s kvapalnými, predovšetkým s dusíkato-foeforečnými hnojivami inhibuje vznik nerozpustných zlúčenín.The trace element carriers with chelating properties form various stable complexes. The sequestering (masking) effect of the complex or chelate is manifested when applied to the soil, in which the carrier prevents the trace element from retrograding, and inhibits the formation of insoluble compounds when combined with the complex form of the trace element with liquid, in particular nitrogen-phosphorous fertilizers.
Postupy přípravy listových hnojív obsahujúcich zinok a přípravy kvapalných zinočniatých koncentrátov sú uvádzané v US pat. 4 025 330 (1974); US pat. č. 4 211 348 (1980); brit. pat. 1 364 464; brit. pat. číslo 1 094 781 a pod.Methods for preparing zinc-containing foliar fertilizers and preparing liquid zinc concentrates are disclosed in US Pat. 4,025,330 (1974); US Pat. no. 4,211,348 (1980); brit. pat. 1,364,464; brit. pat. No. 1 094 781 and the like.
Teraz sa zistilo, že kvapalný zinočnatý koncentrát z kyslých roztokov síranov a/alebo dusičnanov a/alebo chloridov zincčnatých je možno pripraviť spůsobom podía vynálezu, ktorého podstata spočívá v tom., že každých 100 hmotnostných dielov kyslého roztoku dusičnanu a/alebo síranu a/alebo chloridu zinočnatého, obsahujúceho volné minerálně kyseliny v množstvo zodpovedajúcom obsahu 0,01 až 2,0 hmotnostných dielov, s výhodou 0,2 až 1,2 hmotnostných dielov vodíkových iónov, sa nechá reagovat s 0,3 až 124 hmotnostnými dielmi, s výhodou s 5 až 75 hmotnostnými dielmi kysličníka a/alebo hydroxidu a/alebo uhličitanu zinočnatého a/alebo kovového' zinku, pričom kedykoívek v priebehu reakcie vodonerozpustných zdrojov zinku s přítomnými minerálnymi kyselinami alebo- po: ukončení ich reakcie s nimi, nechá reakčná zmes dalej reagovat s 0,5 až 525 hmotnostnými dielmi, s výhodou s 19 až 200 hmotnostnými dielmi kyseliny citróno'vej a pH reakčnej zmesi sa upraví hydroxid-mi a/alebo- uhličitanmi alkalických kovov aíalebo čpavkovou vodou a/alebo plynným a/alebo kvapalným amoniakom a/alebo uhličitá,nom .a/alebo karbarinamom amonným na hodnotu 5,5 až 9,0, s výhodou, -na hodnotu 6,0 až 8,0.It has now been found that liquid zinc concentrate from acidic solutions of sulphates and / or nitrates and / or zinc chlorides can be prepared by the method according to the invention, characterized in that every 100 parts by weight of an acidic nitrate and / or sulphate solution and / or zinc chloride containing free mineral acids in an amount corresponding to 0.01 to 2.0 parts by weight, preferably 0.2 to 1.2 parts by weight of hydrogen ions, is reacted with 0.3 to 124 parts by weight, preferably 5 to 75 parts by weight of zinc oxide and / or zinc hydroxide and / or carbonate, and at any time during the reaction of the water-insoluble zinc sources with the mineral acids present, or after their reaction therewith, the reaction mixture is allowed to react with 0.5 to 525 parts by weight, preferably 19 to 200 parts by weight of citric acid; The pH of the reaction mixture is adjusted to a value of 5.5 to 9.0 with alkali metal hydroxides and / or carbonates and / or ammonia water and / or gaseous and / or liquid ammonia and / or carbon dioxide, nom. preferably to a value of 6.0 to 8.0.
Hlavnou výhodou spůsobu podía vynálezu je, že umožňuje zvýšit obsah zinku v kyslých roztokoch síranov, dusičnanov a chloridov zinočnatých.The main advantage of the process according to the invention is that it makes it possible to increase the zinc content in acidic solutions of zinc sulphates, nitrates and chlorides.
Ďalšou výhodou spůsobu podía vynálezu je, že umožňuje využit a Zhodnotit zriedené roztoky dusičnanov a/alebo síranov a/alebo chloridov zinočnatých, ktoré vznikajú ako druhotná surovina například v polygrafickom priemysle pri rýchloleptaní zinkových štočkov pre reprodukčnú tlačovú techniku alebo pri moření zinkových plechov a pod., umožňuje zo zriedených roztokov obsahujúcich zinok pripraviť kvapalné zinočnaté koncentráty o relativné vyso-kom obsahu zinku VO' formo organo-metalokomplexov na báze citrónovej kyseliny, s vlastnosťami chelátov. Kvapalný zinočnatý koncentrát připravený spůsobom podía vynálezu je mie234987 šatelný nielen s bežne vyrábanými typmi kvapalných dusíkatých hmojív, ale aj s kvapalnými dusíkato-fosforečnými hnojivami or.tofosforečnamového typu (napr. 8-24-0; suspenzným hnojivom 10-30-0 a pod.] a polyfosforečnanového typu (10-34-0; 11-37-0 a pod.), ako aj s1 kvapalnými PK hnojivami (0-20-24) a důležitou skutočnosťou je fakt, že cítrátová forma je biologicky plné odbúratelná.A further advantage of the method according to the invention is that it makes it possible to utilize and evaluate dilute solutions of nitrates and / or sulphates and / or zinc chlorides which are produced as secondary raw materials, for example in the printing industry during rapid etching of zinc plates for reproduction printing techniques or zinc sheet pickling. , makes it possible to prepare liquid zinc concentrates having a relatively high zinc content V0 'formo of citric acid-based organo-metal complexes with chelating properties from dilute zinc-containing solutions. The liquid zinc concentrate prepared by the process of the present invention is compatible not only with commonly manufactured types of liquid nitrogen fertilizers, but also with liquid phosphorus or phosphorus-phosphate fertilizers (e.g., 8-24-0; suspension fertilizer 10-30-0 and the like). ] and polyphosphate type (10-34-0; 11-37-0 and the like) as well as 1 liquid PK fertilizer (0-20-24) and the important fact is that the citrate form is biodegradable.
Nespornou přednostou spósobu podía vynálezu je, že představuje prakticky bezodpadová technológiu, pri ktorej inie je potřebná separáciu tuhej fázy a pri ktorej nevznifcajú ďalšie odpady.An indisputable advantage of the process according to the invention is that it is a practically waste-free technology, in which the solid phase separation is otherwise required and in which no other waste is ignited.
Dalej uvedené příklady objasňujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the invention.
Příklad 1Example 1
Do skloněného kotlíka opatřeného miešadlom·, teplomerom a spatným chladičom sa předložilo· 100 hmotnostných dielov kyslého· roztoku dusičnanu zinočnatého, ktorý odpadá pri leptaní zinkových štočkov pre reprodukčnú tlačovú techniku, s obsahom 3,36 hmotnostných % Zn a 0,736 hmotnostných % H+. Za stálého miešania pri teplote 80 °C sa přidalo 3,04 hmotnostných· dielov· technického· ZnO obsahujúceho 78,44 % Zn. Teplota reakčinej zmesi sa udržiavala na 80° Celsia po dobu 2 hodin. Po skončení reakcie ZnO s kyslým roztokom Zn(NO3)2 sa takto získaná reakčná zmes· nechala ďalej reagovat s 18,67 hmotnostnými dielmi krystalické j 99 %-nej kyseliny citrónovej a pH reakčnej zmesi sa upravilo na hodnotu 6,9 neutralizáciou s 31,69 hmotnostnými dielmi čpavkovej vody· o koncentrácii 21,93 % NH3.In an inclined cauldron equipped with a stirrer, a thermometer and a reflux condenser, 100 parts by weight of an acidic solution of zinc nitrate, which is omitted when etching zinc plates for reproduction printing, containing 3.36% by weight of Zn and 0.736% by weight of H + were submitted. While stirring at 80 ° C, 3.04 parts by weight of technical ZnO containing 78.44% Zn were added. The temperature of the reaction mixture was maintained at 80 ° C for 2 hours. Upon completion of the reaction of ZnO with an acidic solution of Zn (NO3) 2, the reaction mixture thus obtained was reacted further with 18.67 parts by weight of crystalline 99% citric acid and the pH of the reaction mixture was adjusted to 6.9 by neutralization with 31%. 69 parts by weight of ammonia water at a concentration of 21.93% NH3.
Získal sa roztok s malým podielom nerozpustného zvyšku (< 0,5 % j o tejto specifikách:A solution with a small amount of insoluble residue (<0.5%) having the following specificities was obtained:
předpokládaný obsah Zn: 3,63 % skutočný obsah Zn 3,50 % výťažok: 96,10 % pH 6,9 měrná hmotoosť: 1148,8 kg . m~3 expected Zn content: 3.63% actual Zn content 3.50% yield: 96.10% pH 6.9 specific gravity: 1148.8 kg. m ~ 3
Příklad 2Example 2
Obdobné ako· v příklade 1 sa do reaktora předložila zmes pozostávajúca z 39,93 hmotnostných dielov roztoku odpadajúceho pri leptaní zinkových štočkov o specifikách ako v příklade 1 a z 60,07 hmotnostných dielov HNO3 o koncentrácii 66,17 %. 100 hmotnostných dielov tejto zmesi ohsahujúcej 0,66515 hmotnostných dielov H+ sa nechalo reagovat s 27,5 hmotnostnými dielmi technického ZnO (78,44 ,%. Zn), pričom· sa· zmes uvolněným reakčným teplom vyhriala na teplotu °C. Po· 1 hodinovom miešaní sa zmes nechala reagovat so 74,4 hmotnostnými dielmi %-nej kryštalickej kyseliny citrónovej a ipH výslednej reakčnej zmesi sa upravilo na hodnotu 6,5 neutralizáciou s 97,35 hmotnostnými dielmi NHiOH o koncentrácii 28,45 % NH3.Similar to Example 1, a blend consisting of 39.93 parts by weight of the solution resulting from the etching of zinc plates having the specificities of Example 1 and 60.07 parts by weight of HNO3 at a concentration of 66.17% was introduced into the reactor. 100 parts by weight of this mixture, containing 0.66515 parts by weight of H + , were reacted with 27.5 parts by weight of technical ZnO (78.44% Zn), and the mixture was heated to ° C by the reaction heat released. · After 1 h stirring, the mixture was allowed to react with 74.4 parts by weight of crystalline% strength citric acid and IPH resulting reaction mixture was adjusted to 6.5 by neutralizing with 97.35 parts by weight of NHiOH a concentration of 28.45% NH third
Získal sa produkt o tejto specifikách:A product with the following specifications was obtained:
předpokládány obsah Zn: 6,61 % skutečný obsah Zn: 7,52 % výťažok: 93,17 % pH: 6,5 měrná hmotnost pri 20 ~‘C: 1268,7 kg . m~3 assumed Zn content: 6.61% actual Zn content: 7.52% yield: 93.17% pH: 6.5 density at 20 ° C: 1268.7 kg. m ~ 3
Příklad 3Example 3
100 hmotnostných· dielov. kyslého roztoku síranu zinočnatého, ktorý obsahoval 3,5 % Zn a 10,5 % voínej kyseliny sírovej, čo· zodpovedalo obsahu 0,21582 hmotnostných dielov· H+ sa za intenzívneho miešania nechalo reagovař s 8,92 hmotnostnými dielmi technického· ZnO (78,44 % Znj. Po 30 minútovém miešaní reakčnej zmesi sa zadávkovalo 34,1 hmotnostných dielov 99 %-nej kyseliny citrónovej a pH reakčnej zmesi sa upravilo na hodnotu 7,1 až 7,5 neutralizáciou so 44,12 hmotnostnými dielmi čpavkovej vody o koncentrácii 28,46 % NH3.100 parts by weight. an acidic solution of zinc sulphate containing 3.5% Zn and 10.5% free sulfuric acid, corresponding to a content of 0.21582 parts by weight · H + , was reacted with vigorous stirring with 8.92 parts by weight of technical · ZnO (78 After stirring the reaction mixture for 30 minutes, 34.1 parts by weight of 99% citric acid were charged and the pH of the reaction mixture was adjusted to pH 7.1 to 7.5 by neutralization with 44.12 parts by weight of ammonia water at a concentration of 44% by weight. 28.46% NH 3.
Získal sa roztok o· tejto špecifikácii:A solution having the following specification was obtained:
předpokládaný obsah Zn: 6,61 % skutočný' obsah Zn: 5,40 % výťažok: 96,26 % pH: 7,1 měrná hmotnost pri 20 °C: 1233,0 kg . nm3 assumed Zn content: 6.61% actual Zn content: 5.40% yield: 96.26% pH: 7.1 density at 20 ° C: 1233.0 kg. nm 3
PřikladlEXAMPLE
Do zariadenia ako v příklade 1 sa předložilo· 86,88 hmotnostných dielov kyslého roztoku dusičnanu zinočnatého, ktorý odpadá pri leptaní zinkových štočkov používaných pre reprodukčnú tlačovú techniku, obsahujúceho· 3,82 % Zn [9,50 % Zn(NO3)2] a 4,98 % HNO3, ku -ktorému sa přidalo 13,12 hmotnostných dielov H2SG4 o koncentrácii 97,9 %. Takto připravených 100 hmotnostných dielov kyslej zmesi, ohsahujúcej 2,85 % Zn (hmotnostných dielov Zn) a 0,3332 hmotnostných dielov H+ sa za neustálého miešania nechalo reagovat s 13,78 hmotnostnými dielmi technického ZnO (78,44 % Znj po· dobu 1 hodiny, pričom sa uvolněným zriedovacím a reakčným teplom vyhriala reakčná zmes na teplotu cca 70 °C. V priebehu reakcie (asi po 30 minútach) sa postupné zadávkovalo 44,35 hmotnostných dielov· 99 %-nej kryštalickej kyseliny citrónovej a po· jej zadávkovaní sa pH výslednej zmesi upravilo reakciou s 75,61 hmotnostnými dielmi čpavkovej vody o· koncentrácii 21,93 % NH3 na hodnotu 6,6.A device as in Example 1 was fed with 86.88 parts by weight of an acidic zinc nitrate solution which is omitted when etching zinc printing plates used for reproduction printing, containing · 3.82% Zn [9.50% Zn (NO3) 2] and 4.98% HNO3, to which 13.12 parts by weight of H2SG4 at a concentration of 97.9% was added. The thus prepared 100 parts by weight of an acidic mixture containing 2.85% Zn (parts by weight of Zn) and 0.3332 parts by weight of H + was reacted with 13.78 parts by weight of technical ZnO (78.44% Znj) with stirring. The reaction mixture was heated to about 70 [deg.] C. during the reaction (after about 30 minutes), and 44.35 parts by weight of > the pH of the resulting mixture was adjusted to 6.6 with 75.61 parts by weight of ammonia water at a concentration of 21.93% NH 3.
Získaný produkt mal túto špecifikáciu:The product obtained had the following specification:
předpokládaný obsah Zn: 5,84 % skutočný obsah Zn: 5,64 % výťažok: 96,57 % pH: 6,6estimated Zn content: 5.84% actual Zn content: 5.64% yield: 96.57% pH: 6.6
Příklad 5Example 5
Do- zariadenia ako v příklade 1 sa předložilo 33,76 % hmotnostných dielov, kyslého roztoku Zn(NO3)2 o specifikách ako je uvedené v příklade 4, ku kterému sa přidalo 66,24 hmotnostných dielov HC1 o koncentrácii 32,2 %. Takto připravených 100 hmotnostných dielov kyslej zmesi obsahujúcej 1,12 hmotnostných dielov Zn, 1,688 hmotnostných dielov HNO3, 21,34 hmotnostných dielov HC1 a 0,617 hmotnostných dielov H+ sa za neustálého miešania nechalo· reagovat s 2,5,51 hmotnostnými dielmi technického ZnO (78,44 °/o Znj a asi po 2 hodlnovom33.76 parts by weight of an acidic solution of Zn (NO3) 2 having the specificities of Example 4 were added to the apparatus as in Example 1, to which 66.24 parts by weight of 32.2% HCl were added. The thus prepared 100 parts by weight of an acidic mixture containing 1.12 parts by weight of Zn, 1.688 parts by weight of HNO3, 21.34 parts by weight of HCl and 0.617 parts by weight of H + were reacted with 2.5.51 parts by weight of technical ZnO (with stirring). 78.44 ° / o Znj and after about 2 hours
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS403382A CS234967B1 (en) | 1982-06-01 | 1982-06-01 | Method of liquid zinc concentrate preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS403382A CS234967B1 (en) | 1982-06-01 | 1982-06-01 | Method of liquid zinc concentrate preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS234967B1 true CS234967B1 (en) | 1985-04-16 |
Family
ID=5382111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS403382A CS234967B1 (en) | 1982-06-01 | 1982-06-01 | Method of liquid zinc concentrate preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS234967B1 (en) |
-
1982
- 1982-06-01 CS CS403382A patent/CS234967B1/en unknown
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