CS226535B1 - Method of freparing cyclic nitrosoamines - Google Patents
Method of freparing cyclic nitrosoamines Download PDFInfo
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- CS226535B1 CS226535B1 CS409481A CS409481A CS226535B1 CS 226535 B1 CS226535 B1 CS 226535B1 CS 409481 A CS409481 A CS 409481A CS 409481 A CS409481 A CS 409481A CS 226535 B1 CS226535 B1 CS 226535B1
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- Czechoslovakia
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- weight
- hexamethylenetetramine
- surfactants
- ethylene oxide
- moles
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- 238000000034 method Methods 0.000 title description 17
- -1 cyclic nitrosoamines Chemical class 0.000 title description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 46
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 23
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 19
- 229960004011 methenamine Drugs 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 238000005187 foaming Methods 0.000 description 7
- 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 6
- 238000003776 cleavage reaction Methods 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 230000009935 nitrosation Effects 0.000 description 6
- 238000007034 nitrosation reaction Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000007017 scission Effects 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 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 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález sa týká sposobu výroby cyklických nitrózoamínov, pričom podmíenky sú volené tak, že vhodným výberom tenzidu sa v podstatnej miere ovplyvňuje výťažok a kvalita produktu bez ovplyvnenia ekonomiky.The present invention relates to a process for the production of cyclic nitrosamines, wherein the conditions are chosen such that the choice of surfactant substantially affects the yield and quality of the product without affecting the economy.
Nitrozačmé štiepemie hexametyléntetramínu (HMT) v kyslom prostředí, najmá za pomoci dusitanov alkalických kovov a/alebo alkalických zemin je priemyslovo najschodnejší sposob výroby l,5-endometylén-3,7-dinitrózo-l,3,5,7-tetraazacyklooktánu známého tiež pod názvom N,N‘-dinitrózopentametyléintetramín (DNPT) ako aj 1,3,5-trlmitrózo-1,3,5-triazacyklohexánu, nazývaného tiež R-soIou.The nitro-nitrous cleavage of hexamethylenetetramine (HMT) in acidic environments, particularly with the aid of alkali metal and / or alkaline earth nitrites, is the most industrially viable process for the production of 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacyclooctane also known as N, N'-dinitrosopentamethylenetetramine (DNPT) as well as 1,3,5-trlmitroso-1,3,5-triazacyclohexane, also called R-salt.
Z celého radu spósobov výroby cyklických nitrózoamínov, popísaných v dostupnej literatúre, len vo francúzskom patente č. 1 580 636 sa venuje váčšia pozornost použitiu teinzidov, ktorého podstata spočívá v nitrozácii hexametylémtetramínu vo vodnom roztoku za přítomnosti malých množstiev tenzidov ako sú alkylsulfonát sodný, dimetyl-palmitylamín, alkylester trietanolaminu a/ /alebo polyglykoléter nonyl-fenolu. Potřebné je uviesť, že Ide o pěnivé a biologicky neodbúratelné tenzidy. Nedostatkom uvedeného vynálezu je tá skutočnosť, že sa nevenuje dostatečná .pozornost výběru tenzidov z hlaí* diiska penivOsti a bílogickej odbúrateínosti. Týtato výbeťom sa dá dosiahnut vyšší účinok, najma v smere zníženia chemických rizik pri použití roztokov hexametyléntetramínu s obsahom produktov typu polyolov Cs až C7, respektive cukrom Cs až C7 korešpondiujúcim N-Manichovým bázam, ktorých přítomnost evidentne vplýva na zníženie výtěžnosti procesu. Ďalej je to zamedzenie úniku reakčnej masy zo zariadenia, ako aj zníženie trvalého znečištenia vodných zdrojov apod. Χ4Ϊ0Of the numerous processes for the production of cyclic nitrosoamines described in the available literature, only the French patent no. 1,580,636 pays more attention to the use of theinzides, which is based on the nitrosation of hexamethylmethetramine in aqueous solution in the presence of small amounts of surfactants such as sodium alkyl sulfonate, dimethyl palmitylamine, alkyl ester of triethanolamine and / or polyglycol ether of nonylphenol. It should be noted that these are foaming and non-biodegradable surfactants. A drawback of the present invention is that insufficient attention is paid to the selection of surfactants from the foaming point and the biodegradability. These extracts can achieve a higher effect, in particular in reducing the chemical hazards of hexamethylene tetramine solutions containing C8-C7 polyols and C8-C7 sugar, respectively, corresponding to N-Manich bases, the presence of which evidently affects the yield of the process. Furthermore, it prevents the escape of the reaction mass from the plant, as well as the reduction of permanent pollution of water sources, etc. Χ4Ϊ0
Tieto a ďalšie nedostatky uvedeného postupu rieši tento vynález.These and other drawbacks of the above process are solved by the present invention.
Podía tohto vynálezu sa sposob výroby cyklických nitrózoamínov všeobecného vzorcaAccording to the present invention, there is provided a process for the preparation of cyclic nitrosamines of the general formula
NO kdeNO where
Ri, R2 reprezentujú —NOR 1, R 2 represent —NO
226538 alebo epoluzoskupenie —CH2—N—CH2, > I226538 or an epoluzo group —CH2 —N — CH2,> I
NO nitrolýzou hexametyléntetramínu, aplikovaného vo formě vodného roztoku a/aleho matečných lúhov z výroby hexametyléntetiramínu, v kyslom prostředí pri pH 1 až 6, spojenou ©o separácíou, stabilizáciou a/alebo úpravou produktu praním, uskutečněný v přítomnosti tenzidov, pričom sa používajú biologicky odbúrateřné a/alebo nepenivé teinzidy, najma zo skupiny oxyetylovaných mastných alkoholov všeobecného vzorceNO by nitrolysis of hexamethylenetetramine, applied in the form of an aqueous solution and / or mother liquors from the manufacture of hexamethylenetetiramine, in an acidic environment at pH 1 to 6, coupled with separation, stabilization and / or treatment by washing, in the presence of surfactants using biodegradable and / or non-foaming theinzides, in particular from the group of oxyethylated fatty alcohols of the general formula
R—OfCžHiOJnH, kde R je alkyl s počtom uhlíkových atómov Clo až Ci6 a počet mólov n je 3 až 16, samostatné alebo v zmesi is oxyetylovainýimi diglyceridmi mastných kyselin a/alebo s kopolymérmi na báze propylénoxidu a etyléinoxidu všeobecného vzorcaWherein R is alkyl having a carbon number of C10 to C16 and a number of moles of n is 3 to 16, alone or in admixture with oxyethylated fatty acid diglycerides and / or copolymers based on propylene oxide and ethylene oxide of the general formula
HO (C2H4O )x( QsHeO )y (CteHáO )XH, kde počet mólov etylenoxidu x+z je v rozmedzí 2 až 50 a počet mólov propylénoxidu y je 15 až 40, s výhodou 31,0, v množstve 0,005 až 2,5 °/o hmot,, vztiahnuté na izolovaný pradukt.HO (C 2 H 4 O) x (C 6 H 6 O) y (C 6 H 6 O) X H, wherein the number of moles of ethylene oxide x + z ranges from 2 to 50 and the number of moles of propylene oxide y is 15 to 40, preferably 31.0; 5% by weight, based on the isolated product.
Medzi výhody postupu podlia vynálezu je potřebné predovšetkým zařadit tú skutečnost, že aplikáciou technicky a ekonomicky 1'ahko dostupných nelonových biologicky odbúrateíiných a/alebo nepenivých tenzidov sa zvýši výťažnosť procesu, a tým aj ekonomika výroby. Okrem zivýšemia selektivity nitrózolýzy sa lepšie využijú suroviny a zvýši sa čistota a kvalita žiadaného produktu. Ďalej sa znížia nároky na kvalitu vstupujúceho hexametyléntetramínu, čo umožňuje využitie odpadajúclch matečných lúhov z výroby hexametyléntetramínu amoniakolizáciou formaldehydu. Použitím nepenivých tenzidov sa zamedzí stratám spósobeným úmikom reakčnej masy v podobě Hotovaného produktu.Among the advantages of the process according to the invention is, in particular, the fact that the application of technically and economically readily available non-ionic biodegradable and / or non-foaming surfactants increases the yield of the process and hence the economics of production. In addition to increasing the selectivity of nitrosolysis, raw materials are better utilized and the purity and quality of the desired product is improved. Further, the quality requirements of the incoming hexamethylenetetramine are reduced, allowing the use of the waste mother liquors from the production of hexamethylenetetramine by the ammoniacolization of formaldehyde. The use of non-foaming surfactants avoids losses due to the intake of the reaction mass in the form of a finished product.
Velkou přednostou je zemedzenie trvalého znečistenia vodných zdrojov používáním biologicky odbúrateliných tenzidov, čo přispěje k zníženiu rizika negativného vplyvu ,na zdravie l'udí, život vodného vtáctva, ina vodnú faunu a flóru, na bakterie a ryby, na technologický proces biologického a/alebo chemického čistenia odpadných vód. apod.A major advantage is the prevention of permanent pollution of water resources by the use of biodegradable surfactants, which will contribute to reducing the risk of negative impacts on human health, aquatic bird life, other aquatic and flora, bacteria and fish, the technological process of biological and / or chemical waste water treatment. etc.
Tenzidy, ktoré sa móžu použiť ako biologicky odbúratellné a/alebo nepenivé sú látky na báze oxyetylovaných mastných alkoholov s přídavným obsahom derivátov mastných kyselin, najmá ich diglyceridov a/alebo kopolymérov ma báze propylénoxidu a etylénoxidu, pričom sa upřednostňuje také zloženie, ktoré zaisťuje malú penivosť a l'ahkú odlbúratelnosť.Surfactants which can be used as biodegradable and / or non-foaming agents are those based on oxyethylated fatty alcohols with an additional content of fatty acid derivatives, in particular diglycerides and / or copolymers thereof, based on propylene oxide and ethylene oxide, preferably having a low foaming composition and easy degradability.
Uvedené tenzidy je možné aplikoivať buď jednotlivo alebo v zmesiach. Ich aplikácia sa realizuje přidáním naraz alebo postupné počas nitrozačného štiepenia a/alebo přidáním do premývacej vody.The surfactants may be applied either singly or in mixtures. Their application is effected by adding simultaneously or sequentially during the nitrosation cleavage and / or adding to the wash water.
K paraimetrom, ktoré ovplyvňujú potřebné mmožstvá přidávaného prostriedku, patří predovšetkým obsah aktívmych zložiek tenzidu, spósob aplikácie, zloženie aplikovaného roztoku hexametyléntetramínu. S prihliadinutím na uvedené skutečnosti pohybuje sa množstvo aplikovaného tenzidu obvykle v braniciach 0,005 až 2,5 % hmot, vztlalhnuté na izolovaný produkt a len výnimočne je potřebné přidávat váčšie množstvo.The paraimeters which affect the required amounts of the composition to be added include, in particular, the content of the active components of the surfactant, the method of application, the composition of the applied solution of hexamethylenetetramine. In view of the above, the amount of surfactant applied usually ranges from 0.005 to 2.5% by weight, based on the isolated product, and only exceptionally it is necessary to add a larger amount.
Následujúce příklady ukazujú niektoré typické příklady použitia biologicky odbúirateřných a/alebo nepenivých tenzidov.The following examples show some typical examples of the use of biodegradable and / or non-foaming surfactants.
Příklad 1Example 1
Do nitrozátoru si plochým dnom je předložený roztok připravený rozpuštěním 50,5 g hexametyléntetramínu v 59 ml vody. K tomuto roztoku je přidaný roztok obsahujúci 67,3 g dusitanu sodného v 150 ml vody. Za chladenia a miešania je pod hladinu roztokov (dopriestorumiešadlaj postupné dávkované 206,5 ml 22,1 %-nej kyseliny dusičnej tak, aby teplota reakčnej zmesi neprestúpila 12 °C. Miešanie je takej intenzity, že vylučujúci sa l,5-endometylén-3,7-dinltrózo-l,3,5,7-tetraazacyklooktán počas reakcie je vo <A flat bottom nitrosator is provided with a solution prepared by dissolving 50.5 g of hexamethylenetetramine in 59 ml of water. To this solution is added a solution containing 67.3 g of sodium nitrite in 150 ml of water. While cooling and stirring, 206.5 ml of 22.1% nitric acid are successively dosed below the stirrer so that the temperature of the reaction mixture does not exceed 12 [deg.] C. Stirring is at a rate such that the exiting 1,5-endomethylene-3 precipitates. The 7-dinltrose-1,3,5,7-tetraazacyclooctane during the reaction is in <
vznose. Po nadávkovaní kyseliny sa realizu- 1 je 15-minútové doreagovanie pri 12 až 15 °C.suspension. Following loading of the realizu- 1 is a 15-minute post-reaction at 12 to 15 ° C.
Potom je reakčná zmes zneutralizovaná cca 20 %-iným roztokom hydroxidu sodného na pH 8 až 9. Produkt sa izoluje filtráciou a «. suší v tenkej vrstvě 20 hodin pri 50 až 55 stupňoív Celsia.The reaction mixture is then neutralized with about 20% sodium hydroxide solution to pH 8-9. The product is isolated by filtration and filtration. dried in a thin layer for 20 hours at 50 to 55 degrees Celsius.
Nitrózolýza je ešte 3-krát opakovaná s tým rozdielom, že před dávkováním kyseliny dusičnej je k předloženým roztokom hexametyléntetramínu a dusitanu sodného přidané určité množstvo glukózy.The nitrosolysis is repeated 3 times, except that a certain amount of glucose is added to the present solutions of hexamethylenetetramine and sodium nitrite prior to nitric acid dosing.
Získané výsledky reprezentuje tabulka 1.The results obtained are shown in Table 1.
21SMS21SMS
T a: b' u 1' k a 1T a: b 'u 1' to a 1
Množstvo glukózy v reakčenej zmesi (:g)< %' hmotnosti na (g) hmotnost roztoku HMTAmount of glucose in the reaction mixture (: g) <% by weight per (g) weight of HMT solution
Výtažky DN-PT % hmot. oproti teoriiExtraction DN-PT% w / w against theory
Pr í k-1 ad 3Ex-1 ad 3
Příklad 2-Example 2-
Postupuje sa ako v příklade 1, s prídavsenntz) m nuodR/vrs §> Z‘0 b Azpyntg § g uioy oxyetylovainých mastných alkoholov, ktorá obsahuje; 8Qi %f> Jhmot. mastných alkoholov. CtoažCias 13 mok. etiylénoířidu;, 20 % hmot. maslnýffihi aflkaítetov’ Car až Cla: a. 4,5i mek. etylénoxidu!,, v/ podobě, vodného· roztoku — ofeisafe vody 15 % hmot. )· k roztoku hexiametyíéntetramínu. a dusitanu! sodteámu. Vzniká. 56,1 g produktu DNPT,. čo představuje 80(5°/o oproti teorii.The procedure is as in Example 1, with the addition of a zinc-containing fatty alcohol containing alcohol; 8Qi% f> Mass fatty alcohols. CtoažCias 13 mok. 20 wt. l ff ff až až až až až až až až 4,5i mek. % of ethylene oxide, in the form of an aqueous solution of 15% by weight of water; To the hexiamethylenetetramine solution. and nitrite! sodteámu. Arises. 56.1 g of DNPT. which represents 80 (5 ° / o vs. theory).
Postupom podlte příkladu· 1 je realizovaná .nitrozolýz-as za použití» modelových, rozfiotoov hexametyléntetramínw ai diusitami, sodného,. Roztok Ihexametyiéntetramíniu obsahuje vždy určité množstvo1 glukózy; Roztok dusitanu •pozostáva z; 67-,3 g. dusitanu sodného;, 27' g dusičnanui sodného a 130; g- vodý. Žata®®©* nie niitrozalýzy je realizované filtrácious kyslej reakcnej zrnesi s nasledujúcini premytím kyslého fiitraěného, koláča. DNTP roztokom 20 ml konc. amoniaku v 150 ml vody.In the process of Example 1, nitrosolysis is accomplished using modeled hexamethylenetetramine and sodium diusites. The hexamethylenetetramine solution always contains a certain amount of 1 glucose; The nitrite solution consists of; 67-, 3 g. sodium nitrite; 27 g of sodium nitrate and 130; g- aqueous. The rye®® © niitrozalysis is accomplished by filtration through an acid reaction mixture followed by washing of the acidic cake. DNTP solution 20 ml conc. ammonia in 150 ml of water.
Získané výsledky reprezentuje tabulka č. 2 T a hu ii k a 2The results are shown in Table no. 2 T and hu ii k and 2
Množstvo glukózy v reakčenej zmesi Výtažky DNP'.i,' (gj % hmotnosti na (g) % (hmot. oproti!teorii hmotnost roztoku ΗΜΊ!Amount of glucose in the reaction mixture Extracts DNP 'i,' (gj% by weight to (g)% (weight by weight of solution ΗΜΊ!
Pr ík 1 a di 4Example 1 a di 4
Postupom podta příkladu 1 a 3 sa ireali2uujj£ nitítolýzat © modelovými roztokmi: he»fc* imhíyiéwBetramínu.. a. dusitanu. .sodného: s< panfrd&atau© 3· g ghikózy. V jednotlivých, niittro zolýizach sú k roztoku hexametyléntetramínu přidané tenzidy Slovapon G-60 (zřmes oxyetylovaných mastných alkoholov a diglyceriotav mastnýck kyselá^, ktorá obsahuje· 75 %) hmot. mastných? alkoholov- Cio a& Ci® ser 4^5> mol. etyléaoxidui 25? %j hmot diglyceritdev/ mastných kyselíte (kysslitoy palmitavej; 2di až; 37' %> hmot.,, kyseliny- staarovejj 55? a& 75'%)hinot(., kyselina olejová. I,až3 θ/οΊοηοίλ,, kyselínai. myrtetavá? 2; až. 8? %) 'huňatý ,s. 201 mol. etylénoKidu,, v podOtte vodnáto®· rotí»·· kw — obsah vady 40 % .hmot.,, Slovapon hfi (zmes oxyetylouaných mastných- alkoholov, ktorá obsahuijp: 80 % hmot. mastných alkoholov Cio až Cí6 s 13 mol. etylénoxidu, 20 % hmot. mastných alkoholov Cio až Clo; s 4-5? mol. etylénoxidu, v podobě vodného roztoku' — ohaah védy--1*5- % hmot..] .a Stowanik NřB-70.: (izntea;. která? obsahuje 90 °/o; hmot., kopolymérui etylénomdiu s, propyiénoxidom vzorca·'Following the procedure of Examples 1 and 3, the nitrite is lysed with model solutions of hexamethylbetramine. nitrite. Sodium: s <panfrd & atau © 3 · g ghicosis. In individual niolysis, surfactants of Slovapon G-60 (a mixture of oxyethylated fatty alcohols and a diglyceride in fatty acid containing 75% by weight) are added to the hexamethylenetetramine solution. Fatty? alcohols - C 10 and C 18 ser 4? 5 mol. ethyléoxidui 25? % by weight of diglycerides / fatty acids (palmitic acid; 2di to 37% by weight of stearic acid 55% and 75% by weight), oleic acid, up to 3% / οΊοηοίλ, myrtetic acid. ? 2; up to 8?%) 'Bushy, p. 201 mol. Ethylene chloride in the waterborne substrate kw - defect content of 40% by weight, Slovapone hfi (a mixture of oxyethylated fatty alcohols containing: 80% by weight of C10 to C16 fatty alcohols with 13 mol% ethylene oxide, 20% by weight of C 10 to C 10 fatty alcohols with 4-5 mol% ethylene oxide in the form of an aqueous solution of science - 1 - 5 wt% and Stowanik NR-70: (izntea; which comprises 90% by weight of a copolymer of ethylene amide with propylene oxide of the formula
HO (C2H4O )x( GsHsO )y(fWáfflij^Hy kde x.+z je 5 a y je 31, 10 % hmot oleylaákoholu s 20 mol. etylénoxidu, v podobě vodného roztoku — ottsaih vody 30 %) hmot.). Iaoláeia se: rohí> podlá? příkladu! 3.HO (C 2 H 4 O) x (G 5 H 5 O) y (fWafflij ^ Hy where x. + Z is 5 and y is 31, 10 wt.% Oleyl alcohol with 20 mol. Iaoláeia se: horns> by? Example! Third
Výsledky reprezentuje následující tabulfe 3í.The results are represented by the following tabulfe 31.
Tabulka 3Table 3
Příklad 5Example 5
Postupuje sa ako v příklade 1, len s tým rozdielom, že modelovo připravený roztok hexametyléntetramínu je nahradený 99 ml matečných lúhov z výroby hexametylémtetramínu amoniakalizáciou formaldehydu. Tieto matečné luhy obsahujú 1,65 % hmot. potyolov Cs až C7, vyjádřených ako- glukóza a 518,2 g sušiny v 1000 ml (s obsahom maximálně 96 % hmot. hexametyléntetramínu) t. j, navážka hexametyléntetramínu robí 49,3 gramu.The procedure is as in Example 1, except that the modeled hexamethylenetetramine solution is replaced by 99 ml of mother liquors from the hexamethylenetetramine production by ammoniacalization of formaldehyde. These mother liquors contain 1.65 wt. of C 3 to C 7, expressed as glucose and 518.2 g of dry matter in 1000 ml (containing not more than 96% by weight of hexamethylenetetramine) m.p. The weight of hexamethylenetetramine is 49.3 grams.
V jednotlivých initrozolýzách je k matečným lúhom před reakciou přidané určité množstvo Slovaniku NT-70 [zmes ktorá obsahuje 90 % hmot. kopolyméru etylénoxidu s propylénoxidom vzorcaIn the individual initrozolysis, a certain amount of Slavic NT-70 [a mixture containing 90% by weight] is added to the mother liquors prior to the reaction. a copolymer of ethylene oxide with propylene oxide of the formula
HO (C2H4O )x( CsHeO) y (C2H4O) ZH, kde x+z je 5 a y je 31, 10 % hmot. oleylalkoholu s 20 mol. etylénoxidu, v podobě vodného roztoku — obsah vody 30 % hmot.]. Je sledované množstvo matečných lúhov z nitrozačného štiepeinia a u DNPT aktivačmá energia vzbuchu, stanovená podl'a Novotného. Výsledky reprezentuje tabulka č. 4.HO (C 2 H 4 O) x (C 5 H 6 O) y (C 2 H 4 O) Z H, wherein x + z is 5 and y is 31, 10 wt. of oleyl alcohol with 20 mol. ethylene oxide, in the form of an aqueous solution - water content of 30% by weight]. The amount of mother liquors from nitrosation cleavage and the DNPT activation energy determined according to Novotny are monitored. The results are represented in Table no. 4th
Tabulka 4Table 4
hexametyléntetramínu) poskytuje nitrozolýza 52,19 g DNPT, čo je 74,89 % oproti teórii.hexamethylenetetramine) gives nitrosolysis of 52.19 g of DNPT, which is 74.89% of theory.
Postupuje sa ako; v příklade 1, len s tým rozdielom, že množstvo hexametyléintetramínu je do reakcie birané vo formě roztoku obsahujúceho 430,3 g čistej substancie v 1000 ml. Vzniká 55,4 g DNPT, čo je 79,49 °/o hmot. oproti teorii.It proceeds as; in Example 1, except that the amount of hexamethylenintetramine is reacted in the form of a solution containing 430.3 g of pure substance in 1000 ml. 55.4 g of DNPT are obtained, which is 79.49% by weight. against theory.
Příklad 7Example 7
Postupuje s,a ako v příklade 6, len s tým rozdielom, že hexaimetyléntetramín je do reakcie braný vo formě zmesi roztoku a matečných lúhov z výroby menovanej substain.cie amoniakalizáciou vodného formaldehydu. Táto zmes obsahuje 430,3 g. I1 hexametyléntetramínu, 6,2 g.l-1 amínov počítaných ako imetylamín minimálně-1,1 g.l-1 amoniaku a 0,86 % himot. polyolov Cs až C7, počítaných ako glukóza. Z nitrozačného štiepenia hexametyléntetramínu v tejto podobě rezultuje 44,02 g DNPT, čo je 63,17 % oproti teorii. Po přidaní k zmesi hoře uvedeného zloženia Slovasolu O (oleyl-cetylalkohol s 20 až 25 mólami etylénoxidu) v mnložstveThe procedure is, and as in Example 6, except that hexaimethylenetetramine is reacted in the form of a mixture of the solution and mother liquors from the production of the said substance by ammoniacalization of aqueous formaldehyde. This mixture contains 430.3 g. 11 hexamethylenetetramine, 6.2 gl -1 amines calculated as imethylamine of at least -1.1 gl -1 ammonia and 0.86% himot. polyols Cs to C7, calculated as glucose. The nitrosation cleavage of hexamethylenetetramine in this form results in 44.02 g of DNPT, which is 63.17% of theory. When added to a mixture of the above formulation of Slovasol O (oleyl cetyl alcohol with 20 to 25 moles of ethylene oxide) in an amount of
Příklad 8Example 8
Pre nitrozačné štiepenie sú použité matečné luhy z výroby hexametyléntetraimínu, rovnakého zloženia ako v příklade 5. 10,5 ml týchto lúhov (5,22 g HMT) je v nitrolyzátore zrledené 65 ml vody a po vychladení na teplotu 0 °C je za dobrého miešani a ďalšieho chladenia započaté s dávkováním 85 ml kyseliny dusičinej (22,1 %-nej) a roztoku 15 g dusitanu sodného v 50 ml vody. Pri dávkovaní je teplota udržovaná v rozmedzí —5 až 0 °C. Doreagovanie je 15 minútové pri teplote —5 až 0 °C.The mother liquors from hexamethylenetetraimine production of the same composition as in Example 5 are used for nitrosation cleavage. 10.5 ml of these liquors (5.22 g HMT) are bleached with 65 ml of water in the nitrolizer and after cooling to 0 ° C, stirring well and further cooling started with the addition of 85 ml of nitric acid (22.1%) and a solution of 15 g of sodium nitrite in 50 ml of water. During dosing, the temperature is maintained at -5 to 0 ° C. The reaction was 15 minutes at -5 to 0 ° C.
Potom je R-Sol' izolovaná filtráciou a po premytí do neutrálnej reakcie filtrátu je vákuovo sušená pri 60 °C. Reakcia je realizovaná i v přítomnosti tenzidov Slovaponu N (zmes oxyetylovaných mastných alkoholov, ktorá obsahuje 80 % hmot. mastných alkoholov C10 až Cie s 13 mol. etylénoxidu, 20 %' hmot. mastných alkoholov C10 až Ct6 s 4,5 mol. etylénoxidu, v podobě vodného roztoku — obsah vody 15 °/o hmot.) a Slovanlku NT-70 [zmes, ktorá obsahuje 90 % hmot. kopolyméru etylénoxidu s propylénoxidom vzorceThen the R-Sol 'is isolated by filtration and after washing to neutral reaction of the filtrate is vacuum dried at 60 ° C. The reaction is also carried out in the presence of surfactants Slovapone N (a mixture of oxyethylated fatty alcohols containing 80% by weight of C10 to C18 fatty alcohols with 13 moles of ethylene oxide, 20% by weight of C10 to C16 fatty alcohols with 4.5 moles of ethylene oxide, in aqueous solution - water content 15% w / w) and Slovanl NT-70 [a mixture containing 90% by weight of water]. a copolymer of ethylene oxide with propylene oxide of the formula
HO (C2H4O) x (CsHeO) y (C2H4O )ZH, kde x+z je 5 a y je 31, 10 °/o hmot. oleylalboholu s 20 mol. etylénoxidu, v podobě vodného roztioku — obsah vody 30 % hmot.] v aplikovaných matečných lúihoch. Výsledky reprezentuje tabulka č. 5.HO (C 2 H 4 O) x (C 5 H 6 O) y (C 2 H 4 O) Z H, where x + z is 5 and y is 31, 10% w / w; oleylalcohol with 20 mol. ethylene oxide, in the form of an aqueous solution - a water content of 30% by weight] in the applied mother liquors. The results are represented in Table no. 5th
Tabulka 5Table 5
Druh a množstvo použitého tenzidu (g)Type and amount of surfactant used (g)
Výtažky R-Soli (g) % hmot. oproti teoriiExtracts R-Salts (g) wt. against theory
Slovapon N 0,1Slovapone N 0.1
Slovanik NT-70 0,0063 bez tenzidu —Slovanik NT-70 0,0063 surfactant-free -
Příklad 9Example 9
Postupuje sa ako v příklade 6, len s tým rozdielom, že rezultujúca suspenzia z nitrozačného štiepenia sa odfiltruje za nasledujúceho premytia filtračného koláča vodouThe procedure is as in Example 6, except that the resulting nitrosation cleavage slurry is filtered off, followed by washing the filter cake with water.
2,52.5
3,03.0
2,42.4
38,5438.54
46,2546,25
37,00 v množstve trojnásobnom na hmotnost rezultujúceho DNPT. Táto premývacia voda obsahuje tenzidy rovinakého druhu ako v příklade č, 4 v množstve 2,5 g na 1 kg suchého produktu. Vlhkosti koláča produktu sa pohybujú od 6 do 11 % hmot.37.00 in an amount three times the weight of the resulting DNPT. This washing water contains surfactants of the same kind as in Example 4 in an amount of 2.5 g per kg of dry product. The moisture content of the product cake ranges from 6 to 11% by weight.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS409481A CS226535B1 (en) | 1981-06-03 | 1981-06-03 | Method of freparing cyclic nitrosoamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS409481A CS226535B1 (en) | 1981-06-03 | 1981-06-03 | Method of freparing cyclic nitrosoamines |
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| Publication Number | Publication Date |
|---|---|
| CS226535B1 true CS226535B1 (en) | 1984-04-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS409481A CS226535B1 (en) | 1981-06-03 | 1981-06-03 | Method of freparing cyclic nitrosoamines |
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| CS (1) | CS226535B1 (en) |
-
1981
- 1981-06-03 CS CS409481A patent/CS226535B1/en unknown
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