CS259285B1

CS259285B1 - Process for the production of liquid nitrogen-sulfur fertilizers

Info

Publication number: CS259285B1
Application number: CS869826A
Authority: CS
Inventors: Milan Gabco; Jan Teren; Eduard Hutar; Boris Stec
Original assignee: Milan Gabco; Jan Teren; Eduard Hutar; Boris Stec
Priority date: 1986-12-23
Filing date: 1986-12-23
Publication date: 1988-10-14
Also published as: CS982686A1

Abstract

Riešenie sa týká sposobu výroby dusíkato-sírnych hnojiv na báze dusičnanu a síranu amonného, močoviny a vody. Spósob výroby spočívá v tom, že roztok síranu amónneho v kyselině sírovej pochádzajúci s výhodou z výroby metylmetakrylátov sa neutralizuje amoniakátom dusičnanu amonného. Před, počas, alebo po ukončení neutralizačnej reakcie sa přidává močovina a připadne tiež dusičnan amonný, síran amónny a amoniak.The solution relates to a method for producing nitrogen-sulfur fertilizers based on nitrate and ammonium sulfate, urea and water. The method of production consists in neutralizing a solution of ammonium sulfate in sulfuric acid, preferably originating from the production of methyl methacrylates, with ammonium nitrate ammonia. Before, during, or after the neutralization reaction, urea is added and, if necessary, ammonium nitrate, ammonium sulfate and ammonia.

Description

Vynález sa týká spósobu výroby kvapalných dusíkato-sírnych hnojiv na báze dusičňanu a síranu amonného, močoviny a vody.The invention relates to a method of producing liquid nitrogen-sulfur fertilizers based on ammonium nitrate and sulfate, urea and water.

Dusíkaté hnojivá, sú pre ekonomiku ČSSR významnou záťažou z energetického i devizového hladiska, pretože rozhodujúce suroviny pre ich výrobu dovážame. Z domácích zdrojov dusíkatých hnojiv je k dispozícii dostatok síranu amonného, ako vedlajšieho produktu predovšetkým z výroby kaprolaktamu, Napriek jeho vhodnosti pre niektoré plodiny, a to predovšetkým v predsejbovej príprave pody a na zásaditých pódach, je o síran amónny v polnohospodárskej praxi nižší záujem, ako je reálna ponuka. Jeho efektívnejšie využitie podmiňuje tiež celospolečensky požadovaný nárast výroby niektorých hlavných produktov (kaprolaktamu, železnatých pigmentov, metylmetakrylátov).Nitrogen fertilizers are a significant burden on the economy of the Czechoslovak Socialist Republic from an energy and foreign exchange perspective, because we import the crucial raw materials for their production. From domestic sources of nitrogen fertilizers, there is enough ammonium sulfate available as a by-product, primarily from the production of caprolactam. Despite its suitability for some crops, especially in pre-sowing soil preparation and on alkaline soils, there is less interest in ammonium sulfate in agricultural practice than there is real supply. Its more effective use is also conditioned by the socially desired increase in the production of some main products (caprolactam, iron pigments, methyl methacrylates).

Vzhladom na už uvedenú energetická náročnost výroby dusíkatých hnojiv má uplatnenie síranu amonného, ako vedlajšieho produktu, v polnohospodárstve mimoriadny význam. V celosvetovom meradle nachádza síran amónny ako hnojivo uplatnenie predovšetkým v tropických oblastiach Ázie, Afriky, Strednej a Južnej Ameriky. Vo vlhké) tropickej klíme je jeho významnou pred-Due to the already mentioned energy-intensive production of nitrogen fertilizers, the use of ammonium sulfate as a by-product in agriculture is of particular importance. On a global scale, ammonium sulfate is used as a fertilizer primarily in the tropical regions of Asia, Africa, Central and South America. In a humid tropical climate, its significant advantage is

% N %N T°C Temperature SADAM 260 SADAM 260 20,5 20.5 —23 —23 260 260 20,5 20.5 <-15 <-15 286 286 22,5 22.5 <—15 <—15 310 310 24,2 24.2 <—15 <—15

nosťou predovšetkým nízká hygroskopicita. Ďalšie široké uplatnenie nachádza v oblastiach s nedostatkom síry a pri pěstovaní plodin priaznivo reagujúcich na hnojenie sírou („Ammonium sulphate-past, present and future“, Nitrogen No. 141, January— —February 1983).Its main characteristic is its low hygroscopicity. It finds further wide application in areas with a lack of sulphur and in the cultivation of crops that respond favourably to sulphur fertilization ("Ammonium sulphate-past, present and future", Nitrogen No. 141, January— —February 1983).

Podmienkou úspěšného používania síranu amónneho v polnohospodárskej praxi i ČSSR je hladanie takých foriem a sposobov jeho využitia, ktoré minimalizujúi niéktoBé jeho negativné vlastnosti, predovšetkým relativné nižší obsah živin, menej vhodná aplikačnú formu (jemne krystalický’ produkt) a hlavně vysokú fyziologickú kyslosť, ktorá pri dlhodobom používaní síranu amónneho a nedostatočnom vápnění významné zhoršuje fyzlkálnochemické vlastnosti- půd.The condition for the successful use of ammonium sulfate in agricultural practice in the Czechoslovak Republic is to find forms and methods of its use that minimize some of its negative properties, especially the relatively lower nutrient content, the less suitable application form (finely crystalline product) and, most importantly, the high physiological acidity, which, with long-term use of ammonium sulfate and insufficient liming, significantly worsens the physicochemical properties of the soil.

Výrobně a aplikačně najvhodnejšími formami hnojiv sú kvapalné — roztokové a suspenzné hnojivá. Vhodnost formy eliminuje pri zapracovaní síranu amónneho do kvapalných hnojiv zníženie celkovej koncentrácie dusíka v produkte. V zahraničí je známa výroba rožtokových typov hnojiv na báze močoviny, dusičnanu amónneho a síranu amónneho. Z mnohých možností uvádzame následovně typy:The most suitable forms of fertilizers for production and application are liquid — solution and suspension fertilizers. The suitability of the form eliminates the reduction of the total nitrogen concentration in the product when incorporating ammonium sulfate into liquid fertilizers. Abroad, the production of liquid types of fertilizers based on urea, ammonium nitrate and ammonium sulfate is known. Of the many options, we list the following types:

% Močoviny % NH1NO3 % (NHs)zSOj% Urea % NH1NO3 % (NHs)zSOj

25,7 25.7 10,0 10.0 23,9 23.9 23,2 23.2 14,5 14.5 21,7 21.7 28,5 28.5 13,3 13.3 22,2 22.2 29,1 29.1 20,0 20.0 18,2 18.2

V porovnaní s u nás vyrábaným roztokovým hnojivom typu DAM 390 sa uvedené hnojivá vyznačujú vyššou fázovou stabilitou (až —23 °C), zvýšeným podielom amoniakálneho dusíka a umožňujú predovšetkým efektívne využitie síranu amónneho, ktorého ponuka v, kryštalickej formě převyšuje v rámci ČSSR dopyt polnohospodárskej praxe. Síran amónny v ČSSR vzniká predovšetkým ako vedlajší produkt pri výrobě kaprolaktamu a metylmetakrylátov. Z výroby odpadajúce kyslé výluhy sa neutralizujú amoniakom, zahusťujú sa a kryštalizáciou sa získává síran amónny. Významné predovšetkým energetické úspory je možné získat pri spracovaní odpadných kyslých výluhov na kvapalné hnojivá typu SADAM podlá vynálezu. Predmetom vynálezu je spósob výroby kvapalných dusíkato-sírnych hnojiv na báze dusičnanu a síranu amónneho, močoviny a vody vyznačujúci sa tým, že neutra]izačnej reakci! sa podrobí roztok síranu amónneho v kyselině sírovej s amoniakátom dusičnanu amónneho, pričom k reakčnej zmesi sa před, v priebehu neutralizačnej reakcie, alebo po jej ukončení ďalej přidává močovina a připadne tiež kyselina dusičná a/alebo dusičnan amónny, a/alebo síran amónny, a/alebo amoniak.Compared to the DAM 390 solution fertilizer produced in our country, the above-mentioned fertilizers are characterized by higher phase stability (up to -23 °C), an increased proportion of ammoniacal nitrogen and, in particular, enable the effective use of ammonium sulfate, the supply of which in crystalline form exceeds the demand for agricultural practice within the Czechoslovak Socialist Republic. Ammonium sulfate in the Czechoslovak Socialist Republic is mainly produced as a by-product in the production of caprolactam and methyl methacrylates. The acid leachates that are left over from production are neutralized with ammonia, concentrated and ammonium sulfate is obtained by crystallization. Significant energy savings can be obtained in particular when processing waste acid leachates into liquid fertilizers of the SADAM type according to the invention. The subject of the invention is a method for producing liquid nitrogen-sulfur fertilizers based on nitrate and ammonium sulfate, urea and water, characterized in that the neutralization reaction! a solution of ammonium sulfate in sulfuric acid is subjected to ammonium nitrate ammonia, with urea and optionally nitric acid and/or ammonium nitrate, and/or ammonium sulfate, and/or ammonia being further added to the reaction mixture before, during, or after the neutralization reaction.

V šúvislosti s uplatněním- spósobu výroby v zmysle vynálezu sa> ukázalo ako zvlášť výhodné použiť ako'roztok Síranu amonného v kysélihéT sírovej vedlajšlé produkty: z výroby metylmétakrylátú^? a/alebo z výroby kaprolaktamu.In connection with the application of the production method according to the invention, it has proven to be particularly advantageous to use as a solution of ammonium ^sulfate in sulfuric acid by-products from the production of methyl methacrylate and/or from the production of caprolactam.

Z ekonomického a prevádzkového hlediska sa javí účelným použit na neutralizáciu amoniakáty dusičnanu amónneho o tomto zložéní:From an economic and operational point of view, it seems expedient to use ammonium nitrate ammonia with the following composition for neutralization:

il ’it's

53,5 — 64,5 % hmotnostného· NH4NO353.5 — 64.5 % by weight NH4NO3

18,8 — 27,2 % hmotnostného NH₃ 18.8 — 27.2 % by weight NH ₃

14,3 — 21,7 % hmotnostného H₂Ó.14.3 — 21.7% by weight H ₂ O.

Experimentálně sa potvrdilo, že močovinu je možné přidávat do reakčného systému v tuhom stave, vo formě taveniny, alebo vo formě vodného roztoku.It was experimentally confirmed that urea can be added to the reaction system in a solid state, in the form of a melt, or in the form of an aqueous solution.

Přednostou navrhovaného riešenia je významná úspora energie a možnost výroby v ČSSR doteraz nevyrábaných typov kvapalných hnojiv po úpravě a doplnění strojnotechnologických zariadení v jestvujúcich výrobniach síranu amónneho.The advantage of the proposed solution is significant energy savings and the possibility of producing types of liquid fertilizers not previously produced in the Czechoslovak Socialist Republic after modifying and supplementing mechanical and technological equipment in existing ammonium sulfate production plants.

Přidáváním močoviny vo formě taveniny, resp. roztoku je možné dosiahnúť ďalšiu významnú úsporu energie potrebnej pri jej kryštalizácii, resp. prílovaní.By adding urea in the form of a melt or solution, it is possible to achieve further significant savings in the energy required for its crystallization or addition.

Potřebné suroviny — močovina a amoniakát dusičnanu amonného sú z domácej produkcie a je zvládnutý ich transport, skladovanie a dávkovanie do technologického procesu. V n. p. Duslo Šal'a sa v súčasnosti vyrábajú dva typy amoniakátov dusičnanu amonného. Tzv. letný typ ADA nasledovného zloženia:The necessary raw materials — urea and ammonium nitrate ammonia are from domestic production and their transport, storage and dosing into the technological process are managed. In the Duslo Šal'a plant, two types of ammonium nitrate ammonia are currently produced. The so-called summer type ADA of the following composition:

NH4NO3 — 63,0 ± 1,5 %;NH4NO3 — 63.0 ± 1.5%;

H2O — 17,0 + 2,7 %;H2O — 17.0 + 2.7%;

NH3 - 20,0 + 1,2 %;NH3 - 20.0 + 1.2%;

bod kryštalizácie — cca 0 °C a zimný typ ADA zloženia:crystallization point — approx. 0 °C and winter type ADA composition:

NH4NO3- 55,0 + 1,5 %;NH4NO3- 55.0 + 1.5%;

H2O — 19,0 + 2,7 %;H2O — 19.0 + 2.7%;

NH3 — 26 + 1,2 °/o;NH3 — 26 + 1.2 %;

bod kryštalizácie — cca — 31,7 °C.crystallization point — approx. — 31.7 °C.

Podlá zistení (Prof. Fecenko, DrSc., VŠP Nitra, Ing. Synak, CSc., VÚCHT Bratislava) nie sú v produkte přítomné organické látky (ako zvyšky z výroby kaprolaktamu, resp. metylmetakrylátov), fytotoxické a v pode dochádza lahko k ich odbúraniu.According to the findings (Prof. Fecenko, DrSc., VŠP Nitra, Ing. Synak, CSc., VÚCHT Bratislava), the product does not contain organic substances (such as residues from the production of caprolactam or methyl methacrylates), phytotoxic substances, and they are easily degraded in the soil.

Predmet vynálezu ozrejmujú, ale nijako neobmedzujú nasledujúce příklady.The following examples illustrate, but do not limit, the subject matter of the invention.

Příklad 1Example 1

V 3-1 sulfonačnej banke sa 100 hmotnostných dielov odpadného kyslého roztoku z výroby metylmetakrylátov (po oddestilovaní nízkovrúcich organických podielov] zloženia 43,2 % H2SO1, 5,69 % N — amoniakálneho a 2,17 % organických látok, neutralizovalo 41. hmotnostnými dielmi amoniakátu dusičnanu amonného (ADA-letný typ) zloženia 19,8 % NH3, 62,2 % NH4NO3 a 18 % H2O. K sústave sa přidalo 2.5 hmotnostného dielu síranu amónneho, 65 dielov granulovanej močoviny a 46 hmotnostných dielov vody. Po ochladení reakčnej zmesi sa získalo kvapalné hnojivo typu SADAM 260 nasledovného zloženia:In a 3-1 sulfonation flask, 100 parts by weight of waste acidic solution from the production of methyl methacrylates (after distillation of low-boiling organic components) with a composition of 43.2% H2SO1, 5.69% N — ammoniacal and 2.17% organic substances, were neutralized with 41 parts by weight of ammonium nitrate ammonia (ADA-summer type) with a composition of 19.8% NH3, 62.2% NH4NO3 and 18% H2O. 2.5 parts by weight of ammonium sulfate, 65 parts by weight of granulated urea and 46 parts by weight of water were added to the system. After cooling the reaction mixture, a liquid fertilizer of the SADAM 260 type with the following composition was obtained:

39,62 % vody,39.62% water,

Claims

The required raw materials - urea and ammonium nitrate ammonium nitrate - are produced domestically and transported, stored and dispensed into the technological process. At present, two types of nitrate ammonium ammonium are produced in Duslo Shal'a. So-called. summer type ADA of the following composition: NH 4 NO 3 - 63.0 ± 1.5%; H2O - 17.0 + 2.7%; NH 3 - 20.0 + 1.2%; crystallization point - about 0 ° C and winter type of ADA composition: NH 4 NO 3 - 55.0 + 1.5%; H2O - 19.0 + 2.7%; NH 3 - 26 + 1.2 ° / o; crystallization point - approx. - 31.7 ° C. According to the findings (Prof. Fecenko, DrSc., VŠPNitra, Ing. Synak, CSc., VĎCHT Bratislava), there are no organic substances present in the product (as residues from the production of caprolactam or methyl methacrylates), phytotoxic and in the water there are 1 easy to their destruction. The following examples illustrate, but do not limit, the invention. EXAMPLE 1 In a 3-1 sulfonation flask, 100 parts by weight of the waste acidic solution was made up of methyl methacrylates (after distillation of the low-boiling organic portions) with 43.2% H2SO4, 5.69% N-ammonia and 2.17%. % by weight, 41% by weight of ammonium nitrate ammonium nitrate (ADA) was 19.8% NH 3, 62.2% NH 4 NO 3 and 18% H 2 O. 2.5 parts by weight of ammonium sulfate, 65 parts by weight of granulated urea and 46 parts by weight of water were added to the system. After cooling the reaction mixture, a SA-DAM 260 liquid fertilizer of the following composition was obtained: 39.62% water, SUBJECT

A process for the production of nitrate-sulphamic-ammonium, urea-water-based liquid nitrogen-sulfur fertilizers, characterized in that the neutralization reaction is a solution of ammonium sulphate in sulfuric acid with ammonium nitrate ammonia, the reaction mixture being subjected to, before during the neutralization reaction, or urea is added thereto.

2. A process according to claim 1, wherein nitric acid and / or ammonium nitrate or ammonium sulfate and / or ammonia are added to the reaction mixture.

3. Method of production according to item 1, characterized by: 23.91% ammonium sulfate, 10.04% ammonium nitrate, 25.58% urea, 0.85% organic substances, total N = 20.42%, pH = 6.38 = 1.268 g / cm 3. Example 2 To 100 parts by weight of an effluent solution of the same composition with Example 1 was added 8.0 parts by weight of 55% HNO3 and neutralized with 47 parts of ADA-summer type with the addition of 74.5% by weight of urea and 35.5 parts of water. Cooling the reaction mixture to room temperature gave liquid SADAM 286 nitrogen-sulfur fertilizer of the following composition: 35.70% water, 22.10% ammonium sulfate, 13.20% ammonium nitrate, 28.20% urea, 0 , 82% organic matter, total N - 22.43 ° / o; pH = 6.52. EXAMPLE 3 100 parts by weight of the waste composition of Example 1 were neutralized with 31 parts of ADA - winter type, compound: 25.4% NH3, 55.3% NH4NO3, 19.3% H2O. To the neutralization mixture was added 7 µl ammonium nitrate and 64 parts urea and 50 parts water. A SADAM 260 fertilizer of the following composition was obtained: 42.0% water, 23.5% ammonium sulfate, 9.8% ammonium nitrate, 25.9% urea, 0.88% organic, total N = 20.39%; pH = 6.52 = 1.265 g / cm 3. SUMMARY OF THE INVENTION that the ammonium nitrate ammonium salt contains 53.5 to 64.5 wt. ammonium nitrate, 18.8 to 27.2 wt. % ammonia, 14.3 to 21.7 wt. water.

4. The method of manufacture of claim 1 wherein the ammonium sulphate solution and the sulfuric acid are derived from the production of methyl methacrylate.

5. A method according to claim 1, wherein the urea is added in the solid state, in the melt farm, or in the form of an aqueous solution.