Ammonia, purification

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Fig. 38. Caustic purification system a, 50% caustic feed tank b, 50% caustic feed pumps c, caustic feed preheater d, amonia feed pumps e, ammonia feed preheater f, extractor g, trim heater h, ammonia subcooler i, stripper condenser j, anhydrous ammonia storage tank k, primary flash tank 1, evaporator reboiler m, evaporator n, caustic product transfer pumps o, purified caustic product cooler p, purified caustic storage tank q, ammonia stripper r, purified caustic transfer pumps t, overheads condenser u, evaporator v, evaporator vacuum pump w, aqueous storage ammonia tank x, ammonia scmbber y, scmbber condenser 2, ammonia recirculating pump aa, ammonia recycle pump. CW stands for chilled water.

The technology of urea production is highly advanced. The raw materials requited ate ammonia and carbon dioxide. Invariably, urea plants ate located adjacent to ammonia production faciUties which conveniently furnish not only the ammonia but also the carbon dioxide, because carbon dioxide is a by-product of synthesis gas production and purification. The ammonia and carbon dioxide ate fed to a high pressure (up to 30 MPa (300 atm)) reactor at temperatures of about 200°C where ammonium carbamate [111-78-0] CH N202, urea, and water ate formed. 

There has been an increasing interest in utilising off-gas technology to produce ammonia. A number of ammonia plants have been built that use methanol plant purge gas, which consists typically of 80% hydrogen. A 1250 t/d methanol plant can supply a sufficient amount of purge gas to produce 544 t/d of ammonia. The purge gas is first subjected to a number of purification steps prior to the ammonia synthesis. 

Feedstock Purification Manufacture of Synthesis Gases Hydrogen, Ammonia, Methanol, product bulletin. United Catalysts, Inc., Louisville, Ky. 

Ammonium lactate [34302-65-3] ia coaceatrated aqueous solutioas has beea coaverted to ammonia and the ester by alcoholysis at temperatures ranging from 100—200°C usiag a variety of alcohols and water entrainers, such as toluene. Ester yields ranging from 50—80% were obtained. This method has also been suggested as a recovery and purification method from impure solutions of lactate (29). However, a considerable amount of the lactate is not converted to the recoverable ester and is lost as lactamide (6). 

The removal of copper from the pregnant nickel solution in the Sherritt-Gordon process is an example of purification by precipitation of a fairly insoluble compound. First, in the copper boil step, ammonia is driven off by heating the solution, and some copper sulfide precipitates. The residual copper is removed by a dding hydrogen sulfide for the chemical precipitation of mote copper sulfide. 

Gas Reduction. The use of a gaseous reduciag agent is attractive because the metal is produced as a powder that can easily be separated from the solution. Carbon dioxide, sulfur dioxide, and hydrogen can be used to precipitate copper, nickel, and cobalt, but only hydrogen reduction is appHed on an iadustrial scale. In the Sherritt-Gordon process, the excess ammonia is removed duting the purification to achieve a 2 1 ratio of NH iNi ia solution. Nickel powder is then precipitated by... 

Trickle bed reaction of diol (12) using amine solvents (41) has been found effective for producing PDCHA, and heavy hydrocarbon codistiUation may be used to enhance diamine purification from contaminant monoamines (42). Continuous flow amination of the cycloaUphatic diol in a Hquid ammonia mixed feed gives >90% yields of cycloaUphatic diamine over reduced Co /Ni/Cu catalyst on phosphoric acid-treated alumina at 220°C with to yield a system pressure of 30 MPa (4350 psi) (43). 

A number of perhalides aie known, and one of the most stable is ammonium tetiachloioiodide [19702 3-3] NH IQ. Ammonia reacts with chlorine in dilute solution to give chloramines, a reaction important in water purification (see Cm,ORAMINES AND BROMAMINEs). Depending upon the pH of the water, either monochloramine [10599-90-3] NH2CI, or dichloramine [3400-09-7] NHCI2, is formed. In the dilutions encountered in waterworks practice, monochloramine is neady always found, except in the case of very acidic water (see Bleaching AGENTS Water). 

Steam-Reforming Natural Gas. Natural gas is the single most common raw material for the manufacture of ammonia. A typical flow sheet for a high capacity single-train ammonia plant is iadicated ia Figure 12. The important process steps are feedstock purification, primary and secondary reforming, shift conversion, carbon dioxide removal, synthesis gas purification, ammonia synthesis, and recovery. 

Final Purification. Oxygen containing compounds (CO, CO2, H2O) poison the ammonia synthesis catalyst and must be effectively removed or converted to inert species before entering the synthesis loop. Additionally, the presence of carbon dioxide in the synthesis gas can lead to the formation of ammonium carbamate, which can cause fouHng and stress-corrosion cracking in the compressor. Most plants use methanation to convert carbon oxides to methane. Cryogenic processes that are suitable for purification of synthesis gas have also been developed. 

Ammonium bicarbonate is produced as both food and standard grade and the available products are normally very pure. Although purification is possible by sublimation at low temperatures, it is more economical to prepare the desired product directiy by using ammonia and carbon dioxide of high purity. 

Cyclohexanone oxime is converted quantitatively to caprolactam by Beckmann rearrangement in the presence of oleum, which is of sufficient strength to consume the several percent water in the molten oxime. The reaction mass is neutralized with aqueous ammonia to a cmde caprolactam layer and a saturated solution of ammonium sulfate. Approximately 1.5 kg of the total 4.4 kg ammonium sulfate per kilogram of caprolactam is produced in this step. Purification is by multistage vacuum crystallization from aqueous solution in neatly quantitative yield. 

The oxime is converted to caprolactam by Beckmann rearrangement neutralization with ammonia gives ca 1.8 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. A no-sulfate, extraction process has been described, but incineration of the ammonium bisulfate recovers only sulfur values and it is not practiced commercially (14). 

Toray. The photonitrosation of cyclohexane or PNC process results in the direct conversion of cyclohexane to cyclohexanone oxime hydrochloride by reaction with nitrosyl chloride in the presence of uv light (15) (see Photochemical technology). Beckmann rearrangement of the cyclohexanone oxime hydrochloride in oleum results in the evolution of HCl, which is recycled to form NOCl by reaction with nitrosylsulfuric acid. The latter is produced by conventional absorption of NO from ammonia oxidation in oleum. Neutralization of the rearrangement mass with ammonia yields 1.7 kg ammonium sulfate per kilogram of caprolactam. Purification is by vacuum distillation. The novel chemistry is as follows ... 

The residue is leached to give cesium sulfate solution, which can be converted to cesium chloride by ion exchange on Dowex 50 resin and elution with 10% HCl, treatment using ammonia or lime, to precipitate the alurninum, or by solvent extraction, followed by purification at neutral pH using hydrogen peroxide or ammonia. 

Other options for the purification of CA include dissolution in hot water, aqueous ammonia, aqueous formaldehyde, or hot dimethylformamide followed by filtration to remove most of the impurities. The CA is recoverable by cooling the aqueous solution (84), acidifying the ammonium hydroxide solution (85), or cooling the dimethylform amide solution with further precipitation of CA by addition of carbon tetrachloride (86). Sodium hydroxide addition precipitates monosodium cyanurate from the formaldehyde solution (87). 

Ethanolamines. These are produced by the reaction of ethylene oxide and ammonia (see Alkanolamines). Approximately one-third of the production is used in detergents. Other appHcations include natural gas purification, cosmetics, metalworking, textiles, and chemical intermediates (282). 

Gas purification or the removal of relatively small amounts of impurities such as CO2, CO, COS, SO2, H2S, NO, and others from air, natural gas, hydrogen for ammonia synthesis, and others... 

Cellulose for chromatography is purified by sequential washing with chloroform, ethanol, water, ethanol, chloroform and acetone. More extensive purification uses aqueous ammonia, water, hydrochloric acid, water, acetone and diethyl ether, followed by drying in a vacuum. Trace metals can be removed from filter paper by washing for several hours with O.IM oxalic or citric acid, followed by repeated washing with distilled water. 

Acids that are solids can be purified in this way, except that distillation is replaced by repeated crystallisation (preferable from at least two different solvents such as water, alcohol or aqueous alcohol, toluene, toluene/petroleum ether or acetic acid.) Water-insoluble acids can be partially purified by dissolution in N sodium hydroxide solution and precipitation with dilute mineral acid. If the acid is required to be free from sodium ions, then it is better to dissolve the acid in hot N ammonia, heat to ca 80°, adding slightly more than an equal volume of N formic acid and allowing to cool slowly for crystallisation. Any ammonia, formic acid or ammonium formate that adhere to the acid are removed when the acid is dried in a vacuum — they are volatile. The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (Ed.), Fatty Acids, 2nd Edn, part 3, Chap. 20, Interscience, New York, 1964. 

Amides are stable compounds. The lower-melting members (such as acetamide) can be readily purified by fractional distillation. Most amides are solids which have low solubilities in water. They can be recrystallised from large quantities of water, ethanol, ethanol/ether, aqueous ethanol, chloroform/toluene, chloroform or acetic acid. The likely impurities are the parent acids or the alkyl esters from which they have been made. The former can be removed by thorough washing with aqueous ammonia followed by recrystallisation, whereas elimination of the latter is by trituration or recrystallisation from an organic solvent. Amides can be freed from solvent or water by drying below their melting points. These purifications can also be used for sulfonamides and acid hydrazides. 

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