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chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Research and Design

j ourna l ho me page: www.elsev ier .com/ locate /cherd

rocess engineering development for the manufacturing ofanganese octoate on a pilot plant scale

hmed Farid Shaabana,∗, Hamdy Abd-El-Aziz Mostafab, Maaly Abd-El-Monem Khedra,arwa Saeid Mohameda

National Research Centre, Chemical Engineering and Pilot Plant Department, 12622 Cairo, EgyptFaculty of Engineering, Chemical Engineering Department, Cairo University, Cairo, Egypt

a b s t r a c t

A technically and economically feasible process is developed for the manufacturing of manganese octoate as a

powerful paint drier in a pilot plant unit. Such material is an environmentally safe through drier, catalyzes cross

linking within the whole coating layer and is highly recommended for both hard and durable finishes. Scaling-up is

based upon successful studying, evaluation and optimization of all operating parameters affecting process chemical

reaction kinetics, product recovery and purification, and finally the vacuum crystallization stage. The performance

of the pilot unit, overall conversion of reactants (>85%) were in excellent conformity with laboratory results.

Full characterization of the final product is accomplished through practicing a variety of instrumental XRF, FTIR,

XRD, ED-XRF, elemental and HPLC analyses. The developed product has been used in different commercially practiced

formulations proved excellent drier characteristics including adhesive strength, film hardness and ductility.

The design capacity of the pilot plant could match excellently with local commercial market demands that depend

on price–consumption rate relationships. The process techno-economic evaluation reveals high profitability poten-

tials including % annual return on investment and payback period.

© 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Paint driers; Manganese octoate; Metallic soaps; Cobalt-free driers; Paint-film characterization

mental legislations will force the paint industry to replace

. Introduction

lthough used in small amounts, paint driers have specificunctions and play a very important role in the final qualitynd properties of alkyd paints. Without their addition, therying of alkyd paints would be too slow for most practicalpplications (Bieleman, 2000). Typical driers for alkyd systemssed in decorative paints are metal salts of long chain fattycids (soaps) according to the formula (Mn+)(X−)n in which Ms a metal (V, Mn, Fe, Co, Ce, Ca, Zr and Pb), and X is a syn-hetic C6–C18 aliphatic carboxylate. Typical carboxylates areranched monocarboxylic acids such as 2-ethylhexanoic- andeodecanoic-acids.

Primary and secondary driers affect the drying rate bynteracting with transition metal driers and reinforcing the-dimensional polymer network by interacting with hydroxylnd carbonyl groups of binders via formation of oxygen-metal-

xygen bridges (Bieleman, 2000; Landau et al., 1979; Turner,

∗ Corresponding author. Tel.: +20 2 337 5626; fax: +20 2 337 0931.E-mail addresses: drahmedshaaban@yahoo.com (A.F. Shaaban), pro

aalykhedr@yahoo.com (M.A.-E.-M. Khedr), marwashalaby u@yahoo.cReceived 2 March 2011; Received in revised form 23 August 2011; Acce

263-8762/$ – see front matter © 2011 The Institution of Chemical Engioi:10.1016/j.cherd.2011.09.007

1986; Erich et al., 2006a,b). The metal part is responsible fordrying and catalytic actions, while the acid portion influencesthe physical properties.

Cobalt driers are the most active primary driers in bothsolvent- and water-born paints (Gorkum and Bouwman, 2005;Land et al., 1971; Tanase et al., 2004). However, a disad-vantage of Co-based driers is that their catalytic activity inair drying coatings and paint compositions diminishes uponstanding. The decrease is worst in waterborne systems (Hurleyand Buono, 1982), being ascribed to hydrolysis of metal car-boxylates and/or adsorption of the drier on the surface ofthe pigments. Another disadvantage is their suspect toxicity(carcinogenicity) to tissues and lungs (Miccichè et al., 2005;European Commission, 2003; Lisbon et al., 2001; Bucher et al.,1999; De Boeck et al., 2003; Bieleman, 2002; Danish EPA, 2002).As a consequence, in the near future more stringent environ-

fhamostafa2002@yahoo.com (H.A.-E.-A. Mostafa),om (M.S. Mohamed).pted 8 September 2011

Co-based driers with environmentally friendly alternatives

neers. Published by Elsevier B.V. All rights reserved.

644 chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650

Nomenclature

A01 Arrhenius frequency factor of Na-octoate for-mation reaction (gmol/l s)

A02 Arrhenius frequency factor of Mn-octoate for-mation reaction (gmol/l s)

E1 activation energy of Na-octoate formation reac-tion (J/gmol)

E2 activation energy of Mn-octoate formationreaction (J/gmol)

ED-XRF Energy dispersive X-ray fluorescenceFTIR Fourier transform infraredHPLC high performance liquid chromatographyk1 specific rate constant of Na-octoate formation

reaction (gmol/l s)k2 specific rate constant of Mn-octoate formation

reaction (gmol/l s)m specific mass of waterM specific mass of ethanolRMR1 multiples or fractions of stoichiometric

alkali/octoic acid molar ratios of Na-octoateformation reaction

RMR2 multiples or fractions of stoichiometric man-ganese sulfate/sodium octoate molar ratios ofMn-octoate formation reaction

XRD X-ray diffractionXRF X-ray fluorescence� absolute (dynamic) viscosity (cp)� reciprocal of wave length (cm−1)�1 time of Na-octoate formation reaction (min)�2 time of Mn-octoate formation reaction (s)�c Cooling time (min)

0

10

20

30

40

50

60

70

80

90

100

403020100

%O

vera

ll Co

nver

sion

τ1, min

1.5 RMR1 2.5 RMR1 1 RMR1 0.4RMR 1

RMR1 = stoichio metric react ant s molar ra�oτ1 = Time of Na -Octoate form a�on reac�on (min )

Fig. 1 – Kinetic data of Na-octoate formation reaction atdifferent RMR1 and 75 ◦C.

Fig. 2 – Kinetic data of Na-octoate formation reaction atdifferent temperatures and RMR = 1.

(coating containing cobalt catalysts are no longer accepted tohold the blue angle label in Germany). Among the environ-mental challenges concerning the substitution of suspectedtoxic components in common organic coatings, the search foracceptable alternatives to toxic chemical additives in alkydpaints, especially the anti-skinning agents and the cobaltdrier catalysts, has recently become a subject of intenseindustrial and academic interest (Bieleman, 2000; Jones, 1985;http://www.epa.gov; De Hek et al., 1998; http://www.cepe.org;Van Haveren et al., 2005; Wu et al., 2004a,b; Oostveen et al.,2003; Miccichè et al., 2005; Hurley and Buono, 1982).

Manganese octoate is the most important primary drierafter cobalt. It is a promising environmentally safe drier,having excellent auto-oxidation and catalytic properties (Liuet al., 2007; Van Gorkum et al., 2004; Hoogenraad et al., 1998;Oyman et al., 2004; Erich et al., 2006a,b; Shipley, 1983), pro-moting surface and through drying (Frankel, 1998; Oostveenet al., 2003; Van Gorkum et al., 2007, 2008; Bouwman and VanGorkurn, 2007; Bieleman, 1998; Hein, 1998). Mn-based driersare preferred to be used in low concentrations when light- orwhite-colored paints are used (Gorkum and Bouwman, 2005;Bieleman, 2002). Complexes of manganese carboxylates withchelating-nitrogen ligands will significantly improve their dry-ing and catalytic effects (Oyman et al., 2005; Wu et al., 2004a,b;Warzeska et al., 2002).

The objective of this work is to develop a reliable processtechnology for the production of pure manganese octoate.

Quality control test-results of product-drier-formulationsguarantee its successful industrial application as an efficient

1

highly potent and environmentally safe primary paint drierand could probably diminish the use of cobalt driers in thealkyd paint industry.

Optimization of the operating parameters affecting reac-tion kinetics and final product yield were carefully studied.Process experiments have been carried out on both laboratory-and pilot-plant scales (50 kg/batch) .The experimental resultsreveal an optimum temperature of 75 ◦C with stoichiometricreactants molar ratios for carrying out the double decomposi-tion consecutive reactions. The corresponding overall reactionconversion is >85% (Figs. 1–4).

Full characterization of final product was accomplishedthrough a variety of instrumental analyses including XRF,FTIR, XRD, HPLC, acid value, elemental and ED-XRF techniques(ASTM, 1998, 2005a,b). A comparative study was conductedbetween different commercially practiced drier-formulationsand those using the developed product. The developed for-mulations have proved excellent experimental results thatfulfill requirements of international standards concerning filmadhesive strength, hardness and ductility (ASTM, 2002, 2003,2005a,b; Kopeks, 1995).

A solvent extraction technique was used to purify crude

product. Maximum extraction efficiency (92%) was verified at atemperature of 60 ◦C with water- and ethanol–specific masses

chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650 645

1

% o

vera

ll Co

nver

sion

0

10

20

30

40

50

60

70

80

90

100

0 100

RMR2 = Stτ 2 = Tim

τ 2

toichio metricme of Mn-Octo

200,sec.

React ant s Moate fo rma�o n

300

Mola r Ra�on reac�o n(s )

400

0.75

1

2

4

5 RMR2

RMR2

RMR2

RMR2

Fig. 3 – Kinetic data of Mn-octoate formation reaction atdifferent RMR2 and 75 ◦C.

0

10

20

30

40

50

60

70

80

90

100

0

% O

vera

ll co

nver

sion

50 150100

25

React aReact aTempe

200

τ2 , sec.

C 40°C

ants molar ra tants molar ra terature of Na-

250

55°C 7

tio of Na -Octotio of Mn -Oct-Oct oat e form

300

5°C 80°C

oate fo rma�otoat e fo rma�ma�on reac� o

350 40 0

on reac�on (Ron reac�on(Ron (T1)=75⁰C

RMR1)=1RMR2)=1

Fig. 4 – Kinetic data of Mn-octoate formation reaction atdifferent temperatures.

0

10

20

30

40

50

60

70

80

90

100

21.510.50

%Ex

trac

�on

Specific mass of water, m

M=1M=2M=3M=4M=5M=6

M=Speci fic mass of ethano l

Fig. 5 – Effect of specific mass of water (m) on %extraction atdifferent ethanol specific masses (M) and 60 ◦C.

oppwlt

0

10

20

30

40

50

60

70

80

90

100

151050

% E

xtra

c�on

Ethanol specific mass (M)

18 °C

40°C

60°C

Fig. 6 – Effect of specific mass of ethanol on %extraction atdifferent temperatures and water specific mass (m) = 1.2.

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

200150100500

Wei

ght %

of d

ried

pro

duct

τc ,min.

30°C 18°C 5°C -2°C -5°C

Fig. 7 – Kinetic data of %weight of extracted dried product

The process flow diagram (Fig. 8) describes the sequentialstages for the manufacturing of a 50 kg batch of Mn-octoate

f 1.2 and 5 respectively (Figs. 5 and 6). At such conditions theroduct concentration in the filtered cake was minimum asroven by EDIX analysis (<4% carbon). Final purified crystalsere recovered from ethanol solutions by vacuum crystal-

ization. Maximum product recovery (95%) was achieved at aemperature of −5 ◦C (Fig. 7).

with cooling time at different temperatures.

The conducted techno-economic feasibility study proveshigh profitability figures for the return on investment and pay-back period.

2. Process chemistry

The precipitation process was selected to manufacture man-ganese octoate according to the following two consecutiveirreversible elementary chemical reactions:

C8H16O2 + NaOH → C8H15O2Na + H2O (1)

2C8H15O2Na + MnSO4 → (C8H15O2)Mn + Na2SO4 (2)

The kinetic data of both formation and precipitation reac-tions were analyzed to assess reaction orders (n = 2 for bothreactions), specific reaction rate constants (k) and activationenergies (E), together with the Arrhenius frequency factor (A).The results are summarized in Table 1.

3. Process description

646 chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650

Table 1 – Kinetic parameters of both Na-octoate formation- and Mn-octoate precipitation reactions.

Reaction Reaction rate constants at 75 ◦C Arrhenius’ constants

k1 (gmol/l s) k2 (gmol/l s) E1 (J/gmol) A01 (gmol/l s) E2 (J/gmol) A02 (gmol/l s)

Na-octoate formation 0.003 – 8720 0.078 – –Mn-octoate precipitation – 0.063 – – 26.6 592

crystals. The main jacketed reaction vessel (MR-1) is fed with2-ethylhexanoic acid (S1), petroleum ether (2), and processwater (S3) respectively under thorough agitating conditions.The mixture is heated by circulating saturated steam (S27).8.4 M (33%, w/w) sodium hydroxide solution (S4) is fed to themain reactor in a single shot. The whole reacting mass is con-tinuously heated at 75 ◦C for 30 min. 34% (w/w) manganesesulfate solution (S5) is fed from a storage tank (ST-5) to thereactor under total reflux conditions. Stirring is continued for20 min while maintaining the temperature at 75 ◦C. A brine-cooled overhead condenser (RC-1) is used to condense andrecycle any distilled solvent vapours.

After reaction completion, heating and stirring werestopped in order to decant the mass (S6). This will resulted inimmediate separation of the upper organic product phase andlower aqueous layer. Continuous pumping of bottom layer (S8)to a surge tank (SRT-2) was accomplished while observing the2-phases separating surface by a sight-glass at the reactor’sbottom.

The organic layer (S7) is thoroughly washed twice with pro-cess water under agitating conditions followed by decantation

Fig. 8 – Process flow diagram for m

to remove any entrained impurities. The whole product massis then continuously heated till about 90% of the formedwater–ether azeotropic mixture is distilled-off in the distil-lation column (DC-1). The condensate (S11) is pumped to asurge tank (SRT-3) and reused in another batch.

95% ethanol (S13), which amounted to five times the resid-ual product mass was added to the product mass (S12) undercontinuous stirring. The temperature is raised gradually to60 ◦C and maintained at this level for 15 min to guaranteecomplete dissolution. The ethanol/product solution (S17) wasmixed with a controlled amount of process water (S16) whilemaintaining agitation. A brown precipitate is formed and theslurry mixture (S18) is then pumped to a Nutsch vacuum fil-ter (VF-1) to separate the suspended manganese oxides. Themoisted cake (S20) was fed to rotary drier (RD-1) to furnish asecondary product (S21) that stored in silos (SS-3) packed andsold.

The clear product solution (S19) is recycled (P-1) to the mainreactor where it was partially distilled under vacuum then

rapidly cooled to −5 ◦C by circulating ethylene glycol brine(S28). Continuous formation of product crystals takes place,

anganese octoate production.

chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650 647

ese

atm(r(

(ctd

4

Aapc

Fig. 9 – HPLC-monograph of mangan

nd the slurry mixture (S22) is pumped to the vacuum filtero separate pure Mn-octoate (S23) which were dried (S29) for-

ulated in storage silos (SS-1, 2) and sold. The effluent filtrateS24) is fed to a surge tank (SRT-1) and recycled to the maineactor to distill-off the ethanol (S25) for reuse. Finally effluentS26) environmentally safe was drained.

The aqueous effluent (S8) was pumped from surge tankSRT-2) to the main reactor to vaporize 75% of water (S9) byirculating steam (S27). The formed slurry liquor (S10) was fil-ered to furnish Na2SO4-decahydrate crystals (S14) that wereried (S15) stored (SS-4), packed and sold.

. Instrumental analysis of Mn-octoate

n Agilent 1200-series HPLC was used to conduct qualitativend quantitative concentration measurements of the formed

roduct. The major sharp 3rd peak (retention time = 3.149 min)orresponds to main product, while the 2nd peak (retention

Fig. 10 – XRD of mangan

octoate solution in petroleum ether.

time = 2.482 min) belongs to associated impurities (Fig. 9).The calibration of the peak areas in the HPLC-monographwas accomplished by analyzing their corresponding aqueousphase solutions using XRF.

The XRD-spectrum (Brukurd8 advance, CuK�, target withsecondary mono chromator �� = 40, mA = 40, Germany) is illus-trated in (Fig. 10) that reflects the amorphous state of the finalproduct nano-molecules. The 1st and 2nd peaks (d = 14.97797and d = 13.48040) correspond to the associated organic impu-rities, while the major sharp peak (d = 6.66883) belongs to themain product. The developed HPLC- and XRD-monographs arereally considered as figure-prints for product identification.

The final purified product crystals were subjected to FTIR-spectrum (FTIR = JASCO FTIR-6100, absorbance 400–4000 cm−1

and resolution 4 cm−1, Japan). The IR-spectrum (Fig. 11) wassuper-imposable on that of the authentic sample particularlyin the figure print region (1500–650 cm−1). The main distin-

guishing features of this IR spectrum were: (i) the presenceof strong absorption bands (peaks nos. 6, 7, and 8) at 2960,

ese octoate crystals.

648 chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650

Table 2 – Full assay data-sheet of manganese octoate paint drier.

Test Experimental value Literature value

(1) Elemental analysis (solid crystals). C = 56%, H = 8% C = 56.3%, H = 8.80% from chemical structuralformula

(2) Fourier transform infrared FTIR-solid crystals. � (cm−1): 2959, 2932, 2860, 1542,1458, 1416, 1317, 1235, and 1104

� (cm−1): 1200–1800 for product film uponphotolysis for 0.5, 10, 25 and 45 min (Zhu andHill, 2002)

(3) High performance liquid chromatography –HPLCMn-octoate in petroleum ether.

Area (mAU s) = 1.74e4 N/A

(4) Acid value (liquid phase). 3% free fatty acid N/A

(5) Absolute (dynamic) viscosity (�) (40% w/wMn-octoate in white spirit).

30.9 cp Viscosity gardner, 25 ◦C: (a)10%Mn-content = Amax(50 cp)(b) 6%Mn-content = (A-2) → Amax(30cp)

(6) % Mn-content:(6-1) Solid crystals. 15% N/A(6-2) 40% Mn-octoate in white spirit. 6.1%

(7) % Non-volatiles and ash-content of solid crystals.(7.1) Non-volatiles. 55% N/A(7.2) Ash-content. 20%

(8) Specific gravity of 40% Mn-octoate in whitespirit (6% Mn-content).

0.9 0.89 ± 0.02

(9) Color (40% Mn-octoate in white spirit). Red-brown 3744 I/m N/A

N/A: not available.

Table 3 – Long alkyd resin with different drier combinations.

Components Formulation no.

1b 2b 3b 4c

Long alkyd resin, g 100 100 100 100Lead octoate drier (36%) 0 0 0.833 (0.3PbOct + 0.533WS) 0.833 (0.3PbOct + 0.533WS)Cobalt octoate drier (10%) 0 3.5 (0.35CoOct + 3.15WSa) 0 0Calcium octoate drier (5%) 0 16.00 (0.8CaOct + 15.2WS) 16.00 (0.8CaOct + 15.2WS) 16.00 (0.8CaOct + 15.2WS)Zirconium octoate drier (12%) 0 4.17 (0.5ZrOct + 3.67WS) 4.17 (0.5ZrOct + 3.67WS) 4.17 (0.5ZrOct + 3.67WS)Manganese octoate drier (10%) 0 0 5.00 (0.5MnOct + 4.5WS) 0Manganese octoate drier (10%)

(developed)0 0 0 5.00 (0.5MnOct + 4.5WS)

a WS = white spirit.b Formulations are supplied by the “Egyptian Swiss for Industry and Trading Co.”, http://www.swisschem.com.c Formulation developed in the National Research Centre laboratories, Cairo, Egypt.

Fig. 11 – FTIR spectrum of manganese octoate crystals.

2935, 2868 cm−1 respectively (C–H, aliphatic), (ii) peak no. 12 at1692 cm−1 (C O, carboxylate), and (iii) peak no. 15 at 1410 cm−1

(C–O, stretching). Fig. 11 proves excellent IR-agreement withpublished literature (Zhu and Hill, 2002).

Product elemental analysis (VARIO El-analyzer, Germany)was in exact conformity with its chemical structural formula(C = 56%, H = 8%). A full product assay is presented in Table 2.

5. Product quality control

The developed product was used with other paint-drier-constituents to produce different commercially marketedformulations (Table 3). Standard test procedures for paint-films (ASTM, 2005a,b) were used to measure hardness,ductility and adhesion (ASTM, 2002, 2003, 2005a,b; Kopeks,1995).

The film hardness was measured using the standardKönig pendulum technique (ASTM, 2003). An Erichsen cuppingstandard test machine was used for ductility measurement

(Kopeks, 1995), while the removal of a pressure sensitive taptechnique was practiced for film adhesion assessment (ASTM,

chemical engineering research and design 9 0 ( 2 0 1 2 ) 643–650 649

Table 4 – Physical and mechanical results of different paint-drier-formulations.

Formulations

1a 2a 3a 4b

Film thickness 60 �m 120 �m 60 �m 120 �m 60 �m 120 �m 60 �m 120 �mHardness, s 18 12 102 60 50 35 56 37Adhesion 5B 5B 5B 5B 5B 5B 5B 5BDuctility, mm 6 6 6.1 5.8 6.3 6.2 6.6 6.4

a Formulations are supplied by the “Egyptian Swiss for Industry and Trading Co.”, http://www.swisschem.com.b s, Cai

2ei

6

Aosp

tbsrc

tXtwo

ppvf

e

A

Si

R

A

A

A

A

A

B

B

Formulation developed in the National Research Centre laboratorie

002). All test results are summarized in Table 4 demonstratingxcellent agreement with the recommended values specifiedn international standards.

. Conclusion

n integrated process has been developed for the productionf pure Mn-octoate crystals. The superior product propertiesupport its use as an efficient, environmentally safe, primaryaint drier.

Optimization of the operating parameters affecting reac-ion kinetics and final product yield were carefully studied onoth laboratory- and pilot-plant scales. The double decompo-ition consecutive reaction process with stoichiometric molaratios of reactants was selected, furnishing an overall reactiononversion of >85%.

Full characterization of final product is accomplishedhrough a variety of instrumental analysis including XRF, FTIR,RD, HPLC, elemental and ED-XRF. Excellent material proper-

ies, such as adhesive strength, film hardness and ductilityere measured upon formulating the developed product withther driers.

A solvent extraction technique was used to purify cruderoduct by salting out any associated impurities. Final purifiedroduct crystals were precipitated from ethanol solutions in aacuum crystallizer equipped with a brine-cooled condenseror solvent recovery.

The estimated total product cost reinforces the techno-conomic feasibility of the developed process.

ppendix A. Supplementary data

upplementary data associated with this article can be found,n the online version, at doi:10.1016/j.cherd.2011.09.007.

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