MORPHOLINE

MORPHOLINE

CAS No: 110-91-8
EC No: 203-815-1

Synonyms:

Morpholine; Tetrahydro-1, 4-oxazine; Diethylenimide oxide; 1,4-Oxazinane; Tetrahydro-1,4-oxazine; Diethylene imidoxide; Diethylene oximide; Tetrahydro-p-oxazine; 1-Oxa-4-azacyclohexane; Diethyleneimide oxide; Drewamine; morpholin; Tetrahydro-2H-1,4-oxazine; Tetrahydro-p-oxazine; p-Isoxazine, tetrahydro-; Tetrahydro-1,4-isoxazine; 2H-1,4-Oxazine, tetrahydro-; 4H-1,4-Oxazine, tetrahydro-; Tetrahydro-4H-1-4-oxazine; [UN2054]; [Flammable liquid]; morfoline; morfolin; Tetrahydro-p-isoxazine; morphline; morpho line; morpholine-; EINECS 263-172-8; 4H-1, tetrahydro-; 1,4$l^{2}-oxazinane; EC 203-815-1; Tetrahydro-1, 4-isoxazine; Tetryhydro-2H-1,4-oxazine; Tetrahydro-4H-1,4-Oxazine; Oxazinanes; C4H9NO; 1,4-Oxazinan; MORPHOLINE; 1-Oxa-4-azacyclohexane; tetrahydro-1,4-oxazine; Diethylene imide oxide; Tetrahydro-p-isooxazine; Diethylenimide oxide; 1-Oxa-4-azacyclohexane; Tetrahydro-1,4-isooxazine; Diethylenoximid; Tetrahydro-1,4-oxazin; Tetrahydro-p-oxazin; Diethylenimidoxid; O (CH₂CH₂) ₂NH; 1-oxa-4-azacyclohexane; 1, 4-oxazinan; tetrahydro-2h-1, 4-oxazine; tetrahydro-1, 4-oxazine; tetrahydro-1, 4-isoxazine; diethylene oximide; diethyleneimide oxide; diethylene imidoxide 1; 1,4-Oxazinan; Morpholine; MORPHOLINE,ACS; 1-Oxa-4-azacyclohexane; tetrahydro-1,4-oxazine; perhydro-1,4-oxazine; Morpholine, 99+%; C4H9NO; CAS Number-110-91-8; 1-oxa-4-azacyclohexane; diethyleneimide oxide; diethylene imidoxide; diethylene oximide; diethylenimide oxide; drewamine; p-isoxazine; tetrahydro; tetrahydro-1,4-oxazine; tetrahydro-2h-1,4-oxazine; tetrahydro-p-oxazine, 1L, 99% min. (GC), 27, 5; [13C4]-Morpholine; Drewamine-13C4; 1-Oxa-4-azacyclohexane-13C4; Diethylenimide Oxide-13C4; 2H-1,4-Oxazin; Diethylenimide Oxide-d8; Morpholine-d8; Tetrahydro-2H-1,4-oxazine-d8; Drewamine-d8; 1-Oxa-4-azacyclohexane-

MORPHOLINE

Morpholine is an organic chemical compound having the chemical formula O(CH2CH2)2NH. This heterocycle features both amine and ether functional groups. Because of the amine, morpholine is a base; its conjugate acid is called morpholinium. For example, treating morpholine with hydrochloric acid makes the salt morpholinium chloride.

Morpholine is often produced industrially by the dehydration of diethanolamine with sulfuric acid.

Morpholine can be used as a buffer component in the separation of peptides and pathogenic lipopolysaccharides during on-line chromatographic preconcentration coupled to capillary zone electrophoresis–electrospray mass spectrometry (cPC–CZE–ES-MS) analysis from colony isolates.

Morpholine (1,4-tetrahydro-oxazine) is a simple heterocyclic compound that has great industrial importance and a wide range of applications. This chemical compound and its derivatives have been used as rubber additives, corrosion inhibitors, solvents, optical brighteners, antioxidants and in the manufacture of a range of drugs and herbicides. Consequently, morpholine can occur in a number of industrials effluents and can be disseminated in the environment. Morpholine is subject to N-nitrosation by nitrites and this reaction gives the potent mutagen N-nitrosomorpholin. These inconveniences can be avoided by elimination of morpholine from wastewater and effluents by biological treatments.

This chemical compound and its derivatives have been used as rubber additives, corrosion inhibitors, solvents, optical brighteners, antioxidants and in the manufacture of a range of drugs and herbicides. Consequently, morpholine can occur in a number of industrials effluents and can be disseminated in the environment.

Morpholines have been produced by various methods. For example, it is known to produce morpholine by the intramolecular dehydration of diethanolamine by means of sulfuric acid. This process is inconvenient in that it requires the handling of large quantities of sulfuric acid and caustic and involves the disposal of considerable quantities of by-product sodium sulfate. Morpholine has also been obtained as a by-product of the reaction of diethylene glycol with ammonia to produce Z-(Z-hydroxyethoxy) ethylarnine as the main product. This latter preparation has the disadvantage that the yields of morpholine are exceedingly low, resulting in an economically unattractive process when morpholine is the desired product. In contrast with the known methods, the process of the instant invention produces morpholines in high yields from readily available and relatively inexpensive glycols.

In accordance with this invention, a dialkylene glycol, described hereinabove, and including such glycols as diethylene glycol, dipropylene glycol, di-l,2-butylene glycol, di-2,3-butylene glycol, is reacted with ammonia in the presence of hydrogen and a hydrogenation catalyst to produce morpholines. The term morpholines employed herein, is used in the generic sense and is meant to in- (ilude the compound from which the name is derived and the carbon substituted alkyl and aryl derivatives thereof. Thus, for example, this term includes morpholine and its mono, di, tri, and tetra alkyl or aryl substituted derivatives. In general, the substituted group will be a lower alkyl radical. It is important to note that only those glycols having the hydroxyl radical attached to a primary or secondary carbon atom are suitable for this reaction.

The process of this invention is generally conducted at an elevated temperature and under pressure. The reaction temperature, therefore, may be between about 150 C. to about 400 (1., although it has been found preferable to operate in the relatively narrow temperature range between 200 C. to 300 C. Desirably, the process is conducted under relatively high pressures ranging from about 30 to about 400 atmospheres. As a general rule, however, operation of the process between 65 to 225 atmospheres is preferred.

The presence of hydrogen is critical for the proper and efficient conduct of the instant process. While it is not necessary for hydrogen to constitute the entire at- 3,15 1,1 12 Patented Sept. 29, 1964 mosphere within the reaction vessel, it is necessary that the hydrogen partial pressure amount to a substantial part of the reaction atmosphere. Thus, the hydrogen should contribute at least 10 and preferably between 20 to 200 atmospheres of pressure to the total pressure in the system. Generally, the reaction vessel is swept clean with hydrogen gas and thereafter a predetermined amount of hydrogen is pumped into the sealed vessel. When the vessel is heated to bring it up to reaction temperatures, the hydrogen and reactants contained therein will bring the total pressure into the operating range indicated above.

The effect of hydrogen partial pressure on the process is best illustrated by the data shown in Table I, which was obtained from reacting diethylene glycol and ammonia at diiferent hydrogen partial pressures:

A large number of hydrogenation catalysts may be employed in this process. Such catalysts, also known as hydrogenation-dehydrogenation catalysts, include one or more of the metals from the group including copper, nickel, cobalt, chromium, molybdenum, manganese, platinum, palladium and rhodium and the oxides of these metals. The metals or their oxides may be employed in combination with the normally nonreducible oxides such as chromium oxide Cr O molybdenum oxide M0 0 and manganese oxide MnO. The amount of the nonreducible oxide employed may be varied considerably but preferably should be present in minor amounts. The preferred catalysts, that is those most effective for the reaction, are the metals or oxides of copper, nickel, cobalt and chromium. A particularly satisfactory catalyst is one in which the active components consist essentially of mole percent nickel, 22 mole percent copper and 1.6 mole percent chromium. This catalyst is readily prepared by ignition of a mixture of the corresponding nitrate salts followed by a reducing treatment, although other well known means of preparation may be employed.

The catalyst may be carried on an inert support, such as silica, Filtros and alumina, and is suitable, either with or without a support, for use in a batch process or in a fixed-bed continuous flow system. In a batch process, the amount of catalyst generally employed is between about 5% to 20% of the weight of the glycol.

In the event that the catalyst isin the metal oxide form, it may be directly introduced in the reaction zone or prereduced and subsequently introduced in the reaction zone. Both methods are generally suitable since the reaction is conducted under reducing conditions.

The aforementioned catalysts may be modified to obtain better results. Thus, suitable modifiers or catalyst stabilizers, such as sodium and potassium sulfate, may be deposited on the catalyst. These are generally effective for prolonging the catalyst life.

The ratio of reactants, that is the ratio of ammonia to glycol, has a surprising effect on the efficiency of this process. While the process may be conducted by reacting equal molar amounts of ammonia and glycol, it has been observed that if there is a molar excess of ammonia the yields of the desired product are sharply increased. Optimum yields will be obtained when the molar ratio of ammonia to glycol is about 3:1. Molar ratios may be employed in the range from 1:1 to about 10:1. It is 3: not necessary that the reagents for this reaction be in an anhydrous condition. The following table relating to the reaction of diethylene glycol with ammonia illustrates how conversion to morpholine is affected by changes in the proportion of reactants.

Morpholine is a pale hygroscopic liquid with the chemical formula of O(CH2CH2)2NH free of foreign matter. It bears its characteristic amine odour that is detectable above 0.1 ppm concentration in boiler feed. It is a widely used neutralizing amine in combating carbonic acid corrosion in condensate return lines of steam boiler systems. It volatilizes and condenses with the steam from the boilers, thereby affording protection to the lines, which otherwise would be subjected to corrosion from the carbonic acid present in the steam condensate. Its vapours protect silver and other metals against corrosion and tarnishing by acrid fumes, such as  sulphur dioxide and hydrogen sulfide.

Morpholine is a common additive, in parts per million concentrations, for pH adjustment in both fossil fuel and nuclear power plant steam systems. Morpholine is used because its volatility is about the same as water, so once it is added to the water, its concentration becomes distributed rather evenly in both the water and steam phases. Its pH-adjusting qualities then become distributed throughout the steam plant to provide corrosion protection. Morpholine is often used in conjunction with low concentrations of hydrazine or ammonia to provide a comprehensive all-volatile treatment chemistry for corrosion protection for the steam systems of such plants. Morpholine decomposes reasonably slowly in the absence of oxygen at the high temperatures and pressures in these steam systems.

Morpholine is used as a boiler water treatment additive in steam systems of power plants and refineries. It forms an even wax like coating as morpholine oleate. It prevents decomposition of a chlorinated hydrocarbon in a composition containing the chlorinated hydrocarbon and a large amount of water. It is often used in conjunction with low concentrations of hydrazine or ammonia to provide a comprehensive all-volatile boiler water treatment chemistry for corrosion protection for the steam systems of such plants. Morpholine decomposes reasonably slowly in the absence of oxygen at the high temperatures and pressures in these steam systems. Because of its volatility being the same as water, upon addition to water, its concentration becomes distributed rather evenly in both the water and steam phases. Its pH-adjusting qualities become more distributed throughout the steam plant to provide corrosion protection.

Key Features & Benefits of Morpholine:

Prevents corrosion due to stress cracking

Reduces blow down requirement

Compatible with other boiler water treatment chemicals

Returns to the feed line with the condensate return so raises the feed water pH

Corrosion of metal aerosol containers and valves can be prevented by use of low levels of morpholine. It increases the pH of boiler water to protect boiler against corrosion. Due to its amine based formulation, it does not add salt to the boiler and hence does not contribute to the TDS, which results in reduced blow down and fuel savings. Morpholine can be used in all types, size and pressure of boilers.

Morpholine is an organic chemical compound having the chemical formula O(CH2CH2)2NH. This heterocycle features both amine and ether functional groups. Because of the amine, morpholine is a base; its conjugate acid is called morpholinium.

The morpholine chemical is a colorless hygroscopic liquid with a particular smell (smells like ammonia or fishy smell). It is entirely miscible with water, as well as with lots of organic solvents. But the morpholine solubility is restricted in an alkaline aqueous liquid.

Morpholine has a low distribution ratio and is commonly blended with other amines. The short distribution ratio makes morpholine effective on short run systems and also for the protection of steam turbines. 

Form: liquid

Colour: colourless

Odour: amine-like

pH: 11

Melting point: -5 °C

Boiling point/boiling range: 129 °C at 1,013 hPa,

Flash point: 32 °C at 1,013.25 hPa

Lower explosion limit: 1.4 %(V)

Upper explosion limit: 15.2 %(V)

Vapour pressure: 9.8 hPa at 20.3 °C

Viscosity, dynamic 2.23 mPa.s at 20 °C

Ignition temperature: 275 °C

Viscosity, kinematic: 2.2 mm2/s at 20 °C

First aid measures

First aider needs to protect himself.
After inhalation: fresh air. Call in physician.
If breathing stops: mouth-to-mouth breathing or artificial respiration.
In case of skin contact: Take off immediately all contaminated clothing. Rinse skin with water/ shower. Call a physician immediately.
After eye contact: rinse out with plenty of water. Immediately call in ophthalmologist. Remove contact lenses.
After swallowing: make victim drink water (two glasses at most), avoid vomiting (risk of perforation). Call a physician immediately. Do not attempt to neutralise.

Most important symptoms and effects, both acute and delayed:
Irritation and corrosion, Cough, Shortness of breath
Risk of blindness!

Firefighting measures

Suitable extinguishing media:
Water, Foam, Carbon dioxide (CO2), Dry powder

Vapours are heavier than air and may spread along floors.
Forms explosive mixtures with air at elevated temperatures.
Development of hazardous combustion gases or vapours possible in the event of fire.

Personal precautions, protective equipment and emergency procedures

Advice for non-emergency personnel: Do not breathe vapours, aerosols. Avoid substance contact. Ensure adequate ventilation. Keep away from heat and sources of ignition. Evacuate the danger area, observe emergency procedures, consult an expert.

Environmental precautions
Do not let product enter drains. Risk of explosion.

Methods and materials for containment and cleaning up
Cover drains. Collect, bind, and pump off spills. Observe possible material restrictions (see sections 7 and 10). Take up carefully with liquid-absorbent material.

Precautions for safe handling
Advice on safe handling
Observe label precautions.
Work under hood. Do not inhale substance/mixture. Avoid generation of vapours/aerosols.
Advice on protection against fire and explosion
Keep away from open flames, hot surfaces and sources of ignition. Take precautionary measures against static discharge.
Hygiene measures
Immediately change contaminated clothing. Apply preventive skin protection. Wash hands and face after working with substance.

Conditions for safe storage, including any incompatibilities
Storage conditions
Keep container tightly closed in a dry and well-ventilated place. Keep away from heat and sources of ignition. Keep locked up or in an area accessible only to qualified or authorised persons.
Recommended storage temperature see product label.

UN number: UN 2054

Proper shipping name: MORPHOLINE

Class: 8 (3)

Packing group: I

Environmentally hazardous

Tunnel restriction code: D/E