Chemical Engineering Science 134 (2015) 758–766

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Kinetics of synthesis of polyoxymethylene dimethyl ethers

from paraformaldehyde and dimethoxymethane catalyzed
by ion-exchange resin
Yanyan Zheng, Qiang Tang, Tiefeng Wang n, Jinfu Wang n
Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

H I G H L I G H T S

Kinetics of synthesis of PODEn from paraformaldehyde and methylal was studied.

The transient molecular size distribution of PODEn follows Schulz–Flory model.

The rate constants are the same for reversible propagation reactions of PODEn.

The sequential reversible reactions to produce PODEn are exothermic.

art ic l e i nf o a b s t r a c t

Article history: Polyoxymethylene dimethyl ethers (CH3–O–(CH2O)n–CH3, PODEn, n 41) are new concerned environ-
Received 1 February 2015 mental benign alternative components for diesel fuels. This work aimed to investigate the kinetics of
Received in revised form synthesis of PODEn from paraformaldehyde and dimethoxymethane catalyzed by ion-exchange resin
27 May 2015
NKC-9. Experiments were conducted in a designed space, namely reaction temperatures (60, 70, and
Accepted 30 May 2015
80 1C) vs. reaction times (2, 5, 10, 20, 30, 60, and 90 min), in a batch stirred autoclave. The transient
Available online 12 June 2015
molecular size distribution of PODEn compounds from paraformaldehyde and methylal followed Schulz–
Keywords: Flory distribution model. In this system, the concentration of formaldehyde in the homogenous solution
Polyoxymethylene dimethyl ethers (CF) was nearly constant. The sequential reversible reactions to produce PODEn were verified to follow a
Kinetics
second-order kinetics for propagation and a first-order kinetics for depolymerization. The rate constants
Schulz–Flory distribution
of propagation (kp) and depolymerization (kd) and the reaction equilibrium constant Kn were the same
Sequential reversible reactions
for the series of PODEn synthesis reactions. Respecting to 5 wt% dosage of NKC-9 resin catalyst, the pre-
exponential factors Ap for propagation and Ad for depolymerization were 1.84  107 L mol–1 min–1 and
5.36  106 min–1, respectively. The activation energy Ep (39.52 kJ mol–1) for propagation was lower than
Ed (52.01 kJ mol–1) for depolymerization, validating that the reversible reactions of producing PODEn
compounds were exothermic.
& 2015 Elsevier Ltd. All rights reserved.

1. Introduction
The combustion of petroleum-derived fuels is an important
source of key precursors to the formation of secondary organic
aerosol (Hallquist et al., 2009; Volkamer et al., 2006; Worton et al.,
2014). The accumulation of secondary organic aerosol in air
contributes to particulate pollution during haze events (Huang
et al., 2014). In China, the concentration of PM 2.5 (particulate
n
Corresponding authors. Tel.: þ 86 10 62794132; fax: þ86 10 62772051.
E-mail addresses: wangtf@tsinghua.edu.cn (T. Wang),
wangjfu@tsinghua.edu.cn (J. Wang).
matter with an aerodynamic diameter less than 2.5 mm) in air
usually exceeds 100 mg m–3, which is seriously detrimental to
human health (Lin et al., 2009). Reducing the emissions of
precursors to secondary aerosol from gasoline and diesel vehicle
emissions is important for controlling the PM 2.5 levels and
improving environmental and air qualities in China (Huang et al.,
2014). Diesel engines have a higher thermal efficiency than gaso-
line engines. However, diesel exhaust is seven times higher in
forming aerosol than gasoline exhaust (Gentner et al., 2012).
Generally, the combustion of diesel is responsible for 65 90% of
vehicular-derived secondary organic aerosol (Gentner et al., 2012).
Polyoxymethylene dimethyl ethers (CH3–O–(CH2–O)n–CH3,
PODEn, where n 41), which are environmental benign alternative

http://dx.doi.org/10.1016/j.ces.2015.05.067
0009-2509/& 2015 Elsevier Ltd. All rights reserved.
 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766
components for diesel fuels, are receiving increasing attentions in
recent years (Burger and Hasse, 2013; Burger et al., 2010, 2012,
2013; Lumpp et al., 2011). Compared with the reference diesel fuel,
the PM emissions are reduced by 18% with 10% blend and by 77%
with pure PODEn (Pellegrini et al., 2013). Among the PODEn
oligomers, PODE3–5 compounds are the most ideal diesel additives,
while PODE2 does not fulfil the security criteria due to its low flash
point, and PODEn 4 5 precipitate at low temperatures due to their
high melting points (Zheng et al., 2013). Compared with methanol,
dimethyl ether (DME) and dimethoxymethane (DMM), the physi-
cochemical properties of PODE3–5 match well with that of petro-
leum diesel, thus allowing the use of PODE3–5 in modern diesel
engines without any change of the engine infrastructure
(Pellegrini et al., 2013; Zheng et al., 2013). The application of
PODEn is promising to relieving both air pollution and petroleum
shortage.
The PODEn compounds are prepared from end-group (–CH3, –
O–CH3) provider (DMM or methanol) and chain-group (–CH2O)
provider (paraformaldehyde (PF), trioxane, or formaldehyde solu-
tion) over acid catalysts. Recent papers on synthesis of PODEn have
focused on catalyst preparation and characterization, and process
optimization. Various acidic catalysts, including acidic ion-
exchange resins (Wang et al., 2014; Zheng et al., 2013, 2014;
Burger et al., 2012), ionic liquids (Wu et al., 2014), molecule sieves
(Zhao et al., 2011), and solid superacids (Li et al., 2015; Zhang et al.,
2014), have been employed in synthesis of PODEn. Burger et al.
(2012) proposed that water reacts with ethers and form alcohols
during the synthesis of PODEn from DMM and trioxane in the acid-
catalyzed system. To illustrate the effect of water on the synthesis
of PODEn from DMM and PF, we investigated the product dis-
tribution with different dosages of water added in this work, as
shown in Table 1. The results showed that water induced the
hydrolysis of DMM and PODEn compounds forming methanol and
formaldehyde. In particular, when the added dosage of water
exceeded 5 wt%, the hydrolysis reactions became crucial, and
significantly decreased the yield of PODEn products and increased
the complexity of product purification. To avoid introducing or
generating water, DMM is a better end-group provider than
methanol, while PF and trioxane are better chain-group provider
than formaldehyde solution.
Kinetics is of great importance for the molecular size distribu-
tion regulation, process optimization and reactor design for
synthesis of PODEn. However, the studies on the kinetics of
synthesis of PODEn are very limited. Burger et al. (2012) reported
the reaction kinetics of the heterogeneously catalytic formation of
PODEn from DMM and trioxane, and proposed an adsorption-
based kinetic model to describe the results. Zhang et al. (2014)
synthesized PODEn from methanol and formaldehyde solution and
proposed a kinetic model based on an elimination mechanism. In
our previous work (Zheng et al., 2014), we reported the synthesis
of PODEn from DMM and PF over acidic ion-exchange resins and
Table 1
Compound distribution in PODEn products formed by DMM and PF with different
dosages of water added (80 1C, DMM/CH2O molar ratio 3:1, 5 wt% NKC-9 resin as
catalyst).
Compound distribution Added dosage of water (wt%)
0 5 10 15 20
Methanol (wt%) 1.817 4.825 8.040 10.528 11.610
Formaldehyde (wt%) 0.927 12.049 20.629 27.310 28.206
DMM (wt%) 67.291 60.061 53.934 48.985 48.017
PODE2 (wt%) 20.193 17.502 14.523 11.774 10.976
PODE3–5 (wt%) 9.626 5.516 2.873 1.403 1.192
PODEn 4 5 (wt%) 0.146 0.044 0.000 0.000 0.000
759
proposed an equilibrium molecular size distribution model based
on a sequential reaction mechanism, but did not study the kinetics
in detail. The synthesis of PODEn from PF and DMM involved the
depolymerization of solid PF raw materials and sequential rever-
sible chain propagation reactions, thus possessing very different
kinetic properties from other PODEn synthesis systems.
In the present work, the synthesis of PODEn from PF and DMM
catalyzed by NKC-9 acidic ion-exchange resins was conducted in
the designed space, namely reaction temperatures (60, 70, and
80 1C) and reaction times (2, 5, 10, 20, 30, 60, and 90 min), in a
batch stirred autoclave. To the best of our knowledge, this article is
the first report on kinetics of synthesis of PODEn from DMM and PF
catalyzed by ion-exchange resin. A kinetic model was developed
assuming that the sequential reversible reactions to produce
PODEn compounds follow a second-order kinetics for propagation
and a first-order kinetics for depolymerization. Rate constants at
different temperatures were obtained by least-squares aggression
of the experimental concentration of DMM as a function of
reaction time. The Arrhenius parameters, including the pre-
exponential factor and activation energy, were calculated from
the rate constants at different temperature.
2. Experimental
2.1. Materials
DMM (analytic reagent grade, 4 99 wt%) was purchased from
Alfa Aesar-Johnson Matthey. PF (polymer grade, 4 96 wt%) was
purchased from Sinopharm Chemical Reagent Co., Ltd. The NKC-9
acidic ion-exchange resin (H þ type) was provided by Tianjin
Bohong Resin Technology Co., Ltd.
PODE2–5 (industrial grade, 495%) were provided by a 10 kt/a
PODE industrial plant in Shandong Yuhuang Chemical (Group) Co.,
Ltd. in China using the technology developed by our research
group. In this technology, a fluidized bed reactor was used to
produce PODEn from DMM and PF over solid acid catalyst. These
PODE2–5 samples were further purified to analytic reagent grade
(499%) and used as standard samples in quantitative analysis of
PODEn product.
2.2. Experimental setup and procedure
The schematic of the experimental setup for synthesis of PODEn
from PF and DMM catalyzed by NKC-9 is shown in Fig. 1. Previous
works (Zheng et al., 2013, 2014) showed that NKC-9 had a high
catalytic activity and good stability for the production of PODEn
from PF and DMM. Therefore, NKC-9 was used in this work with a
dosage of 5.0 wt% relative to the mass of feedstocks (PFþ DMM).
To obtain a high conversion of formaldehyde and low yield of long
chain PODEn 4 5 compounds, the DMM/CH2O molar ratio of the
feeding was set 2 (Zheng et al., 2013, 2014). Considering that the
maximum tolerance temperature of NKC-9 resin was  100 1C, the
experiments were carried out in a designed space, namely the
reaction temperatures (T¼ 60, 70, and 80 1C) versus reaction times
(t¼ 2, 5, 10, 20, 30, 60, and 90 min), in a 0.5-L batch stirred
autoclave.
To obtain reliable kinetic data, all the experiments were
conducted strictly using the following procedures. Firstly, PF and
25
DMM were mixed and loaded into the reactor; then, the reactor
13.101 was sealed and heated; once the reactor temperature reached the
29.069 specific value, the catalyst (NKC-9 ion-exchange resin) was
47.518 released from the fragile bottle and then uniformly dispersed by
9.580 stirring at 500 rpm. This moment was considered as the starting
0.732
0.000
time of reaction. The liquid phase was sampled at different
reaction times for analysis.
760 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766

Fig. 2. Scheme of the formation of PODEn compounds from PF and DMM catalyzed
over NKC-9 ion-exchange resin.
Fig. 1. Schematic of the experimental setup for synthesis of PODEn from PF and
DMM catalyzed over NKC-9.

2.3. Analysis
The product distribution of the PODEn compounds was quantita-
tively analyzed using gas chromatography–mass spectrometry (GC–
MS). The product sample (0.5 mL) was diluted with 5 mL of unde-
cane. One microliter of the solution was injected into a Shimadzu
2010 plus GC equipped with an MXT-5 column (5% diphenylþ 95%
dimethyl polysiloxane, 30 m  0.25 mm  0.1 mm) and a flame ioni-
zation detector (FID). The detailed temperature program of the GC
column was described elsewhere (Zheng et al., 2013, 2014). Nitrogen
was used as carrier gas. An Agilent G2579A MS was used to identify
the species with different residence times in the GC column.
Although water can induce significant side reactions, the use of
anhydrous DMM (99%) and paraformaldehyde (496%) decreases the
Fig. 2. The NKC-9 strong acidic ion-exchange resin was made of
polystyrene sulfonate. The featured sulfonic acid groups work as
the reactive sites. In this scheme, the depolymerization of PF to
formaldehyde (reaction (1)) and the sequential chain propagation
reactions of PODEn compounds (reactions (2) and (3)) occurred on
the acid sites. The sequential chain propagation reactions are
reversible: DMM and PODEn react with formaldehyde to propa-
gate, and PODEn þ 1 reversely depolymerize to PODEn and formal-
dehyde.
Hþ
HOðCH2 OÞm H ⇌ mCH2 Oþ H 2 O ð1Þ
kp;1
DMM þ CH2 O ⇌ PODE2 ð2Þ
kd;1

water content to a very low concentration. Even if all the impurity in

kp;n
the feedstocks is water, the amount of water is o0.70 wt% in the PODEn þ CH2 O ⇌ PODEn þ 1 ðn⪢1Þ ð3Þ
feedstocks. Less than 1 wt% side-product methanol was formed and kd;n

was neglected in further analysis. A set of relative mass correction where kp,j (j¼1, n) and kd,j (j¼ 1, n) are the rate constants of the
factors of PODEn compounds (with DMM as reference) were mea- forward (propagation) and reverse (depolymerization) reactions,
sured using standard samples PODE2–PODE5. It was found that the respectively. For reactions (2) and (3), the values of kp,j and kd,j
relative mass correction factors for PODEn (n¼ 2–5) is a geometrical were independent of j, as shown in Eqs. (4) and (5), which was
series, which was similar to the results Burger et al. (2012) found validated by our previous study (Zheng et al., 2014) on molecular
during their PODEn quantitative analysis. The relative mass correction size distribution model for the same process.
factors for PODEn with longer polymerization degree were calculated
by extrapolation. Using the above correction factors, the error in kp;1 ¼ kp;2 ¼ ⋯ ¼ kp;n ¼ kp ð4Þ
carbon balance was within 73%.
The concentration of formaldehyde was determined using kd;1 ¼ kd;2 ¼ … ¼ kd;n ¼ kd ð5Þ
titration by the sodium sulfite method provided by ASTM D2194- The theoretical molecular size distribution model of PODEn was
02 (2012). Different from Burger's attempt in PODEn system from developed based on the sequential reaction mechanism (Zheng
DMM and trioxane (Burger et al., 2012), the titration by the et al., 2013, 2014). The molecular size distribution model followed
sodium sulfite method used in this work could be calibrated and the Schulz–Flory distribution (Zheng et al., 2014):
had a good reproducibility. The difference was attributed to the

M DMM þ M CH2 O ðn  1Þ an  1
different depolymerization properties of trioxane and PF in wn ¼ ð6Þ
sodium sulfite solution (Kiernan, 2000; Maurer, 1986). The repro- M DMM þM CH2 O a ð1 þ aÞn
ducibility experiments were conducted for three times for each where wn is the mass fraction of PODEn compound, MDMM is the
sample, and the relative error was estimated to be within 73%. molecular weight of DMM, M CH2 O is the molecular weight of
formaldehyde, and a is a dimensionless factor equaling to the
ratio of reacted amount of formaldehyde to initial amount of
3. Reactions and product molecular size distribution DMM.
N CH2 O;R
The scheme of the formation of PODEn compounds from PF and a¼ ð7Þ
N DMM;0
DMM catalyzed by NKC-9 ion-exchange resin is demonstrated in
 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766
The natural logarithm form of Eq. (6) is
 
wn a 1
ln ¼ n ln þ ln
n þ 1:533 aþ1 að2:533 þaÞ
By analogy with the formation of poly-(oxymethylene) glycols
(Burger et al., 2012), the sequential propagation mechanism leads
to an equilibrium molecular size distribution of PODEn compounds
that depends on the factor a. By definition, the factor a is
determined by conversion of formaldehyde and initial molar
feeding ratio of DMM/CH2O.
Although derived from equilibrium state (Zheng et al., 2014),
the theoretical molecular size distribution model was found to be
applicable to transient state in the present work. As illustrated in
Fig. 3, the plots of ln(wn/(n þ 1.533)) exhibited a good linear
relationship with respect to n corresponding to the transient
molecular size distribution of PODEn compounds in the design
space, validating the application of the model at transient state.
This is because the values of kp and kd are independtent of n,
which means the same reactivity of PODEn compounds indepen-
dent of molecular size during the chain propagation. Using
statistical method (Flory, 1940; Kissin, 1995; Schulz, 1999;
Tavakoli et al., 2008), the same reactivity of PODEn compounds
lead to transient molecular size distribution model the same
expression with Eq. (6), accounting for the applicability of the
molecualr size distribution model at transient state.
Fig. 3. Plots of ln(wn/(nþ 1.533)) with respect to n and the calculated a value at different reaction times and different reaction temperatures (DMM/CH2O molar ratio of 2:1,
dosage of NKC-9 at 5 wt%).
761
Based on Eq. (8), the value of a was determined from the slope or
intercept of the line between ln(wn/(nþ 1.533)) and n. The calculated
values of a from the slope and from the intercept are the same within
ð8Þ
the deviation 73%. The average of the calculated values of a from the
slope and from the intercept was used. Fig. 3(d) presents the values of
a as a function of reaction time at 60, 70 and 80 1C. The corresponding
value of a at different reaction times reflects the extent of chain
propagation. The value of a gradually increased with increasing
reaction time until the equilibrium was approached, indicating the
gradual shift of the product distribution to longer chains. In the range
of 60–80 1C, the equilibrium value of a increased with increasing
reaction temperature. This was because depolymerization of PF to
formaldehyde was endothermic while propagation of DMM or PODEn
was exothermic, and the whole reaction system showed an overall
weak endothermic effect, which accounted for the shift of the
distribution to longer chains with increasing temperature. In another
perspective, the increased temperature enhanced the equilibrium
concentration of formaldehyde in solution, thus shifted the distribu-
tion to long chain, which was in consistent with to the results of
Burger et al. (2012) on synthesis of PODEn from DMM and trioxane.
4. Kinetic modeling
In the kinetic modeling, the reaction system was assumed to
have a constant volume with an average density of 1.0 g cm–3.
762 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766

Thus, the mass fraction (wi) and mole concentration (Ci) has the
following relationship:
wi
Ci ¼ ði ¼ F; 1; nÞ ð9Þ
Mi

where wi is the mass fraction of compound i relative to the total

mass of all the homogeneous compounds (including homogenous
formaldehyde, DMM, and PODEn compounds), Mi is the molecular
weight of compound i, and Ci is the concentration of compound i.
The subscripts F, 1 and n (41) refer to formaldehyde, DMM and
PODEn, respectively.
Formaldehyde is a substance with complex existence forms in
the PODEn solution (Maurer, 1986). In this work, the concentration
of formaldehyde in the solution measured by titration with
sodium sulfite included formaldehyde of different forms. The
formaldehyde in different forms simultaneously react with PODEn
propagating to PODEn þ 1 with the same reaction rate constant
(Zhang et al., 2014). To simplifying the model, formaldehyde of Fig. 5. Equilibrium constant Kn at different temperatures for propagation of PODEn
compounds (DMM/CH2O molar ratio of 2:1, dosage of NKC-9 at 5 wt%).
different forms in the solution were all included in the concentra-
tion of formaldehyde (CF) in the kinetics model. As shown in Fig. 4,
CF increased at initial period before 10 min and then kept at a
constant level, suggesting that depolymerization of paraformalde- The effects of internal and external diffusions on the conversion
hyde is not the rate limiting step. With a DMM/CH2O molar of formaldehyde at 60 min were investigated at 80 1C with DMM/
feeding ratio of 2 and NKC-9 dosage of 5 wt%, the average value CH2O molar feeding ratio of 2 over 5 wt% NKC-9 catalyst, as shown
of CF was 0.901, 1.067 and 1.217 mol L  1 at 60, 70 and 80 1C, in Fig. 6. The diffusion affected the conversion of formaldehyde at
respectively. This indicated a favorable effect of higher tempera- 60 min when the reaction did not reach equilibrium. The effect of
ture on the depolymerization of PF. According to the experimental internal diffusion was eliminated when the catalyst particle
data, CF was considered as a constant during the kinetic modeling diameter was smaller than 1000 mm and that of external diffusion
of the chain propagation of PODEn. The study on the kinetics of was eliminated at a stirring speed higher than 300 rpm. In this
depolymerization of paraformaldehyde is complex and will be work, the experiments were carried out with catalyst particle
considered separately in our future work. diameter of 800 mm and stirring speed of 500 rpm. Thus, the
The reversible chain propagation reactions of PODEn com- experimental data represented the intrinsic kinetics for the for-
pounds followed a sequential reaction mechanism, and have the mation of PODEn from DMM and PF.
following equilibrium constants: In this system, the amount of water introduced by feeding PF
was less than 0.70 wt% relative to the mass of feedstocks. The
C PODE2 results showed that the methanol content at equilibrium in the
K1 ¼ ð10Þ
C DMM C F system was less than 1 wt%, indicating that the hydrolysis side-
reactions of DMM and PODEn played only a minor role and could
C PODEn þ 1 be neglected, as discussed in Section 2.3. At DMM/CH2O molar
Kn ¼ ðn⪢1Þ ð11Þ
C PODEn C F feeding ratio of 2, the molecular size of PODEn was mainly in the
range of n ¼2–6, and the amount of PODEn 4 6 compounds could be
The values of Kn at different temperatures were calculated from
neglected. To simplify the solution of the reaction rate matrix,
the experimental equilibrium product distribution data, as shown PODE6 was assumed to be the terminal compound in the chain
in Fig. 5. The experimental values of Kn was independent of n. This
propagation of PODEn.
agreed is well with the assumption that kp and kd are independent The chain propagation reaction of PODEn is condensation of
of the molecular size. The average values of Kn were 313.9, 271.0
two molecules (PODEn þCH2O) into one molecule (PODEn þ 1).
and 243.2 at 60, 70 and 80 1C, respectively. Supposing a first-order kinetics with respect to each reactant,
the reversible chain propagation reactions follow a second-order
kinetics for propagation and a first-order kinetics for depolymer-
ization, the reaction rate matrix is expressed as
dC
¼ KC
dt
2 32 3
 kp C F kd 0 0 0 0 C1
6 k C  kp C F  kd 0 7 6 7
6 p F kd 0 0 76 C 2 7
6 76 7
6 0 kp C F  kp C F  kd kd 0 0 7 6 7
6 76 C 3 7
¼6 76 7
6 0 0 kp C F  kp C F  kd kd 0 76 C 4 7
6 76 7
6 0 0 0 kp C F  kp C F  kd kd 7 6 7
4 54 C 5 5
0 0 0 0 kp C F kd C6

ð12Þ

where K is the rate constant matrix, and C is the concentration

matrix.
The initial values for solving Eq. (12) are

Fig. 4. Concentration of formaldehyde in the homogenous solution (CF) at different t ¼ 0; C DMM ¼ c0 ; C PODEi ¼ 0 mol L  1 ði ¼ 2–6Þ ð13Þ
reaction temperatures (DMM/CH2O molar ratio of 2:1, dosage of NKC-9 at 5 wt%).
 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766 763

Fig. 6. The effects of internal and external diffusions on conversion of formaldehyde at 60 min during synthesis of PODEn from PF and DMM (80 1C, DMM/CH2O molar
feeding ratio of 2, 5 wt% NKC-9 catalyst).

The analytical solution of the above matrix, namely the con- X

N
ESS ¼ ðC i;exp  C i;cal Þ2 ð19Þ
centration functions of PODE1–6, could be represented as
i¼1

iX
¼6
where N is the number of the data points, Ci,ave is the average value
C n ¼ f 1 β 1 c0 þ c0 f i βi eλi kd t ð14Þ
of experimental value of Ci, and Ci,exp and Ci,cal are the experi-
i¼2
mental values and calculated values of Ci, respectively.
For n ¼1–6, f are ω, θ, η, ν, κ, δ, respectively. The Arrhenius parameters of propagation reaction of PODEn,
The coefficients in the above solutions are expressed in matrix including the pre-exponential factor (Ap, Ad) and activation energy
as follows: (Ep, Ed), were determined using the following Arrhenius equation

2 pffiffi 3:5 pffiffi 3:5 3

2 3 1A A3 3A þ A3 þ A4  3A þ A3 þ A4 A3:5 þ A3 þ A4 A3 þ A4  A3:5
β 6 1A
6 1þA 12ð1  A þ A2 Þ 12ð1  A þ A2 Þ 4ð1 þ A þ A2 Þ 4ð1 þ A þ A2 Þ 7
6λ7 6 pffiffiffiffiffiffi pffiffiffiffiffiffi pffiffiffi pffiffiffi 7
6 7 6  A 1 3A A  1  3A  A 1 A  A 1  AA1 7
6 7 6 7
6ω7 6 1 A2 A2 A2 A2 A 2 7
6 7 6 pffiffiffiffiffiffi pffiffiffiffiffiffi 7
6θ7 6 2 7
6 7 6 A A ð 3A  1ÞA  2 ð  3A  1ÞA  2 ðA 0:5
 1ÞA  2  2A  1:5
7
6 7¼6 pffiffiffi pffiffiffi 7 ð15Þ
6 η 7 6 A2 A 1
ð2A0:5  3ÞA  1:5 ð2A0:5 þ 3ÞA  1:5  A  1:5  1:5 7
6 7 6 A 7
6ν7 6 3 pffiffiffi pffiffiffi 7
6 7 6 A A1 ð 3  2A0:5 ÞA  1:5  ð2A0:5 þ 3ÞA1:5  A  0:5 A 0:5 7
6 7 6 pffiffiffi pffiffiffi  0:5 7
4κ5 6 4  0:5 7
4 A 1 ðA0:5  3ÞA  0:5 0:5
ðA þ 3ÞA ð1  A0:5 ÞA  0:5 0:5
ð1 þA ÞA 5
δ A5 1 1 1 1 1

as (20)
where E
lnðkÞ ¼ lnðAÞ  ð20Þ
A ¼ K nCF ð16Þ RT

Given the experimental concentrations of PODEn compounds at

different reaction temperatures (60, 70, and 80 1C) and different 5. Model validation and calculations
reaction times (2, 5, 10, 20, 30, 60, and 90 min), the rate constants
were estimated using least-squares regression. The coefficient of The concentrations of formaldehyde and PODE1–6 compounds
determination (R2) defined by Eq. (17) was used to measure the at different operating conditions are listed in Table 2. The PODE2,
agreement between the experimental and calculated data. PODE3, PODE4, PODE5 and PODE6 appeared one by one during the
reaction period, which further validated the sequential propaga-
TSS  ESS tion mechanism in this system. The rate constants kd at different
R2 ¼ ð17Þ
TSS temperatures were obtained by least-squares aggression of the
experimental concentration–time data of DMM using Eq. (14) with
where total sum of squares (TSS) and explained sum of squares
n ¼1. The rate constants kp at different temperatures were calcu-
(ESS) are defined as
lated from the corresponding Kn data. The Arrhenius parameters
X
N including the pre-exponential factor (Ap, Ad) and activation energy
TSS ¼ ðC i;exp  C i;ave Þ2 ð18Þ (Ep, Ed) respecting to 5 wt% dosage of NKC-9 resin catalyst were
i¼1 listed in Table 3. The values of Ap and Ad were
764 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766

Table 2
Concentrations of formaldehyde (CF) and PODE1–6 (C1–C6) in the designed space during synthesis of PODEn from PF and DMM catalyzed by NKC-9.

T (1C) t (min) CF (mol L  1) C1 (mol L  1) C2 (mol L  1) C3 (mol L  1) C4 (mol L  1) C5 (mol L  1) C6 (mol L  1)

60 0 0.758 12.802 0.000 0.000 0.000 0.000 0.000

2 0.801 12.802 0.141 0.001 0.000 0.000 0.000
5 0.867 11.988 0.659 0.029 0.001 0.000 0.000
10 0.901 11.193 1.224 0.107 0.008 0.001 0.000
20 0.901 10.907 1.407 0.145 0.014 0.001 0.000
30 0.901 10.585 1.602 0.194 0.021 0.003 0.000
60 0.904 10.171 1.833 0.264 0.034 0.005 0.001
90 0.903 9.292 2.250 0.435 0.076 0.015 0.003

70 0 0.853 12.645 0.000 0.000 0.000 0.000 0.000

2 0.927 11.890 0.613 0.025 0.001 0.000 0.000
5 0.978 11.356 1.004 0.071 0.005 0.000 0.000
10 1.065 11.001 1.244 0.112 0.009 0.001 0.000
20 1.067 10.450 1.585 0.192 0.021 0.003 0.000
30 1.087 10.040 1.813 0.261 0.034 0.005 0.001
60 1.078 9.436 2.110 0.377 0.061 0.011 0.002
90 1.083 8.771 2.548 0.627 0.140 0.036 0.009

80 0 1.004 12.666 0.000 0.000 0.000 0.000 0.000

2 1.075 12.186 0.398 0.010 0.000 0.000 0.000
5 1.158 10.981 1.271 0.118 0.010 0.001 0.000
10 1.208 10.238 1.718 0.230 0.028 0.004 0.001
20 1.217 9.526 2.079 0.362 0.057 0.010 0.002
30 1.221 9.363 2.153 0.395 0.066 0.013 0.002
60 1.211 8.620 2.542 0.620 0.137 0.035 0.009
90 1.223 8.429 2.625 0.685 0.162 0.044 0.012

Table 3
Rate constants of the propagation (kp) and depolymerization (kd) reactions of
PODEn compounds respecting to 5 wt% dosage of NKC-9 resin catalyst in the
designed space.

k (min–1) Temperature (1C) Arrhenius parameters

60 70 80 E (kJ mol–1) A

kp 11.738 17.693 26.339 39.52 1.84  107 L mol–1 min–1

kd 0.037 0.065 0.108 52.01 5.36  106 min–1

Fig. 8. The parity plot of experimental data (Ci,exp) and calculated data (Ci,cal) using
DMM and PF as feedstocks at different reaction temperatures (DMM/CH2O molar
ratio of 2:1, dosage of NKC-9 at 5 wt%).

The key assumption of the kinetic model is that the rate

Fig. 7. Arrhenius plots and Vant Hoff plots of the reversible propagation reactions
of PODEn compounds in the designed space.
1.84  107 L mol  1 min  1 and 5.36  106 min  1, respectively. The
activation energy Ep (39.52 kJ mol  1) was lower than Ed
(52.01 kJ mol  1), indicating that the reversible propagation reac-
tions of PODEn were exothermic. Corresponding to the Kn values
illustrated in Fig. 5, Vant Hoff plots are of great importance to
evaluate the accuracy of the reversible kinetics data. As shown in
Fig. 7, both the Arrhenius and Vant Hoff plots of the reactions
present good linearity (R2 40.990), confirming that the kinetic
model proposed in this work had a good accuracy.
constants of propagation (kp) and depolymerization (kd) were
the same for the series of PODEn propagation reactions. To verify
the prediction ability of the kinetic model, the concentrations of
PODE2–6 were calculated from Eq. (14) with n¼ 2–6 as a function of
the reaction time with the determined kd and kp from concentra-
tion of DMM, and compared with the experimental data. The
parity plot of the experimental and calculated concentrations of all
compounds is shown in Fig. 8. The R2 value calculated by Eq. (17)
for all involved data points is 0.998, indicating a good agreement
between the experimental and calculated data. The comparison
between the experimental and calculated concentrations of
PODE2–6 at different temperatures and reaction times is shown
in Fig. 9. A good agreement was obtained for the experimental and
calculated concentrations of PODE2–6.
To further verify the prediction ability of the kinetic model, a
mixture of DMM, PODE5 and PODE6 were used as feedstocks at
 Y. Zheng et al. / Chemical Engineering Science 134 (2015) 758–766 765

Fig. 10. Comparison between experimental and calculated C1–C8 data using a
mixture of DMM, PODE5 and PODE6 as feedstocks at 80 1C over 5 wt% dosage of
NKC-9.

model proposed in this work based on chain propagation mechan-

ism. These results show that kinetic model proposed in the
present work has a good prediction ability, and can be used in
designing and scaling-up the process of PODEn synthesis.

6. Conclusions

The kinetics of synthesis of PODEn from PF and DMM catalyzed

by NKC-9 acidic ion exchange resin was investigated in the
designed space, namely reaction temperatures (60, 70, and
80 1C) and reaction times (2, 5, 10, 20, 30, 60, and 90 min), in a
batch stirred autoclave. A kinetic model was proposed based on a
sequential reversible reaction mechanism. The experimental
results and theoretical analysis lead to the following conclusions:

(1) The transient molecular size distribution of PODEn compounds

from PF and DMM followed Schulz–Flory distribution model.
(2) In the reversible sequential propagation of DMM and PODEn,
the propagation reactions followed a second-order kinetics for
propagation and the depolymerization reactions followed a
first-order kinetics. The rate constants for propagation (kp) and
for depolymerization (kd), and the reaction equilibrium con-
stant (Kn) were independent of PODEn molecular size.
(3) Respecting to 5 wt% dosage of NKC-9 resin catalyst, the pre-
exponential factors Ap for propagation and Ad for depolymer-
ization were 1.84  107 L mol–1 min–1 and 5.36  106 min–1,
respectively. While the activation energy Ep (39.52 kJ∙mol–1)
for propagation was lower than Ed (52.01 kJ mol–1) for depo-
lymerization, validating that the reversible propagation reac-
Fig. 9. Comparison between experimental and calculated C1–C6 data using DMM
tions of PODEn compounds were exothermic.
and PF as feedstocks at different reaction temperatures (DMM/CH2O molar ratio of
2:1, dosage of NKC-9 at 5 wt%).

80 1C over 5 wt% NKC-9 resin catalyst. The initial concentrations of Acknowledgments

DMM, PODE5 and PODE6 were 9.701 mol L  1, 0.995 mol L  1 and
0.303 mol L  1, respectively. During the reaction, the formaldehyde The authors gratefully acknowledge the financial supports by
concentration CF increased in the first 10 min and then kept almost the National Natural Science Foundation of China (No. 20606021).
unchanged at 1.209 mol L  1. Using the kd and kp data at 80 1C in
Table 3, the C1–C8 data at different reaction times were calculated
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