Amine Solution

To 5 ml. of water add 1-2 drops of the amine if the amine does not dissolve, add a drop or two of concentrated hydrochloric acid. Add 0-5-1 ml. of this amine solution to 2-3 ml. of the reagent an almost immediate precipitate indicates the presence of a primary amine. A slight turbidity indicates the presence of a primary amine as an impurity. (Primary aromatic amines generally require 2-3 minutes for the test. Urea and other amides, as well as amino acids, do not react.)... 

Meihylamine hydrochloride method. Place 100 g. of 24 per cent, methyl-amine solution (6) in a tared 500 ml. flask and add concentrated hydrochloric acid (about 78 ml.) until the solution is acid to methyl red. Add water to bring the total weight to 250 g., then introduce lSO g. of urea, and boil the solution gently under reflux for two and three-quarter hours, and then vigorously for 15 minutes. Cool the solution to room temperature, dissolve 55 g. of 95 per cent, sodium nitrite in it, and cool to 0°. Prepare a mixture of 300 g. of crushed ice and 50 g. of concentrated sulphuric acid in a 1500 ml. beaker surrounded by a bath of ice and salt, and add the cold methylurea - nitrite solution slowly and with mechanical stirring and at such a rate (about 1 hour) that the temperature does not rise above 0°. It is recommended that the stem of the funnel containii the methylurea - nitrite solution dip below the surface of the acid solution. The nitrosomethylurea rises to the surface as a crystalline foamy precipitate. Filter at once at the pump, and drain well. Stir the crystals into a paste with about 50 ml. of cold water, suck as dry as possible, and dry in a vacuum desiccator to constant weight. The yield is 55 g. (5). 

Determine the methylamine content of the commercial solution by titration with standard acid using methyl orange as indicator. Adjust the quantity of methyl-amine solution in accordance with the methylamine content for some commercial samples, the figure may be 33-40 per cent. 

So you can see that to make MDA or MDMA using either NH3 or MeNH2 one is going to have to think of a way to keep them in the fray. Strike s first impulse is to dissolve the amine in a solvent. But what solvent And would the reaction even work in any solvent Rhodium thinks that maybe an aqueous amine solution would work considering the clay is moistened with water anyway. 

Fig. 15. Schematic of the interfacial polymerization process. The microporous film is first impregnated with an aqueous amine solution. The film is then treated with a multivalent cross-linking agent dissolved in a water-immiscible organic fluid, such as hexane or Freon-113. An extremely thin polymer film...

Heterogeneous hydrogenation catalysts can be used in either a supported or an unsupported form. The most common supports are based on alurnina, carbon, and siUca. Supports are usually used with the more expensive metals and serve several purposes. Most importandy, they increase the efficiency of the catalyst based on the weight of metal used and they aid in the recovery of the catalyst, both of which help to keep costs low. When supported catalysts are employed, they can be used as a fixed bed or as a slurry (Uquid phase) or a fluidized bed (vapor phase). In a fixed-bed process, the amine or amine solution flows over the immobile catalyst. This eliminates the need for an elaborate catalyst recovery system and minimizes catalyst loss. When a slurry or fluidized bed is used, the catalyst must be separated from the amine by gravity (settling), filtration, or other means. 

Activated tertiary amines such as triethanolamine (TEA) and methyl diethanolamine (MDEA) have gained wide acceptance for CO2 removal. These materials require very low regeneration energy because of weak CO2 amine adduct formation, and do not form carbamates or other corrosive compounds (53). Hybrid CO2 removal systems, such as MDEA —sulfolane—water and DIPA—sulfolane—water, where DIPA is diisopropylamine, are aqueous alkaline solutions in a nonaqueous solvent, and are normally used in tandem with other systems for residual clean-up. Extensive data on the solubiUty of acid gases in amine solutions are available (55,56). 

P. Nasir and co-workers, "Solubility of CO2 and H2S in Amine Solutions," CNGPA Researd) Seminars Nov. 27, 1975. 

Other components in the feed gas may react with and degrade the amine solution. Many of these latter reactions can be reversed by appHcation of heat, as in a reclaimer. Some reaction products cannot be reclaimed, however. Thus to keep the concentration of these materials at an acceptable level, the solution must be purged and fresh amine added periodically. The principal sources of degradation products are the reactions with carbon dioxide, carbonyl sulfide, and carbon disulfide. In refineries, sour gas streams from vacuum distillation or from fluidized catalytic cracking (FCC) units can contain oxygen or sulfur dioxide which form heat-stable salts with the amine solution (see Fluidization Petroleum). 

Dow Chemical was developiag a similar process based on an amine solution as of this writing (1997). 

International Specialty Products (ISP) suppHes ethyl, isopropyl, and -butyl half-esters of PMVEMA as 50% solutions in ethanol or 2-propanol. Typical properties are shown in Table 8. These half-esters do not dissolve in water but are soluble in dilute aqueous alkaU and in aqueous alcohoHc amine solutions. The main appHcation for the half-esters is in hairsprays where they combine excellent hair-holding properties at high humidity without making the hair stiff or harsh. These half-esters are easily removed during shampooing, have a very low order of toxicity, and form tack-free films that exhibit good gloss, luster, and sheen (see Hair preparations). 

SolubiHty of carbon dioxide in ethanolamines is affected by temperature, amine solution strength, and carbon dioxide partial pressure. Information on the performance of amines is available in the Hterature and from amine manufacturers. Values for the solubiHty of carbon dioxide and hydrogen sulfide mixtures in monoethanolamine and for the solubiHty of carbon dioxide in diethanolamine are given (36,37). SolubiHty of carbon dioxide in monoethanolamine is provided (38). The effects of catalysts have been studied to improve the activity of amines and provide absorption data for carbon dioxide in both mono- and diethanolamine solutions with and without sodium arsenite as a catalyst (39). Absorption kinetics over a range of contact times for carbon dioxide in monoethanolamine have also been investigated (40). 

Experience in air separation plant operations and other ciyogenic processing plants has shown that local freeze-out of impurities such as carbon dioxide can occur at concentrations well below the solubihty limit. For this reason, the carbon dioxide content of the feed gas sub-jec t to the minimum operating temperature is usually kept below 50 ppm. The amine process and the molecular sieve adsorption process are the most widely used methods for carbon dioxide removal. The amine process involves adsorption of the impurity by a lean aqueous organic amine solution. With sufficient amine recirculation rate, the carbon dioxide in the treated gas can be reduced to less than 25 ppm. Oxygen is removed by a catalytic reaction with hydrogen to form water. 

Dry air is blown through the solution to remove the excess of ammonia, and the solution is then dissolved in its own volume of absolute alcohol. A sample of this solution is titrated with standard oxalic acid, litmus being used as an outside indicator (Note 3). The amount of oxalic acid (Note 4) necessary to form the acid salt is placed in a large evaporating dish and dissolved in 4 1. of 95 per cent alcohol. The amine solution is then slowly run into the acid with constant stirring. During the addition of the last half of the amine solution, the container must be cooled in order to avoid the formation of the neutral oxalate,... 

A recent article explains why the common practice of caustic addition is bad for amine systems. Heat stable salts do build up in amine systems causing reduction of the amine solution s effective capacity, corrosion, aggravation of foaming, and amine loss. 

Tests to simulate real-world amine plant operations have shown that caustic addition doesn t substantially improve solution corrosivity and in some cases corrosion rates increase. Maintenance of low heat stable salt anion levels is a better way to go. Concentrations as low as 250 ppm are encouraged and 5,000 to 8,000 ppm seem to be tolerable. Caustie doesn t reduce the heat stable salt content of amine solution. 

The temperature of the lean amine solution entering the absorber should be about 10°F higher than the inlet gas temperature to prevent hydrocarbon condensation and subsequent foaming. 

If I ever have to design an amine plant I will know, for example, that the temperature of the lean amine solution entering the absorber should be about 10°F higher than the inlet gas temperature to prevent hydrocarbon condensation and subsequent foaming, that the reboiler tube bundle should be placed on a slide about six inches above the bottom of the shell to provide good circulation, that about two percent of the total circulating flow should pass through the carbon towers, and many other necessary requirements. 

A typical amine system is shown in Figure 7-4. The sour gas enters the system through an inlet separator to remove any entrained water or hydrocarbon liquids. Then the gas enters the bottom of the amine absorber and flows counter-current to the amine solution. The absorber can be either a trayed or packed tower. Conventional packing is usually used for 20-in. or smaller diameter towers, and trays or structured packing for larger towers. An optional outlet separator may be included to recover entrained amines from the sweet gas. 

Commonly, amine absorbers include an integral gas. scrubber section in the bottom of the tower. This scrubber would be the same diameter as required for the tower. The gas entering the tower would have to pass through a mist eliminator and then a chimney tray. The purpose of this scrubber is to remove entrained water and hydrocarbon liquids from the gas to protect the amine solution from contamination. 

The rich amine solution from the absorber is flashed to a separator to remove any hydrocarbons. A small percentage of acid gases will also flash when the pressure is reduced. The dissolved hydrocarbons should flash to the vapor phase and be removed. Flowever, a small amount of hydrocarbon liquid may begin to collect in this separator. Therefore, a provision should be made to remove these liquid hydrocarbons. 

Typically the flash tanks are designed for 2 to 3 minutes of retention time for the amine solution while operating half full. 

A solution of 82 parts by weight of 7-chloromethyl-pyridine-hydrochloride in 60 parts of water is added dropwise, at 0 to 5°C, to 250 parts by weight of a 50% aqueous ethyl amine solution. The mixture is stirred for 1 hour at 60°C, whereupon it is cooled down and separated in the cold with solid potassium hydroxide. The oil formed is separated off, dried over potassium hydroxide and distilled. The ethyl-(7-picolyl)-amine formed boils over at 103° to 104°C under a pressure of 13 mm Hg. Its dihydrochloride melts at 198° to 200°C. 

To preclude thermal degradation of the amine solution, the reboiler pressure must be limited to 10 mm Hg absolute pressure. Total allowable pressure drop is 3 mm Hg. 

These processes are characterized by a high capability of absorbing large amounts of acid gases. They use a solution of a relatively weak base, such as monoethanolamine. The acid gas forms a weak bond with the base which can be regenerated easily. Mono- and diethanolamines are frequently used for this purpose. The amine concentration normally ranges between 15 and 30%. Natural gas is passed through the amine solution where sulfides, carbonates, and bicarbonates are formed. 

Rich amine from the bottom of the HjS contactor goes to a flash separator to remove dissolved hydrocarbons from the amine solution. The rich amine is pumped from the separator to the amine regenerator,... 

In the amine regenerator, the rich amine solution is heated to reverse the acid-base reaction that takes place in the contactor. The heat is supplied by a steam reboiler. The hot, lean amine is pumped from the bottom of the regenerator and exchanges heat with the rich amine in the lean-rich exchanger and a cooler before returning to the contactor. 

A portion of the rich amine flows through a particle filter and a carbon bed filter. The particle filters remove dirt, rust, and iron sulfide The carbon filter, located downstream of the particle filters, remo cs residual hydrocarbons from the amine solution. 

The thermolysis of aryl azides in alcoholic solution has been used to prepare 2-alkoxy-37f-azepines. Thermolysis of 3-azidophenyl methyl ketone in methanol in a sealed ampule furnishes a mixture of the 6-acetyl- (36a) and 4-acetyl-2-methoxy-3//-azepine (37a) in superior yields to those obtained in the corresponding photolytic reaction.78 Other 3-substituted azides behave similarly, with a preference for the 6-substituted isomers 36, as is observed for azide photolyses in amine solutions. 

Photolysis of aryl azides in amine solution, with a tertiary amine as cosolvent to promote stabilization of the singlet nitrene, has met with some success. For example, the yield of 2-piperidino-3 W-azepme. obtained by the photolysis of phenyl azide in piperidine, is increased from 35 to 58% in the presence of A A /V. /V -tetramethylethylenediamine (TMLDA).180 Also, an improved yield (36 to 60 %) of A,(V-diethyl-3W-azepin-2-amine (38, R = Et) can be obtained by irradiating phenyl azide in triethylamine, rather than in dicthylaminc, solution.181 Photolysis (or thermolysis) of phenyl azide in TMEDA produces, in each case, 38 (R = Et) in 40% yield.181 In contrast, irradiation of phenyl azide in aniline with trimethylamine as cosolvent furnishes jV-phenyl-377-azepin-2-amine (32, R = Ph) in only low yield (2%).35... 

Nucleophilic displacement of the butoxy group in 2-butoxy-3//-azepine (1) by the use of excess secondary amine is preferred by some workers64 to the photolysis or thermolysis of aryl azides, or the deoxygenation of nitro- or nitrosoarenes in amine solution, as a preparative route to Ar,Ar-dialkyl-3//-azcpin-2-amines, e.g. 2,... 

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