Paraformaldehyde Production Technology

After many years development, Chinas formaldehyde industry has made big progress in production scale, output, quality and technology, and has approached or reached the international advanced level in many aspects, however, one of formaldehydes down stream products Paraformaldehyde has a broader space for development.

Section A. Paraformaldehyde Properties

Paraformaldehyde, short for PF, is a white solid either in powder form or particle form. It is an important linear polymer in chemical industry, molecular formula (CH2 O)n ,; molecular weight 30 n; density 1.39 (water=1.0), melting point: 120-170; flash combustion :510 point: 71 ; ignition temperature: 300-410; KJ/mol; heat of

KJ/mol; heat of formation:177

vapor pressure:

0.19Kpa/25; low explosion limit of powder dust: 40g/m3 . Paraformaldehyde can be slowly depolymerized to formaldehyde gas at ambient temperature and form formaldehyde water solution. Therefore, it has most of formaldehydes properties. Paraformaldehyde is a mixture of formaldehyde and HO(CH2 O)nH etc.

Paraformaldehyde can be divided into tow types. One is low polymerization degree paraformaldehyde, and the other is solid paraformaldehyde. These two types of PF are uaually distinguished by polymerization degree n( the number of CH2 O- in the chain). Low polymerization degree paraformaldehyde(n100), loose with uniform grains, is easy to dissolve in water and can be depolymerized thoroughly. It is the ideal raw material for formaldehyde, and an excellent substitute for industrial formaldehyde. Thereby it has huge development value and potential.

Section B. Paraformaldehyde Application

Paraformaldehyde is mainly used in Herbicides: synthesis of

glyphosate(accounting for 70-80% of paraformaldehyde use), butachlor, acetochlor and. Medicine and pharmaceutics: production of vitamin A. Coatings: synthesis

of high grade automobile paint.

Resins: preparation of resins such as ion

exchanging resin, melamine resin and phenolic etc. Take phenolic resin preparation for an example, paraformaldehyde is employed to replace 37% industrial formaldehyde. As a result, thermoplastic and thermosetting phenolic resin of high quality is produced; moreover, waste water discharge can be decreased dramatically; also material consumption can be curtailed by over 10%.

Section C. Paraformaldehyde Production Process

So far, there are two paraformaldehyde production processes. One is vacuum drying process with rake, the other is spray drying process. 1. Rake Type Vacuum Drying Process 37% formaldehyde is concentrated via dehydration to give 65% formaldehyde, which is sent to rake type vacuum dryer for further dehydration until dry paraformaldehyde powder is obtained. The whole drying process is operated under vacuum. The 10-15% diluted formaldehyde in evaporation condensate is sent back to formaldehyde sector to form 37% formaldehyde for sale or for methylal and hexamine production. This process involves batch operation. For each batch, the formaldehyde-feeding amount is about 4-5m3 and the drying lasts 4-6 hours. Thus long production period as well as low capacity is inevitable. 2.Spray Drying Process First the concentration of formaldehyde is increased from 37% to 85% via two-stage vacuum concentration. Then 85% formaldehyde is pumped to spray dryer for pulverization and dehydration until high concentrated formaldehyde is sprayed out to form solid particles of paraformaldehyde. This is a continuous process, in which spray granulation is finished within a short time and short linear formaldehyde molecule chain is ensured. Thereby the obtained paraformaldehyde product has favorable water solubility.

Section D. Low polymerization Degree Paraformaldehyde Production Technology

The preparation of low polymerization degree paraformaldehyde is shown below: nCH2 OH2 (CH2 O)n + (n-1)H2 O To produce low polymerization degree paraformaldehyde, be focused on: During formaldehyde concentration process, dehydration, polymerization, depolymerization may occur at the same time. If process conditions are not controlled properly, there is every chance of formaldehyde loss and system clogging. During concentration and drying process, if the formaldehyde concentration is not high enough(i.e., water content is large) , the paraformaldehyde product will be sticky and easy to be agglomerated. During concentration and solidification process, the minor methanol and formic acid contained in formaldehyde material may cause paraformaldehyde to perform further polymerization and yield insoluble polymer. 1.Formaldehyde Concentration Aqueous formaldehyde solution is a mixture of copolymers including methylene glycol CH2 (OH)2 , poly(oxymethylene) glycol HO(CH2 O)n OH and hemiformal HO(CH2 O)n-1 H. It contains no more than 0.1%wtformaldehyde monomer, even in the concentrated formaldehyde solution. Water exists either in free or hydrated form. And the concentration of hydration water is related to polymerization degree and formaldehyde concentration(as the following table shows). Unit: wt% 1 2 3 4 5 6 7 8 polymerization degree water concentration 37.5 23.1 16.7 13.0 10.7 9.1 7.9 7.0 in hydrated form Formaldehyde concentration 62.5 76.9 83.3 87.0 89.3 90.9 92.1 93.0 in hydrated form the following issues must

10

100

300

6.2

5.7

0.6

0.2

93.8

94.3

99.4

99.8

Formaldehyde concentration is related to paraformaldehyde s precipitation temperature. If the temperature is too high, Cannizzaro reaction will take place (i.e., formaldehyde will be converted into methanol and formic acid). Therefore, vacuum dehydration is usually employed for formaldehyde concentration. 1. Concentrated formaldehyde solidification Formaldehyde concentration is also related to the cooling solidification temperature of aqueous formaldehyde solution. High temperature will cause formaldehydes evaporation with water and thereby result in formaldehyde loss; while low temperature will slower formaldehydes dehydration, cause formaldehydes deep polymerization and result in product with poor water solubility. So it is crucial to control polymerization and drying temperature. 2. Equipment Structure Spray dryer design is a comprehensive and systematic work. Factors including spraying pressure, spray angle, diameter and height of sprayer chamber, temperature and flow velocity of cooling medium, and material retaining time in the tower should be taken into account as all these factors have a great influence on product quality.

Process Flow Diagram for Paraformaldehyde

Section E. Material Consumption Quota

No. 1 2 3 4 5 Name Formaldehyde 50% Steam Power Diluted Formaldehyde Cooling Water M 3/t 300-350 287-300 Unit kg/t kg/t KWH/t kg/t Rake Type Dryer 2738-2812 2800-3200 80-120 3000-3380 Spry Dryer 2620-2720 1750-2200 235-300 2583-3000

Proprietary Technology

5000t/a Paraformaldehyde Plant

5000t/a Paraformaldehyde Plant