CS208987B1 - Inhibition method of corrosive effects of nitrogen liquid fertilizers - Google Patents
Inhibition method of corrosive effects of nitrogen liquid fertilizers Download PDFInfo
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- CS208987B1 CS208987B1 CS494979A CS494979A CS208987B1 CS 208987 B1 CS208987 B1 CS 208987B1 CS 494979 A CS494979 A CS 494979A CS 494979 A CS494979 A CS 494979A CS 208987 B1 CS208987 B1 CS 208987B1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 82
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 41
- 239000003337 fertilizer Substances 0.000 title claims description 30
- 239000007788 liquid Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 9
- 230000000694 effects Effects 0.000 title claims description 4
- 230000005764 inhibitory process Effects 0.000 title 1
- 238000005260 corrosion Methods 0.000 claims description 56
- 230000007797 corrosion Effects 0.000 claims description 56
- 239000003112 inhibitor Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 15
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 229920005610 lignin Polymers 0.000 claims description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 7
- 229910001369 Brass Inorganic materials 0.000 claims description 6
- 239000010951 brass Substances 0.000 claims description 6
- -1 ferric Chemical compound 0.000 claims description 6
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010962 carbon steel Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 239000011573 trace mineral Substances 0.000 claims description 3
- 235000013619 trace mineral Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 235000015097 nutrients Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 2
- 239000011572 manganese Substances 0.000 claims 2
- 150000001868 cobalt Chemical class 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- 235000012907 honey Nutrition 0.000 claims 1
- CBEVANLIGJVSHZ-UHFFFAOYSA-N n,n'-diheptyl-n,n'-dimethylbutanediamide Chemical compound CCCCCCCN(C)C(=O)CCC(=O)N(C)CCCCCCC CBEVANLIGJVSHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 16
- 239000003637 basic solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004035 construction material Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 208000010201 Exanthema Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical class O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Fertilizers (AREA)
Description
Vynález sa týká spósobu inhibície koróznej; agresivity dusíkatých kvapalných hnojiv voči kovovým konštrukčným materiálom.The invention relates to a method of inhibiting corrosion; aggressiveness of nitrogenous liquid fertilizers to metallic construction materials.
Jedným z vážných problémov výroby apoužívania dusíkatých, najma beztlakových kvapalných hnojiv je otázka korózie výrobného, skladovacieho, dopravného a aplikačného zariadenia.One of the serious problems of the production and use of nitrogenous, especially non-pressurized liquid fertilizers is the issue of corrosion of production, storage, transport and application equipment.
V odbomej a patentovej literatúre sa publikovalo vela práč zameraných na štúdium koróznej ί odolnosti róznych konštrukčných materiálov v prostředí vodných roztokov obsahujúcich močovinu a dusičnan amónny s celkovým obsahom 28 až i 32 % dusíka (Hatfield a spol.: Agrič. and Food | Chemistry, 6,524 (1968), Grow G. L. a spol.: Fert. Solns., 12, (1) 8 (1968), Achom A. P. a spol.: Fert. > Solns., 20, (3), 34 (1976), Wyma Β. H. a spol.: Chem. Eng. Progr., 60, 3 (1964), Bank W. P.: Materials Protection (March) 35 (1968). Pri teplote okolia a správné nastavenom pH tieto roztoky neposobia korozívne na váčšinu hliníkových zliatin, na nehrdzavejúce ocele, ako aj na váčšinu dnes používaných plastických hmót (PVC, PE, PP, • sklolamináty a podobné).Many papers have been published in the specialist and patent literature to study the corrosion resistance of various construction materials in aqueous solutions containing urea and ammonium nitrate with a total nitrogen content of 28 to 32% (Hatfield et al., Agr. And Food | Chemistry, 6,524). (1968), Grow GL et al .: Fert. Solns., 12, (1) 8 (1968), Achom AP et al .: Fert.> Solns., 20, (3), 34 (1976), Wyma ma H., et al., Chem Eng., Progr., 60, 3 (1964), Bank WP: Materials Protection (March) 35 (1968), at ambient temperature and at the correct pH setting, these solutions do not corrosive to most aluminum alloys, for stainless steels as well as for most of the plastics used today (PVC, PE, PP, • fiberglass and the like).
Naproti tomu vykazujú značnú korozívnosť voči i uhlíkatým oceliam a farebným kovom, najma ak ί neobsahujú niektorý z inhibítorov korózie a ak : hodnota ich pH je menšia ako 7 (Achom a spol.:On the other hand, they show considerable corrosion to even carbon steels and non-ferrous metals, in particular if they do not contain any of the corrosion inhibitors and if: their pH is less than 7 (Achom et al .:
; Fert. Solns., 20, 52 (1976) a 20 (3) 84 (1976), ' 208987 ; Fert. Solns., 20, 52 (1976) and 20 (3) 84 (1976), '208987
Klevke V. A. a spol.: Židkije azotnije udobrenija, Izd. Chimija, Moskva (1973).Klevke, V.A. et al., Jewish Azotnium Udobrenija, Izd. Khimiya, Moscow (1973).
Z toho vyplývá, že použitie kvapalných beztlakových dusíkatých hnojiv na báze močoviny a dusičnanu amonného bez patričnej úpravy, zameranej na zníženie ich koróznej agresivity voči Uvedeným kovovým materiálom by narážalo na ťažkosti najma v polovýrobnom procese (skladovanie, ma- I nipulácia, aplikácia).It follows that the use of liquid, non-pressurized nitrogen fertilizers based on urea and ammonium nitrate without proper treatment aimed at reducing their corrosive aggressiveness towards said metallic materials would encounter difficulties, particularly in the semi-manufacturing process (storage, handling, application).
Riešenie tohoto problému je v zásadě možné niekolkými spósobmi: přísadou inhibítorov koró- ; zie priamo v procese výroby kvapalného hnojivá, vhodnou povrchovou úpravou konštrukčného ma- ; teriálu, ktorý je v styku s kvapalným hnojivom,! použitím takých konštrukčných materiálov, ktoré i sú v danom prostředí proti korózii odolné, elektro- j chemickou, spravidla tzv. anodickou ochranou, j vhodnou na stabilně skladové zásobníky, vhodnou kombináciou spomenutých metod.The solution of this problem is basically possible in several ways: by the addition of corrosion inhibitors; can be directly in the process of liquid fertilizer production, by suitable surface treatment of the construction material; in contact with liquid fertilizer,! using such construction materials, which in the given environment are also resistant to corrosion, electro-chemical, anodic protection, suitable for stable storage containers, by a suitable combination of the aforementioned methods.
V súčasnej praxi sa používajú prevážne prvé tri spósoby protikoróznej ochrany konštrukčných materiálov. Sudbury á spol.: Materials Protection, 4, (6) 81 (1965) odporúčajú anodická ochranu uhlíkatých ocelí voči koróznemu pósobeniu róznych typov kvapalných dusíkatých hnojiv.In the current practice, mainly the first three methods of corrosion protection of construction materials are used. Sudbury et al., Materials Protection, 4, (6) 81 (1965) recommend the anodic protection of carbon steels against the corrosion of various types of liquid nitrogen fertilizers.
Pridavok inhibítorov korózie priamo pri výrobě kvapalných hnojiv je pre svoju jednoduchosť, vysokú účinnosť, prevádzkovú istotu, ako aj kom208987 píexnošť riešenia a v mnohých prípadooh i pre 1 svoju efektivnost' z hladiska ekonomiky, jednou z najprogresívnejších metod protikoróznej ochrany uhlíkatých ocelí v prostředí kvapalných, beztlakových dusíkatých hnojív na báze močoviny a du- : sičnanu amónneho. Ako inhibitory korózie do tohto typu kvapalných hnojív sa popři látkách organickej povahy odporúča rad anorganických látok. Z nich sa najčastejšie udává použitie amoniaku, tiokyanatanu draselného a amónneho, símika sodného, hexametafosforečnanov, dusitanov, boritanov ako aj chrómanov, dvojchrómanov, j arzeničnanov, arzenitov a iných (Achom a spol.: ! pert. solns., 20 (3), 34 (1976), Klevke a spol.: j Židkije azotnije udobrenija, Izd. Chimija, Moskva ' (1973), Sudbury J. D. a spol.: Materials Protection, ( 4, (6), 81 (1965). 'The addition of corrosion inhibitors directly in the production of liquid fertilizers is one of the most progressive methods of corrosion protection of carbon steels in liquid, non-pressurized environments due to its simplicity, high efficiency, operational reliability as well as its many solutions and in many cases for its efficiency. nitrogenous fertilizers based on urea and ammonium nitrate. A number of inorganic substances are recommended as corrosion inhibitors in this type of liquid fertilizer in addition to organic substances. Of these, the use of ammonia, potassium and ammonium thiocyanate, sodium silicon, hexametaphosphates, nitrites, borates as well as chromates, dichromates, arsenates, arsenites and others is most commonly reported (Achom et al .:! Pert. Solns., 20 (3), 34 (1976), Klevke et al., J Jewkije azotnije udobrenija, Izd. Khimija, Moscow (1973), Sudbury JD et al .: Materials Protection, (4, (6), 81 (1965)).
Jedným z jednoduchých spósobov zníženia koróznej agresivity kvapalných dusíkatých hnojív, v dnešnej praxi dosť zaužívaným, je úprava finálneho hnojivá amoniakom. Přidává sa v takom množstve, aby pH upraveného roztokubolo 7 až 7,5.One of the simple ways to reduce the corrosive aggressiveness of liquid nitrogen fertilizers, quite common in today's practice, is to treat the final fertilizer with ammonia. It is added in an amount such that the pH of the treated solution is 7 to 7.5.
Podía údajov literatúry třeba pridať na úpravu j 1 tony kvapalných dusíkatých hnojív přibližnéAccording to the literature, approximately 1 tonne of liquid nitrogen fertilizer should be added for treatment
4,5 kg amoniaku.4.5 kg of ammonia.
Tento spósob inhibície koróznych účinkov dusí- ; katých kvapalných hnojív sa v mnohých prípadoch ί upřednostňuje pre svoju jednoduchosť a ekono- i mickú výhodnosť, má však určité nevýhody, například účinnosť protikoróznej ochrany uhlíkatých ocelí týmto spósobom je relativné nízká a vóbec nerieši ochranu farebných kovov a ich zliatin (Vojáček a spol.: Agrochémia 16, 349 (1976), takže sa odporúča používat ešte ďalšie inhibitory korózie. ίThis method of inhibiting the corrosive effects of nitrogen-; In many cases, liquid fertilizers are preferred for its simplicity and economic advantage, but it has some disadvantages, for example, the effectiveness of the corrosion protection of carbon steels in this way is relatively low and does not at all address the protection of non-ferrous metals and their alloys (Vojáček et al. Agrochemistry 16, 349 (1976), so it is recommended to use other corrosion inhibitors
Pri vyššom obsahu volného amoniaku (pH dusíkatého roztoku vyššie ako 8) sa dosahuje dobrá i protikorózna ochrana uhlíkatých ocelí, avšak zhoršujú sa podmienky hygieny práce a zvyšuje saj korózna agresivita hnojivá voči farebným kovom a ich zliatinám (meď, bronz, mosadz a podobné), ako i voči hliníku v dósledku tvorby vodorozpustných amokomplexov a hydroxyhlinitanov. Korózna ochrana uhlíkatých ocelí sa znižuje v dósledku postupného poklesu obsahu amoniaku v produkte, zapríčinenom manipuláciou, změnami teploty a dlhodobým skladováním, čo má za následok nie celkom zanedbatelné straty dusíka, pričom sa zhoršujú i podmienky z hladiska bezpečnosti práce (možnost vzniku výbušnej zmesi NH3-vzduch). i Obsah volného amoniaku ovplyvňuje kryoskopické vlastnosti produktu (vysolovaciu teplotu, šířku j metastabilnej oblasti). V záujme dodržaniapredpí- [ sáného obsahu volného amoniaku v hnojivé (maximálny obsah obvykle asi 0,1 % NH3) musí sa jeho prebytok v procese výroby často odstraňovat (například desorpciou, prevzdušňovaním, neutralizáciou a podobné).A higher content of free ammonia (pH of nitrogen solution higher than 8) achieves good and anticorrosive protection of carbon steels, but the conditions of work hygiene deteriorate and the corrosion aggressiveness of non-ferrous metals and their alloys (copper, bronze, brass and the like) increases. as well as against aluminum due to the formation of water-soluble amocomplexes and hydroxyaluminates. The corrosion protection of carbon steels decreases due to the gradual decrease of ammonia content in the product, caused by manipulation, temperature changes and long-term storage, resulting in not negligible nitrogen losses, while also deteriorating work safety conditions (potentially explosive NH 3 mixture ) -the air). The free ammonia content affects the cryoscopic properties of the product (salting-out temperature, width j of the metastable region). In order to maintain the prescribed content of free ammonia in the fertilizer (maximum content usually about 0.1% NH 3 ), its excess in the production process must often be removed (for example by desorption, aeration, neutralization and the like).
Vzhladom na spomenuté nevýhody a nedostatky rad významných světových výrobcov kvapalných dusíkatých hnojív v poslednom období ustupuje od používania amoniaku na inhíbíciukorózneho pósobenia týchto hnojív..In view of the above mentioned disadvantages and shortcomings of a number of major world producers of liquid nitrogen fertilizers, the use of ammonia for inhibiting the corrosion of these fertilizers has been decreasing recently.
V súčasnosti sa pri výrobě tohoto typu kvapalI ných dusíkatých hnojív stále viac uplatňujú ako i inhibitory korózie trihydrog|nfosforečná kyselina j a zmesi trihydrogénfosforečnej kyseliny s kondenI zovanými fosforečnými kyselinami typuAt present, trihydrogen phosphoric acid j and mixtures of trihydrogen phosphoric acid with condensed phosphoric acids of the type
Hn+2PnO3n+i vrátane ich solí, najmá amónnych (Teren J. a kol.: Agrochémia, 17,7,192-8 (1977), Teren J. a kol.: „Korózna odolnost konštrukčných materiálov v prostředí DAM-390“, AGRICHEM ’78, sekcia A — Výroba priemysebiých hnojív, 29. 6..1978)., - jH n + 2 P n O 3 n + i including their salts, especially ammonium salts (Teren J. et al .: Agrochemistry, 17,7,192-8 (1977), Teren J. et al .: “Corrosion resistance of structural materials in the environment DAM-390 ', AGRICHEM '78, Section A - Manufacture of fertilizers, June 29, 1978).
Ellam a kolektiv uvádzajú, že prídavkom tzv. „základného“ dusíkato-fosforečného roztoku, prij bližného zloženia 10-34-0, ku kvapalnémuhnojivu „UAN“ (u nás obdobný typ DAM-390) v množstve zodpovedajúcemu 0,2 % fosforečnanov amónnych sa dosiahné podstatné zníženie rýchlosti korózie uhlíkatých ocelí na hodnotu asi 0,025 mm za rok. ____________- —, 14 27/ 7Z Z Z)Ellam et al. Of the "basic" nitrogen-phosphorus solution, acceptance of the approximate composition 10-34-0, to the liquid fertilizer "UAN" (similar to us type DAM-390) in an amount corresponding to 0.2% ammonium phosphates, a significant reduction in the corrosion rate of carbon steel about 0.025 mm per year. ____________-, 14 27 / 7Z Z Z)
V poslednom období sa ako inhibitor korózie dusíkatých kvapalných hnojív obsahujúcich dusičnan amónny a močovinu odporúča používat prídavok 0,5 až 10 % sušiny sulfitového výluhu vo formě i 10 až 60%-ného roztoku (Černý J. — referát na konferencii „Využitie sulfitových výluhov v polnohospodárstve“ — České Budějovice, marec 1979).Recently it has been recommended to use an addition of 0.5 to 10% dry matter of sulphite liquor in the form of 10 to 60% solution as a corrosion inhibitor of nitrogenous liquid fertilizers containing ammonium nitrate and urea (Černý J. - paper at the conference "Utilization of sulphite liquors in agriculture ”- České Budějovice, March 1979).
Z uvedeného vidno, že vo vývoji inhibítorov korózie bol dosiahnutý celý rad pozoruhodných výsledkov a viaceré z uvádzaných inhibítorov sa už s úspechom využívajú aj v praxi. Vývoj sa čoraz viacej· orientuje na inhibitory, ktoré by popři požadovanej účinnostlna zníženie koróznej agresivity boli dostupné v potřebných množstvách, boli by ekonomicky výhodné a ktorých prídavok by , pozitivně ovplyvňoval agrochemická účinnost a fy- i zikálno-chemické vlastnosti dusíkatých kvapal- j ných hnojív.------------------—----------- J It can be seen from the above that a number of remarkable results have been achieved in the development of corrosion inhibitors, and many of these inhibitors have already been successfully used in practice. The development is increasingly oriented towards inhibitors which, in addition to the required effective reduction of corrosion aggressiveness, would be available in the necessary quantities, would be economically advantageous and whose addition would positively influence the agrochemical efficiency and physico-chemical properties of nitrogen liquid fertilizers. .------------------—----------- J
Teráz sa s překvapením zistilo, že velmi výhodný j spósob inhibície koróznej agresivity dusíkatých i _kvapalných hnojívjobsahujúcich dusičnan amónny alebo močovinu spočívá v podstatě v tom, že Jc dusíkatému kvapalnému hnojivu alebo k vodnému roztoku resp. tavenine dusičnanu amónneho alebo močoviny sa před aJebo kedykolvek v priebehu ich homogenizácie přidá jednotlivo j alebo v zmesi najmenej jedna z látok zo skupiny, ktorú tvoří volnákysehnaIignosulfSnová,Ámónna, draselná, horečnatá, železnatá, -železitá, meďnatá, j zinočnatá, manganatá a kobaltnatá sof lignosulfó- í novej kyseliny, produkt získaný oxidáciou sulfito- ί vých výpalkov alebosulfitových výluhov charakΓ terizovaný empirickým vzorcom, získaným prepoi čítáním obsahu uhlíka, vodíka, kyslíka, dušíka, . j síry, vápnika, sodíka, draslíka, chrómu a tiež ! obsahu stopových prvkov alebo prvkov sekundárných rastlinných živin obsiahnutých v 100 g produktu na gramatómy, pričom takto získaný výsledok sa vztiahne na fenylpropánovú jednotku ligninu obsahujúcu v molekule 9 atómov uhlíkaSurprisingly, it has now been found that a very advantageous method of inhibiting the corrosive aggressiveness of both nitrogenous and liquid fertilizers containing ammonium nitrate or urea consists essentially in that the nitrogenous liquid fertilizer or the aqueous solution or the aqueous solution, respectively. at least one of the group consisting of free-ionic sulphonic acid, ammonium, potassium, magnesium, ferrous, ferrous, copper, zinc, manganese, and cobalt is added individually or in a mixture before or at any time during their homogenization. lignosulphonic acid, the product obtained by oxidizing sulphite stillage or orosulphite leachates characterized by an empirical formula obtained by counting the carbon, hydrogen, oxygen, soul content. sulfur, calcium, sodium, potassium, chromium and so on ! the content of trace elements or secondary plant nutrient elements contained in 100 g of product per gramme, the result thus obtained being related to the phenylpropane unit of lignin containing in a molecule of 9 carbon atoms
3208987 ^9^10-1205-7^0,1.0,280,4.1 C^o ,01-0,4 I3208987 ^ 9 ^ 10-1205-7 ^ 0,1.0,280,4.1 C10,01,01,4 I
Na0j05.o,5Ko-0,2CI0-0,2^eo, 1-1 kde Me je hořčík alebo vápník alebo železo alebo meď alebo zinok alebo mangán alebo kobalt alebo molybdén alebo bór, pričom uvederié látky sa pridávajú v množstve 1.10'2 až 20 i hmotových dielov sušiny na každých ÍŮO hmotových dielov dusíkatého kvapalného hnojivá.In 0j 05.o, 5ko-0,2CI0-0,2 ^ e a, 1-1 wherein Me is magnesium or calcium, or iron or a copper or zinc, or manganese, or cobalt, or molybdenum and boron, wherein the peel agents are added in an amount 2 to 20 parts by weight of dry matter for each part by weight of nitrogen liquid fertilizer.
Popři inhibičnom pósobení má použitie vyššie uvedených derivátov ligninu podlá vynálezu tiež viaceré ďalšie výhody, z ktorých možno uviesť například: možnost vhodnej kombinácie inhibítorov koróznych účinkov dusíkatých kvapalnýeh hnojiv s ich obohatením sekundárnými alebo | stopovýmiprvkami, pričom tieto sú viazané ková- i lentnými alebo komplexnými vazbami; zlepšeme zmáčavosti listov a podstatné vyššia přilnavost hnojivá, ktoré sa dosahujú pri foliámej aplikácii dusíkatých kvapalnýeh hnojiv s prídavkom inhibítorov korózie podfa vynálezu; priaznivé ovplyvnenie tvorby humusu a aktivizácie činnosti pódnych mikroorgánizmov, ktoré sa dosahujú použitím prípravkov v zmysle vynálezu, čímsa vnášajú do pódy organické látky zlepšujúce jej štruktúru; zlepšeme fyzikálno-chemických vlastností dusíkatých kvapalnýeh hnojiv, ktoré sa dosahuje prídavkom prevažnej váčšiny inhibítorov korózii podfa vynálezu; systémový účinok biogénnych prvkov viazaných v komplexoch podfa vynálezu prevažne i vo formě kovalentných vazieb, dosiahnutý pri foliárnej aplikácii a ďalšie.In addition to the inhibitory effect, the use of the above-mentioned lignin derivatives according to the invention also has several other advantages, including: the possibility of appropriately combining the corrosion inhibitors of nitrogenous liquid fertilizers with their secondary enrichment; trace elements, which are bonded by covalent or complex bonds; improving the wettability of the leaves and the substantially higher adherence of the fertilizer obtained by foliar application of nitrogenous liquid fertilizers with the addition of the corrosion inhibitors of the invention; favorably affecting humus formation and activating the activity of the soil microorganisms, which are achieved by the use of the preparations according to the invention, thereby bringing to the soil organic substances improving its structure; improve the physicochemical properties of nitrogenous liquid fertilizers by adding the vast majority of the corrosion inhibitors of the invention; the systemic effect of the biogenic elements bound in the complexes of the invention, predominantly also in the form of covalent bonds, achieved by foliar application and others.
Ďalej uvedené příklady objasňujú avšak v žiadnom případe nijako neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the invention in any way.
Přikladl'EXAMPLE '
V laboratórnych podmienkach bolá v statických skúškach sledovaná účinnost’ inhibítorov korózie podfa vynálezu v prostředí základného dusíkatého roztoku pripravénom rozpúšťaním 43,38 % : NH4NO3 (98,8%-ného) a 32,47 % močoviny (99,06%-nej) voči uhlíkatej oceli ČSN triedy 11 amosadze.Under laboratory conditions, the efficacy of the corrosion inhibitors of the present invention in a basic nitrogen solution prepared by dissolution of 43.38%: NH4NO3 (98.8%) and 32.47% urea (99.06%) was investigated in static tests. carbon steel ČSN class 11 amosadze.
Po expozícii vzoriek uhlíkatej ocele v dusíkatom ; roztoku priememej teploty 40 °C, ktorého pH bolo | rovné 6,2, po dobu 374,4 hodin boli dosiahnuté tieto výsledkyAfter exposure to carbon steel samples in nitrogen; a solution having an average temperature of 40 ° C and having a pH of equal to 6.2, for 374.4 hours the following results were obtained
Vysvětlivky: V stípci „rýchlosť korózie“ záporné číselné údaje prezentujú koróžiu (úbytok hmotnosti exponovanej vzorky) a kladné údaje vyjadrujú pasiváciu resp. rýchlosť pasivácie — tvorby ochrannej vrstvy.Explanatory notes: In the "corrosion rate" column, negative numerical data represent corrosion (weight loss of the exposed sample) and positive data indicate passivation, resp. passivation rate - formation of protective layer.
Expozíciou vzoriek mosadze v dusíkatom rozto- ; 7,37 po dobu 365,3 hodin boli priebežným sledoku priememej teploty 40 °C, pH ktorého bolo váním hmotnosti vzoriek určené tieto rýchlosti prídavkom čpavkovej vody .upravené na hodnotu korózieExposure to brass samples in nitrogen mite; 7.37 for 365.3 hours were continuously monitored at an average temperature of 40 ° C, the pH of which was determined by the weight of the samples to determine these rates by addition of ammonia water adjusted to the corrosion value
Příklad 2Example 2
V laboratórnych statických skúškach sa sledovala korózna odolnosť kpnštrukčiiej uhlíkatej pcele i triedy i Ϊ v prostředí základného dusíkatého rozťo' ku, připraveného z dusičnanu amónneho a moéovi• ny, bez a s prídavkom inhibítorov· korózie v zmysle vynálezu. Používaný základný dusíkatý roztok mal pH 6,4 pričom jeho korózna agresivita voči konštrukčnej uhlíkatej ocelí bola porovnávaná s koróznou agresivitou dusíkatého roztoku obsahujúceho4,78 % sušiny horečnatého lignínového komplexu, ktorý obsahoval 4,7 % horčíka a 94,5 % sušiny. Priebeh korózie vzoriek exponovaných pri teplote 40 °C bol sledovaný vážením po dobu 368 hodin. Priememá plocha povrchu exponovaných vzoriek bola P = 30,1 cm2, pričom poměr objemu korózneho média k ploché vzoriek sa pohyboval v rozmedzí V/P = 8,8 až 9,8.In the laboratory static tests, the corrosion resistance to both the carbonaceous cell and the class I Ϊ in a basic nitrogen solution prepared from ammonium nitrate and mono-nitrate, without and with the addition of corrosion inhibitors according to the invention, was monitored. The basic nitrogen solution used had a pH of 6.4 and its corrosive aggressiveness towards structural carbon steels was compared to the corrosive aggressiveness of the nitrogen solution containing 4.78% dry matter of the magnesium lignin complex containing 4.7% magnesium and 94.5% dry matter. The corrosion behavior of the samples exposed at 40 ° C was monitored by weighing for 368 hours. The average surface area of the exposed samples was P = 30.1 cm 2 , with the ratio of the volume of the corrosive medium to the flat samples ranging from V / P = 8.8 to 9.8.
Prepočtom zmien hmotnosti vzoriek sa získali tieto údaje o rýchlosti ich korózie v sledovaných prostrediach:By recalculating the weight changes of the samples, the following data on the rate of corrosion in the monitored environments was obtained:
Rýchlosť korózie vK vUCorrosion rate vK vU
Špecifikácia korózneho prostredia Základný dusíkatý roztok bez přídavku inhibítora korózie pH na začiat. skúšky: 6,4 pH po 368 hod. expoz.: 7,1 —0,38 g. m-2. h-1 —0,42 mm . rok-1 Corrosive environment specification Nitrogen base solution without addition of pH corrosion inhibitor at the beginning. Tests: 6.4 pH after 368 hr. exposure: 7.1 —0.38 g. m -2 . h -1 - 0.42 mm. rok -1
Základný dusíkatý roztok s prídavkom 4,78 % sušiny Mg-LK ako inhibitor korózie pH na začiat. skúšky: 6,8 pH po 368 hod, expoz.: 6,5_—28,90 mg. m~2. h-1 -32,20 μπι. rok-1 Nitrogen stock solution with addition of 4.78% Mg-LK dry matter as pH corrosion inhibitor initially. Tests: 6.8 pH after 368 h, Exp .: 6.5 - 28.90 mg. m ~ 2 . h -1 -32,20 μπι. rok -1
Dosiahnuté výsledky jednoznačné svedčia o in- ověřovala účinnost voínej lignosulfónovej kyseliny hibičnej účinnosti ověřovaného horečnatého ligní- ' a tiež jej horečnatej soli na inhibinovanie koróznej i nového komplexu na koróžnu agresivitu dusíka- agresivity mosadze v prostředí základného dusíka| tých roztokov obsahujúcieh dusičnan amónny voči tého roztoku.The results obtained unequivocally indicate the efficacy of free lignosulfonic acid of the hibicic acid of the verified magnesium lignin as well as its magnesium salt to inhibit both the corrosive and the novel complex on the corrosive nitrogen aggressiveness of the brass in the basic nitrogen environment | solutions containing ammonium nitrate relative to that solution.
: konštrukčnej uhlíkatej oceli (rýchlosť korózie bola | Prepočtom zmien hmotnosti exponovaných vzoznížená o viac než desaťnásobok). ; riek sa získali tieto údaje o ich rýchlosti korózie v jednotlivých prostrediach:: structural carbon steel (corrosion rate was reduced by more than ten times by recalculating the weight changes exposed). ; The following data on their corrosion rates in individual environments were obtained:
Příklad 3Example 3
Za obdobných experimentálnych podmienok saUnder similar experimental conditions,
Ako možno vidieť z výsledkov uvedených v ta- zu podstatné znižujú rýchlosť korózie mosadze bulke, ověřované lignínové deriváty podía vynále- < v prostředí základného dusíkatého roztoku.As can be seen from the results presented in the above, the corrosion rate of brass bead bulks, the tested lignin derivatives according to the invention in a basic nitrogen solution environment, is substantially reduced.
Claims (7)
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| CS494979A CS208987B1 (en) | 1979-07-16 | 1979-07-16 | Inhibition method of corrosive effects of nitrogen liquid fertilizers |
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