CS230306B1 - Method of processing mother liquors from the production of hexamethylene tetramine - Google Patents
Method of processing mother liquors from the production of hexamethylene tetramine Download PDFInfo
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- CS230306B1 CS230306B1 CS230281A CS230281A CS230306B1 CS 230306 B1 CS230306 B1 CS 230306B1 CS 230281 A CS230281 A CS 230281A CS 230281 A CS230281 A CS 230281A CS 230306 B1 CS230306 B1 CS 230306B1
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- hexamethylenetetramine
- mother liquors
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 title claims description 58
- 239000004312 hexamethylene tetramine Substances 0.000 title claims description 29
- 235000010299 hexamethylene tetramine Nutrition 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 13
- 229960004011 methenamine Drugs 0.000 title 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 amino-substituted triazine ring Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000012431 aqueous reaction media Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000002357 guanidines Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QYXHJMXBZWOTJN-UHFFFAOYSA-N formaldehyde;guanidine Chemical compound O=C.NC(N)=N QYXHJMXBZWOTJN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
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- Fertilizers (AREA)
Description
Vynález sa týká Jednoduchého sposobu spracovania matečných lúhov z výroby hexametylémtetrainínu, získaného amoniakalizácicu vodných roztokov fořmaldehydu, na polykondenzačné živice a amónne soli.The invention relates to a simple process for the treatment of mother liquors from the production of hexamethylmethytrainine, obtained by the ammoniacalization of aqueous solutions of formaldehyde, into polycondensation resins and ammonium salts.
Z patentovej literatury sú známe postupy (ZSSR autorského osvedčenia číslo 487 930, 501 678; V. Británia patent číslo 1 390 370 a ďalšie), ktoré používají! hexametylémtetramín pri výrobě polykondenzačných živíc, hlavně na báze močoviny a fořmaldehydu, ako modifikačnú přísadu, za účelom získania živíc k špeciálnym aplikáciam. Avšak nie je známy postup, ktorý by používal pri výrobě polykondenzačných živíc samotný hexametyléntetramín ako zdroj formaldehydu, čo je možné vysvětlit ekonomickou nevýhodnosťou uvažovaného sposobu. Uvedenú nevýhodnost je možné odstrániť využitím matečných lúhov z výroby hexametyléntetramínu, ktoré sú nežiadúcim odpadom. Doposiať nie je z dostupných literárných zdrojov známe zodpovedajúce využitie matečných lúhov z výroby hexametyléntetramínu v chemickej syntéze. V súčasmosti používaným sposobom likvidacie odpadných roziOKov hexametyléntetramínu je ich spa1'ovanie. Ak prihliadame na objektivně stažené podmienky v získávání surovin a vzhladom na ochranu a tvorbu životného prostredia je tento stav nedostatočný. Uvedené problémy rieši tento vynález.Patent procedures disclose methods (USSR Author's Certificate No. 487,930, 501,678; UK Patent No. 1,390,370 et seq.) Which employ! hexamethylmethetramine in the manufacture of polycondensation resins, mainly based on urea and formaldehyde, as a modifying additive, in order to obtain resins for special applications. However, there is no known process using hexamethylenetetramine alone as a source of formaldehyde in the production of polycondensation resins, which can be explained by the economic disadvantage of the present process. This disadvantage can be overcome by using mother liquors from the production of hexamethylenetetramine, which is an undesirable waste. To date, the corresponding use of mother liquors from the production of hexamethylenetetramine in chemical synthesis is not known from the available literature sources. The currently used method of disposing of the waste solutions of hexamethylenetetramine is to incinerate them. Taking into account the objectively withdrawn conditions in the sourcing of raw materials and with regard to the protection and creation of the environment, this situation is insufficient. These problems are solved by the present invention.
Podlá tohto vynálezu sa spósob spracovania matečných lúhov z výroby hexametyléntetramínu, získaného amoniakalizáciou vodných roztokov fořmaldehydu, na polykomdenzačné živice a/alebo amónne soli, uskutočňuje tak, že na matečné lúhy z výroby hexametyléntetramínu vo vodnom reakčnom prostředí aspoň s jednou zlúčentaou s pohyblivým atomoin vodáka všeobecného vzorcaAccording to the present invention, a process for treating mother liquors from the production of hexamethylenetetramine, obtained by ammoniacalizing aqueous solutions of formaldehyde, into polycondensation resins and / or ammonium salts is carried out by treating the mother liquors from the production of hexamethylenetetramine in aqueous reaction medium with at least one aqueous compound. of formula
Ri \Ri \
N—C--NH2N-C - NH 2
Z IIZ II
Rz x kdeRz x where
X je kyslík alebo NH,X is oxygen or NH,
Ri je vodík aR 1 is hydrogen;
R2 znamená vodík, NH2 alebo CN alebo tiež X spolu s Ri a Rz je zbytok amínosubistituovaného triazínovélio prstence, s výhodou močoviny alebo solí guanidínu, v množstve 4 až 8 kmol, s výhodou 4,6 až ,5,7 kmol na 1 kmol přítomného hexametyléntetramínu, sa posobí miinerálnou kyselinou v množstve 1,5 až 4,5 kmol, s výhodou v množstve 1,8 až 3,7 kmol na 1 kmol príítom230306 ného hexametyléntetramínu pri teplote 4 až 103 °C po dobu 5 až 80 minút, s výhodou 23 až 40 minút, za vzniku roztoku alebo siuspeihzie.R 2 is hydrogen, NH 2 or CN, or X together with R 1 and R 2 is the remainder of the amino-substituted triazine ring, preferably urea or guanidine salts, in an amount of 4 to 8 kmol, preferably 4.6 to 5.7 kmol per mole of present hexamethylenetetramine, is impregnated with a mineral acid in an amount of 1.5 to 4.5 kmol, preferably in an amount of 1.8 to 3.7 kmol per mole of the present 230306 hexamethylenetetramine at 4 to 103 ° C for 5 to 80 minutes, s preferably 23 to 40 minutes, to form a solution or siuspeihzie.
Medzi výhody postupu podl'a vynálezu možno zariadiť predovšetkým tú skutočnoísť, že aplikficiou matečných lúhov z výroby hexametyléntetramínu sa spája záujem priemyslu (likvidácia výrobného odpadu) so šetřením nedostatkového formaldehydu, resp. amoniaku. Týmto riešením sa súčasne zamedzí případnému vzniku škod kontamináciou ovzdušia, resp. znečištěním vodných Zdrojov. V neposlednom řade vhodným výběrem minerálnej kyseliny sa možu zároveň vyrábať a) technicky a ekonomicky hodnotné produkty s možnosťou širokého uplatnenia.Among the advantages of the process according to the invention, it is particularly possible to realize that the application of mother liquors from the production of hexamethylenetetramine combines the interest of industry (disposal of production waste) with the investigation of formaldehyde scarcity and / or scarcity. ammonia. At the same time, this solution will prevent potential damage caused by air contamination, resp. pollution of water resources. Last but not least, a suitable choice of mineral acid can produce at the same time: (a) technically and economically valuable products with a wide range of applications.
Pojem matečné lúhy z výroby hexametyléntetramínu označuje vodné roztoky hexametyléntetramínu obyčajne nasýtené, znečistěné polyolmi (Cs až Cz) alebo cukrom Cs až C7 korešpondujúcim N-Mannichovými bfizami.The term mother liquors from the production of hexamethylenetetramine refers to aqueous solutions of hexamethylenetetramine usually saturated, contaminated with polyols (Cs to C 2) or Cs to C 7 sugar corresponding to N-Mannich bismuths.
Vynikajúce výsledky tvorby polykondenzačných živíc s vysokým výtažkem sa dosahujú vhodným zriedením matečných lúhov vodou a/alebo použitím dalších „reaktans“ zodpovedajúcej koncentrácie. Vzhladom ,k reakčnej rýchlosti je možné pracovat v širokom rozmedzí teploty, ktorá obvykle nepřesahuje 105 °C. K vytvoreniu reakčného prostredia sa hodí celý rad kyslo reagujúcich súhstancií, ako je například kysličník sírový, sulfurylchlorid, kyselina sírová, kyselina chlorovodíková, hlavně však kyselina trihydrofosforečná a dusičná.The excellent results of high yield polycondensation resins are obtained by appropriately diluting the mother liquors with water and / or using other "reactants" of appropriate concentration. Because of the reaction rate, it is possible to operate over a wide temperature range, which usually does not exceed 105 ° C. A variety of acid-reactive constituents are suitable for forming the reaction medium, such as, for example, sulfur trioxide, sulfuryl chloride, sulfuric acid, hydrochloric acid, but especially trihydrophosphoric and nitric acid.
Z možnosti použitia k základnému polykondemzačnému viazaniu uvolněného formaldehydu „in šitu“ z matečných lúhov sa hodí celý rad zlúčenin aspoň s jedným pohyblivým atómom vodíka, ako je například močovina, tiomočovina, melamín, guanldín, dikyanamid, amiinoguananidín, aka aj aromatické zlúčeniny, například fenol, kirezol a pod. Vzhladom na širokú technickú dostupnost je však najvýhodnejšia velkotonážne vyrábainá močovina, či už v pevnom stave alebo v roztoku.From the possibility of being used for basic polycondensation binding of released formaldehyde "in situ" from the mother liquors, a variety of compounds with at least one mobile hydrogen atom, such as urea, thiourea, melamine, guanldine, dicyanamide, amiinoguananidine, and aromatic compounds such as phenol , kirezol and the like. However, given the wide technical availability, the bulk urea produced in bulk or in solution is the most preferred.
Získaný nerozpustný reakčný produkt sa připadne odsolí a/alebo spracováva niektorou z běžných technik sušenia.The insoluble reaction product obtained is optionally desalted and / or subjected to one of the conventional drying techniques.
(Pozn.: suspenzie s obsahom dusičnanov sú z bezpečnostného hfadiska nevhodné pre sušenie v rozprašovacích sušlarňach).(NB: from a safety point of view, nitrate suspensions are unsuitable for spray drying).
Produkty získané pódia tohto vynálezu sú vhodné pre aplikáciu vo výrobě kombinovaných hnojív; vo formě práškovej sú aplikovatelné pre antispekavú úpravu hnojív. Ďalej sú použitelné ako komponenty hnojív vo formě suspenzie, či roztoku, alebo ako samotné hnojivo s pomaly posobiacim dusíkom. Použitie vhodnej kyseliny a techniky spracovania rezultujúcej reakčnej zmesi rozširujú možnosti použitia získaných produktov.The products obtained according to the invention are suitable for application in the production of combined fertilizers; in powder form are applicable for antispecific treatment of fertilizers. Furthermore, they are useful as fertilizer components in the form of a suspension or solution, or as a fertilizer with a slow nitrogen scavenger. The use of a suitable acid and the processing technique of the resulting reaction mixture extend the possibilities of using the products obtained.
Příklad 1Example 1
K dispozicii sú matečné lúhy po kryštallzácii hexametyléntetramínu, ktoré obsahiujú 501,2 g hexametyléntetramínu v 1000 ml a ďalšie pirímesi, hlavně polyoly, respektive cukrom C5 až C7 korešpondujúcej zlúčeniny, ktorýeh obsah vyjádřený ako obsah glukózy je 1,65 % hmot.; stanovený odparok 1000 ml uvedeného matečného lúhu je 518,2 gramov.There are mother liquors after crystallization of hexamethylenetetramine containing 501.2 g of hexamethylenetetramine in 1000 ml and other pirimites, mainly polyols, respectively the C5 to C7 sugar of the corresponding compound, which has a glucose content of 1.65% by weight; the determined residue of 1000 ml of said mother liquor is 518.2 grams.
Do aparátu s turbínovým miešadlom sa nadávkuje 2,5 m3 matečných lúhov uvedeného zloženia (t. j. 8,94 kmol hexametyléntetramínu a 81,5 kmol vody), ktoré sa zriedi 3 m3 vody (t. j. 166,67 kmol vody). Ďalej do tohto roztoku sa přidá 2880 kg močoviny (t. j. 48 kmol močoviny). Po rozpuštění močoviny sa pri teplote 4 °C za intenzívneho miešania dávkuje kyselina sírová 94,1 %-ná v množstve 910 litrov (it. j. 15,99 kmol kyseliny sírovej a 5,46 kmol vody) v priebehu 10 minút. V priebehu dávkovania teplota reakčnej zmesi stúpne a na konci dosiahne teplotu varu (t. j. 98 až 101 °C). 20 minút po skončení dávkovania kyseliny sírovej vzniknutá sulspenzia s pH 5 až 6 sa nastrekuje do rozprašovače] sušiarne (teplota na vstupe 176 0,C a na výstupe 90 + 5 °C). Získá sa práškový produkt s obsahom 24,38 % hmot. organicky viazaného dusíka, 9,47 % hmot. amoniakálneho dusíka a 61,1 % hmot. vodonerozpustného močovinoformaldehydového kondenzátu. Pri cca 5 % úlete sa získá 5450 kg produktu.2.5 m 3 of mother liquors of the above composition (ie 8.94 kmol of hexamethylenetetramine and 81.5 kmol of water) are metered into the turbine mixer and diluted with 3 m 3 of water (ie 166.67 kmol of water). Next, 2880 kg of urea (ie 48 kmol of urea) are added to this solution. After dissolution of the urea at 94 DEG C., 910 liters of sulfuric acid (i.e. 15.99 km of sulfuric acid and 5.46 km of water) are metered in with vigorous stirring over a period of 10 minutes. During dosing, the temperature of the reaction mixture rises and at the end reaches the boiling point (i.e. 98-101 ° C). 20 minutes after the end of the sulfuric acid dosing, the resulting sulspension at pH 5-6 was injected into the sprayer of the dryer (inlet temperature 176 ° C and outlet 90 + 5 ° C). A powdered product is obtained having a content of 24.38% by weight. % organically bound nitrogen, 9.47 wt. % of ammonia nitrogen and 61.1 wt. water-insoluble urea-formaldehyde condensate. At about 5% drift, 5450 kg of product are obtained.
Příklad 2Example 2
Do 1 m3 matečných lúhov po kryštalizácii hexametyléntetramínu, rovnakého zloženia ako v příklade 1, (t. j. 3,58 kmol hexametyléntetramínu a 32,6 kmol vody) sa přidá 1180 kg močoviny (t. j. 19,67 kmol močoviny ) a 1,95 m3 kyseliny fosforečnej 37,6 %-nej (t. j. 7,97 kmol kyseliny fosforečnej a 72 kmol vody). Zmes sa za stálého miešania vyhřeje na teplotu 96 až 98 °C a v tomto teplotnom rozmedzí sa udržuje 30 minút. Získá sa poměrně hustá suspenzia s pH 6 až 6,5, ktorá obsahuje 22,05 % hmot. vodonerozpustných močovinoformaldehydových kondenzátov, 3,8 % hmot. amoiniakálneho dulsíka a 5,66 % hmot. fosfátového fosforu.1180 kg of urea (ie 19.67 kmol of urea) and 1.95 m 3 are added to 1 m 3 of mother liquors after crystallization of hexamethylenetetramine of the same composition as in Example 1 (ie 3.58 kmol of hexamethylenetetramine and 32.6 kmol of water). phosphoric acid 37.6% (i.e. 7.97 kmol phosphoric acid and 72 kmol water). The mixture is heated to 96-98 ° C with stirring and maintained at this temperature range for 30 minutes. A relatively thick suspension having a pH of 6 to 6.5 is obtained, which contains 22.05 wt. % water-insoluble urea-formaldehyde condensates, 3.8 wt. % of an amoiacal pulp and 5.66 wt. phosphate phosphorus.
Vysušením suspenzie ako v příklade 1 sa získá práškový produkt, obsahujúci 6,78 % hmot. amoniakálneho dusíka, 23,52 % hmot. organicky viazaného dusíka a 9,95 % hmot. fosfátového fosforu. Pri cca 5 %-ných úletech sa získá 2360 kg sušiny.Drying the slurry as in Example 1 gave a powdered product containing 6.78 wt. % ammonia nitrogen, 23.52 wt. % organically bound nitrogen and 9.95 wt. phosphate phosphorus. At about 5% drift, 2360 kg of dry matter is obtained.
Příklad 3Example 3
K dispozicii sú matečné lúhy po kryštalizácii hexameítyléntetramínu, ktoré obsahiujú 506,8 g substancie v 1000 ml. Obsah vediaj230306There are mother liquors after crystallization of hexamethylenetetramine containing 506.8 g of substance in 1000 ml. Contents ved230306
S ších produktov syntézy hexametyléntetramínu (t.j. polyolov, resp. cukrov Cs až C7) v týchto lúhoch je 1,29 % hmot. vyjádřených ako glukóza a stanovený odparok 1000 ml uvedeného matečného luhu je 522,2 g.The synthesis products of hexamethylenetetramine (i.e. polyols or C8-C7 sugars) in these lyes are 1.29% by weight. expressed as glucose and the determined residue of 1000 ml of said mother liquor is 522.2 g.
Do 1 m3 matečných lúhov uvedenej kvality (t. j. 3,62 kmol hexametyléntetraminu a 32,38 kmol vody) sa přidá 1000 kg močoviny (t. j. 16,67 kmol). Táto zmes sa za miešania vyhřeje na 60 °C. Pri tejto teplote sa nadávkuje 2,4 m3 kyseliny dusičnej 22,18 %-nej (t. j. 9,53 kmol kyseliny dusičnej a 117,01 kmol vody). Zmes sa vyhřeje na teplotu 99 až 103 °C a v tomto teplotnom rozmedzí sa udržuje 40 mlnút. Po vychladnutí na teplotu okolia sa získá zakalený roztok (pH = = 6,5 až 7) s obsahom 3,40 % hmot. dusíka amoniakálneho, 12,48 % dusíka nitrátového a 11,14 % hmot. dusíka organického (pozn.: z 'roztoku je mierne cítit amoniak).To 1 m 3 of mother liquors of the indicated quality (ie 3,62 kmol hexamethylenetetramine and 32,38 kmol water) add 1000 kg of urea (ie 16,67 kmol). This mixture was heated to 60 ° C with stirring. At this temperature, 2.4 m 3 of 22.18% nitric acid (i.e. 9.53 kmol of nitric acid and 117.01 kmol of water) are metered in. The mixture is heated to a temperature of 99-103 ° C and 40 ml is maintained within this temperature range. After cooling to ambient temperature, a cloudy solution (pH = 6.5 to 7) containing 3.40 wt. % ammoniacal nitrogen, 12.48% nitrate nitrogen and 11.14% wt. organic nitrogen (note: ammonia is slightly smelled from the solution).
Příklad 4Example 4
Do 1 m3 matečných lúhov po kryštalizácii hexametyléntetraminu, kvalitou totožných s lúhmi použitými v příklade 3 (t. j. 3,62 k-mol hexametyléntetraminu a 32,38 kmol vody), sa přidá 1240 kg močoviny (t. j. 20,67 kmol) a za nestálého miešania sa rýchlo nadávkuje 1,5 m3 kyseliny duísičnej 44,21 %-nej (t. j. 13,35 kmol kyseliny dusičnej a 58,97 kmol vody). Reakčná zmes sa vyhřeje na teplotu varu (98 až 101 °C) a táto sa udržuje samovolné exotermickou reakciou po dobu 8 mlnút. Po 15 minutovom doreagovaní pri teplote 96 až 98 °C sa získá velmi hustá súspeinzia, pH ktorej je 6 až 6,5. Suspenzia obsahuje 5,33 % hmot. amoniakálneho dusíka, 19,8 % hmot. nitrátového dusíka a 13,9 % hmot. organicky viazaného dusíka, pričom obsah vodonerozpustných močovinoformaldehydových kondenzátor je 31,6 % hmot.1240 kg of urea (ie 20.67 kmol) are added to 1 m 3 of mother liquors after crystallization of hexamethylenetetramine of a quality identical to those used in Example 3 (ie 3,62 k-mol of hexamethylenetetramine and 32,38 kmol of water) and under unstable 1.5 m 3 of 44.21% nitric acid (i.e. 13.35 kmol of nitric acid and 58.97 kmol of water) were added rapidly to the stirring mixture. The reaction mixture is heated to boiling point (98-101 ° C) and this is maintained by spontaneous exothermic reaction for 8 minutes. After a 15-minute reaction at 96-98 ° C, a very dense cohesive pH of 6-6.5 is obtained. The suspension contains 5.33 wt. % ammonia nitrogen, 19.8 wt. % nitrate nitrogen and 13.9 wt. % of organically bound nitrogen, the content of water-insoluble urea-formaldehyde condensers being 31.6% by weight.
Příklad 5Example 5
Do 1 ,m3 matečných lúhov po kryštalizácii hexametyléntetraminu, kvalitou totožných s lúhami, použitými v příklade 3 (t.j. 3,62 kmol hexametyléntetraminu a 32,38 kmol vody] sa přidá 1,1 m3 vody (t. j. 61,11 kmol vody) a 565 kg guanidínnitrátu (t.j. 4,62 kmol guanidínnitrátu). Reakčná zmes sa vyhřeje na teplotu varu (t.j. 98 až 101 °Cj. ktorá sa potom 6 minút samovolné udržuje exotermickou reakciou. Po 30 minútach doreagovania pri 95 až 98 °C sa získá suspenzia, obsahujúca 7,65 % hmot. amoniakálneho dusíka, 2,44 % hmot. nitrátového dusíka, 7,32 % hmot. organicky viazaného dusíka, pričom obsah vodonerozpustných guanidínformaldehydových kondenzátov je 29,8 percenta hmot.1.1 m 3 of water (ie 61.11 kmol of water) is added to 1 m 3 of mother liquors after crystallization of hexamethylenetetramine of the same quality as those used in Example 3 (ie 3.62 kmol of hexamethylenetetramine and 32.38 kmol of water). and 565 kg of guanidine nitrate (i.e. 4.62 kmol guanidine nitrate) The reaction mixture is heated to boiling point (i.e. 98 to 101 ° C), which is then spontaneously maintained for 6 minutes by exothermic reaction. After 30 minutes of reaction at 95 to 98 ° C, a suspension comprising 7.65 wt.% ammoniacal nitrogen, 2.44 wt.% nitrate nitrogen, 7.32 wt.% organically bound nitrogen, the content of water-insoluble guanidine formaldehyde condensates being 29.8 wt.%.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS230281A CS230306B1 (en) | 1981-03-30 | 1981-03-30 | Method of processing mother liquors from the production of hexamethylene tetramine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS230281A CS230306B1 (en) | 1981-03-30 | 1981-03-30 | Method of processing mother liquors from the production of hexamethylene tetramine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS230306B1 true CS230306B1 (en) | 1984-08-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS230281A CS230306B1 (en) | 1981-03-30 | 1981-03-30 | Method of processing mother liquors from the production of hexamethylene tetramine |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS230306B1 (en) |
-
1981
- 1981-03-30 CS CS230281A patent/CS230306B1/en unknown
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