Hexamine Production Technology

Hexamine, short for hexamethylenetetramine, another name: H promoting agent;

molecular formula: (CH2 )6 N4 ; molecular weight140.19; chemical structure:

Hexamine has a wide array of applications in various fields. It is used as hardener

in synthetic resin, curing agent in phenolic plastic, catalyst in amino plastic, vulcanization promoter (H) in rubber industry and anti-shrinkage agent in textile industry. Also it is employed as diuretic agent in pharmaceutics, disinfectant in food industry and raw material for synthesizing many amino compounds, e.g., pesticide in agriculture. Besides, mixed with caustic soda and phenol naphthalene, it can be used as the absorption agent of phosgene for anti-toxic mask; after nitrification, it can be applied to make strong explosives.

Section A. Hexamine Properties

Hexamine is a white color crystal shape powders, odorless with slightly sweet

taste. It has anaphylactic irritation to the skin; specific gravity: 1.331(20 ); flash point: 250; stored in the air, it is stable, but easy to absorb moisture and lump. Hexamine is flammable with colorless flame. Its melting point is 263. When heated to 100 at normal pressure, minor part of it will be sublimated and decomposed into methylamine. Hexamine has a very good solubility in water. At 25, its concentration in saturated aquous solution is 46.5%. Hexamine is a weak alkaline reagent with PH value: 8-8.5. When ammonia concentration increases, the solubility of hexamine in ammonia solution will decrease. Hexamine will be decomposed in presence of hydrochloric acid, sulphuric acid, acetic acid and salicylic acid to form formaldehyde, ammonia, sodium carbonate, and methylamine. The higher H+

concentration is, the faster the decomposition will take place.

Section B. Hexamine Production Technology

Hexamine is prepared either by liquid phase process or by gas phase process. Both processes use formaldehyde and ammonia as raw materials. In liquid phase method, 37% aqueous formaldehyde solution is employed to react with ammonia gas. The formed hexamine solution is dehydrated through evaporation, centrifuged, and dried to receive solid product. As certain amount of steam is consumed in the vaporization, concentration and drying process, the energy consuming is high. This process is superior in mature technology and simple operation. Also the size of obtained hexamine particle is big because of the use of evaporation port and relative long crystallization time. In gas phase method, formaldehyde gas directly converted from methanol is sent to the ammoniation reactor to react with ammonia gas in the saturated hexamine mother liquid to form hexamine product. The feature of this process is that formaldehyde latent heat and hexamine reaction heat is used to evaporate water under vacuum condition.Thus large amount of steam is saved and high purity product is received. 1. Liquid phase production process Liquid phase production process is that 37% aqueous formaldehyde solution reacts with ammonia gas to form hexamine and water in an exothermic way. The reaction equation is as following: 6CH2 O(liquid) + 4NH3 gasCH2 6 N 4 + 6H2O + 81Kcal/mol The process includes several parts, i.e., condensation reaction between formaldehyde and ammonia, hexamine evaporation, concentration, centrifuging and drying. Details are given below : Ammonia gas is filtered, mixed with formaldehyde solution in a certain proportion (ammonia excesses 0.8-1.2%, and then sent to the reactor to yield 24-27% hexamine solution. The reaction heat is transferred out by circulation cooler to keep reaction temperature at 60-65. Hexamine solution is pumped to film

evaporator to be concentrated to 60-65% under vacuum. The generated moisture is condensed . 60-65% hexamine solution is fed to the evaporation boiler for further dehydration and concentration under vacuum. When crystal grains are formed, the mother liquid is sent to the centrifuge for separation. The obtain solid is supplied to the gas flow dryer. After cyclone separation, hexamine is received as final product. In this liquid phase method, evaporation is a continuous process while evaporation port operation is in a batch form , which entails high labor intensity and more waste water. Besides, the use of formaldehyde solution and the batch operation of concentration result in impurities and side reaction. As both of them have negative influence on the product purity, mother liquid filtering device must be set in the process line. 2. Gas phase method production process Gas phase production process is that formaldehyde and ammonia gas go through condensation reaction in alkaline solution. The reaction equation is given below 6CH2 O(gas) + 4NH3 gasCH2 6 N4 + 6H2O +745.29 103Kcal/mol In order to promote the reaction to proceed towards hexamine yielding direction and avoid side reactions(such as the forming of trimethylamine ), which may affect product quality and increase consumption, reaction temperature must be properly controlled and excess ammonia must be supplied. The production details are as follows:

PFD of Gas Phase Method for Hexamine

High temperatured-formaldehyde gas from oxidator is directly pumped to the amination reactor; ammonia gas after filtration and measuring is also sent to the ammoniation reactor. The two gases are bubbled in hexamine mother liquid to react with each other to form hexamine. Formaldehyde latent heat and hexamine reaction heat is used to evaporate water under vacuum. Reaction temperature is controlled at 75-80. The formed hexamine in the amination reactor is sent to receiving tank through sealing port. The mother liquid is returned to amination reactor, while concentrated liquid is supplied to the centrifuge to separate liquid phase. The obtained hexamine solid from the centrifuge is sent to the dryer for further dehydration before final product is received Excess ammonia, with the evaporated gas from reactor, is fed to the ammonia absorption tower for absorption. The unabsorbed gas is condensed and vacuumed to give the final off- gas , which enters into incinerator for burning after scrubbing. The diluted ammonia solution goes through recovery in stripper tower, and then is returned to ammoniation reactor; while the diluted methanol solution goes through recovery in recovering tower and then is returned to evaporator. Gas phase method allows continuous and automatic operation, short process line, less side reactions and high purified products. Also less environmental pollution and consumption is ensured because of ammonia and methanol recovery.

Section C. Material Consumption Quota

Materials Consumption Quota (Calculated based on per ton of 37% formalin) No. 1 2 3 4 5 6 Name Formaldehyde 37% Ammonia100% Circulation Cooling Water Steam0.4mpa Electric Power Salt Free Water Unit t kg t t KW.h t Liquid Phase Process 3.5-3.6 540-550 300 4.0-5.0 200 2 Gas Phase Process 3.5 530 150 0.51.0 300 1-2

10000t/a Hexamine Plant

10000t/a Hexamine Plant

10000t/a Hexamine Plant

20000t/a Hexamine Plant