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Polymerization in Sprays: Atomization and Product Design of Reactive Polymer Solutions

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Abstract

The focus of this novel process is to polymerize a water-based solution in a spray with a conventional spray dryer to produce powder polymers. To achieve a successful process design, this project aims at the atomization of water-based polymer solutions, a novel device to measure reactivity and the design of a pre-reaction nozzle. To overcome the short residence time in a spray dryer a pre-reaction is necessary. It is done within the nozzle, which can be described as a combination of a laminar pipe reactor with a variable length and a twin-fluid nozzle in a lance shape in order to place it easily in a spray dryer. A model to optimize the progress of polymerization within the nozzle is based on kinetics from literature and a viscosity approach. That is made with the help of the novel measurement and the theory of rheokinetics. The increase of viscosity is dependent on the progress of chain growing and the conversion, respectively. A power law is presented to describe the viscosity with changing conversion at a constant initiator ratio. Another important aspect of optimizing the pre-reaction is the influence of the viscosity on the atomization. Investigations show the strong dependency of the molecular weight of the polymer on the drop formation because of its influence on the rheology of the solution. Sprays of different polymer water mixtures are measured by laser diffraction and a two parameter model, RRSB, is successfully used to describe the drop size distribution. The influence of the Sauter mean diameter \( {\overline{x}}_{1;2} \) is only able to be discussed if it is calculated by the RRSB fit. With increasing mass fractions of the high molecular weight polymer a turning point from drop to ligament formation is shown at low shear viscosity compared to lower molecular weight polymers. Finally a laboratory plant is presented that is producing polymer powders in one, but complex, process.

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Abbreviations

A :

Area of heat transfer in m2

A :

Pre-exponential factor in L/(mol · s) or s−1 or Pa · s

a :

Exponent of power function

b :

Exponent of power function

c :

Concentration in mol/L

\( {\tilde{c}}_{\mathrm{p}} \) :

Heat at capacity at constant pressure in J/(kg · K)

d :

Nozzle diameter in m

Da :

Damköhler number

E :

Specific energy in J/mol

f :

Initiator efficiency

h :

Heat transfer coefficient in W/(m2 · K)

\( {\Delta}_{\mathrm{r}}\tilde{H},\ {\Delta}_{\mathrm{v}}\tilde{H} \) :

Specific enthalpie of reaction (r) or evaporation (v) in J/kg

i :

Variable

K :

Empirical constant of viscous flow in Pa · s

k :

Reaction constants in L/(mol · s) or s−1

k c :

Mass transfer coefficient in m/s

L :

Length of nozzle in m

\( \left(\overline{M}\right)\ M \) :

(Mean) molecular mass in g/mol

n :

Exponent of size distribution

Oh :

Ohnesorge number

p :

Pressure in Pa

Q :

Cumulative size distribution

q :

Differential size distribution in m−1

R :

Rate of polymerization in mol/(L · s)

\( \overline{R} \) :

Universal gas constant in J/mol/K

\( {\overline{R}}^2 \) :

Adjusted coefficient of regression

r :

Radius of inner pipe in m

T :

Temperature in K

t :

Time in s

U :

Overall heat transfer coefficient in W/(m2 · K)

w :

Mass fraction in %

X :

Conversion

x :

Particle/drop size

\( {\overline{x}}_{1;2}\kern0.5em \mathrm{or}\kern0.5em {x}_{1;2} \) :

Sauter mean diameter (SMD) in μm3/μm2

z :

Length in m

α :

Pre-exponential factor

β :

Pre-exponential factor

η :

Viscosity in Pa · s

η*:

Complex viscosity in Pa · s

[η]:

Intrinsic viscosity in L/mol

ϑ :

Dimensionless temperature

μ :

Mean value

μ p :

Liquid load

ρ :

Density in g/L

σ 2 :

Variance

τ :

Induction time in s

0:

Initial condition

AA:

Acrylic acid

ad:

Adiabatic

d:

Decomposition

H2O:

Water

I:

Initiator

i:

Initiation

inter:

Intersection

M:

Monomer

m :

Mass

p:

Propagation

poly:

Polymer

r:

Reaction

s:

Solution

spec:

Specific

t:

Termination

W:

Wall

η :

Viscous

τ :

Induction period

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Acknowledgments

We would like to thank the German research foundation for the financial support and the BASF SE for donating materials.

A great thanks to all the co-workers within the SPP, especially to the group of Prof. Nieken and Prof. Moritz from Stuttgart and Hamburg because of the discussion to polymerization in sprays, to the group of Prof. Sommerfeld because of the arrangement of the high-speed camera and to the group of Prof. Windhab because of the discussion on the complex rheology of polymer solutions.

Finally we would like to thank our students, especially Mr. Bergmann, who worked on rheokinetics, Mr. Gärtner for giving a detailed look to rheokinetics and performing stop tests and Mr. Ostmann, who developed the optical measurement to quantify the mixing within the nozzle.

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Authors and Affiliations

  1. Institute of Mechanical Process Engineering and Mineral Processing, TU Bergakademie Freiberg, Freiberg, Germany

    Magnus Tewes & Urs Alexander Peuker

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  1. Magnus Tewes
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  2. Urs Alexander Peuker
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Correspondence to Urs Alexander Peuker .

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Editors and Affiliations

  1. Institute of Materials Science, University of Bremen, Bremen, Germany

    Udo Fritsching

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Tewes, M., Peuker, U.A. (2016). Polymerization in Sprays: Atomization and Product Design of Reactive Polymer Solutions. In: Fritsching, U. (eds) Process-Spray. Springer, Cham. https://doi.org/10.1007/978-3-319-32370-1_20

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