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Adkesson et al.
(54)
US 8,183,417 B2
PURIFICATION OF
(56)
References Cited
BIOLOGICALLY-PRODUCED
1,3_PROPANEDIOL
(75)
4,380,678 A
4/1983 Sirkar
5,034,134 A
321g; 25 31'
535103036 A
5,686,276 A
6,136,576 A
'
'
6,232,512 B1
6,245,879 B1
6/2001
6,358,716 B1
6,361,983 B1
7,919,658 B2 *
4/2011
K 1
tal.
Adkesson et al.
ms) F9161111Gallagherw?mmgton
2004/0198965 A1
2004/0260125 A1
.......... .. 568/868
W0
$8
$8 81/3333; 25 13/5881
OTHER PUBLICATIONS
73
(*)
Notice:
, p11
Final Of?ce Action mailed Aug. 10, 2009, in US. Appl. No.
'
(22)
Filed:
(65)
(51)
(52)
'
N .60/468231 ?l d
e on
ay
Int Cl
(2006 01)
C0 7C 31/18
(200601)
U 5 Cl
.
(57)
ABSTRACT
.
.
C0'7C 2'9/74
.
(58)
c1ted by exammer
(21)
- -
'
.
...................................... ..
13 Claims, No Drawings
US 8,183,417 B2
1
PURIFICATION OF
BIOLOGICALLY-PRODUCED
manufacture of polyesters.
1,3-PROPANEDIOL
500 ppm.
A process for the treatment of aqueous solutions of poly
20
35
45
made therefrom.
Fisher et al. disclose in WO 00/24918 a method for puri
60
exchange step.
US 8,183,417 B2
3
25
30
are removed.
less than about 0.200 and at 250 nm of less than about 0.075
and at 275 nm ofless than about 0.075; or 2) a composition
having L*a*b*b* color value ofless than about 0.15 and an
absorbance at 275 nm of less than about 0.075; or 3) a per
oxide composition of less than about 10 ppm; or 4) a concen
any pair of any upper range limit or preferred value and any
loWer range limit or preferred value, regardless of Whether
ranges are separately disclosed.
US 8,183,417 B2
5
puri?ed 1,3-propanediol.
described beloW:
1. Filtration
25
30
a commercial setting.
40
45
50
exchange resin.
55
3. Distillation
Next, a re?ning process is conducted in order to remove
65
US 8,183,417 B2
7
mately 60 psi.
In a preferred embodiment, micro?ltration comprises
removing molecules having a siZe greater than 0.2 microns.
Nano?ltration
When the micro?ltration and ultra?ltration of the fermen
tation broth is complete, the broth is essentially free of
insoluble material. It is the intent of the nano?ltration process
ions for the anions in the broth. This occurs because the
20
cation beds and caustic through the anion beds. The high
concentration of hydrogen ions in the acid overWhelm the
attraction for the higher charged ions causing them to be
25
30
35
40
able limits. The spent resin is replaced With fresh resin and the
cycles begin again. Resin life is often described in terms of the
number of cycles, Which varies according to individual appli
cation. User speci?cations Will accompany the resins, Which
are readily available commercially.
45
55
400 Daltons.
60
Ion Exchange
Following the ?ltration step(s), the major remaining non
65
US 8,183,417 B2
10
the feed is switched to the second pair and the regenerated
the length of the column. Not only does this alloW for maxi
mum exchange, it also reduces the potential for chemical
reactions caused by extremes in pH. These reactions usually
tion of the mixed bed is unique in that the resins must ?rst be
Evaporation
column is then ready for product again. The mixed bed polish
20
things, pressure drop and desired cycle time. The feed ?oW
rate and viscosity Will dictate the cross-sectional area and
25
alloWable bed depth required for the columns to keep the feed
pressure beloW the target limit (approximately 50 psig). The
cycle time of the resin must alloW su?icient time for proper
product, it takes some time for the Water, product, and chemi
cals to migrate into and out of the resin beads during the
respective steps in the cycle. These time limits are de?ned by
30
sources.
Distillation
40
tWo-stage condenser off the last stage Will be used. The ?rst
condenser Will be designed to recover and recycle any PDO
boiled off. The second condenses the remaining vapors. The
heat from the condensate off the evaporator Will be recovered
With heat reclaim heat exchangers or used Where hot Water is
required.
Polish With Mixed Ion Exchange
After subjection of the fermentation broth to ion exchange,
for example as described above to four ion exchange columns
of the CACA system, and optionally to evaporation, subjec
tion additionally to a strong base anion is preferred for maxi
mum puri?cation. Thus, by adding the strong base mixed bed
65
US 8,183,417 B2
11
12
in its entirety.
In general, applicants preferred distillation train consists
loW boilers and residual Water that come from column 1 and
made from such entities having at least one repeat unit of the
30
45
compound.
miZe the hold-up time in the reboiler and therefore the unde
sirable reactions in the bottom of the column. Steam (200
psig) can be fed to the reboiler to provide the necessary boilup
control over the intrinsic viscosity (IV) and the color index
60
cally, any of the folloWing metals Ni, Co, Ru, Rh, Pd, Ir and
Pt With or Without various promoters are also effective cata
(2001).
US 8,183,417 B2
13
14
Final Distillation
impurities.
Distillation Column 4 (Product Column)
30
35
reactors.
40
55
disposed of.
Final product quality is affected not only by the separation
65
exist for the user relating to the vacuum system selected. TWo
stages can be used, With the ?rst stage an air eductor or a
bloWer instead of a steam jet, and the second might be a dry
screW pump instead of a liquid ring. The non-condensable
vapor from the vacuum system can be sent to a vent scrubber
Vacuum System
45
operations.
US 8,183,417 B2
15
16
gDCW/L (dry cell Weight). The seed ?ask Was used to inocu
late the seed fermentor.
fermentor Was inoculated With the shake ?ask that Was refer
and most preferably less than about 150 ppm. The term ppm
25
30
TABLE 1
less than about 0.200 and at 240 nm is less than about 0.075
and at 270 nm is less than about 0.075.
35
Media Component
cants process.
sulfuric acid
40
45
50
1.4
1.02
MgSO4*7H2O
0.6
FeSO4*7H2O
CaC12*2H2O
0.400
0.1
0.5
0.40
MnSO4 H2O
NaCl
ZnSO4*7H2O
CuSO4*5H2O
H3BO3
NaMoO4*2H2O
0.015
0.005
0.0005
0.00005
0.00005
0.00005
vacuum rated, air sparged, pres sure vessel With a total volume
of 13,000 L. The production fermentor is ?lled to an initial
Example #1
60
1.34
KH2PO4* * *
this invention, and Without departing from the spirit and scope
0.55
65
isolated small colony Was chosen from the streak plate and
US 8,183,417 B2
17
18
TABLE 2
Micro?ltration operation
Cell
Optical Concentration
Density
(gram/L)
Feed
to Micro?ltration
Final Retentate
Volumetric
Flux
Concentration
Ration
(liters/m2/
hr)
194.3
44.3
13.29
N/A
159 .48
12
Average
19. 7
108
4.5 gDCW/L.
The production fermentation cycle is complete within
3.
TABLE 3
30
35
Example #2
Flux
VCR
(l1t61S/1'H2/111)
1.1
170.4
1.3
1.8
2.9
4.7
6.4
7.1
7.3
8.6
11.5
194.3
197.4
138.2
74.6
37.3
24.1
23.0
21.5
19.7
40
Example #3
45
Ultra?ltration
50
60
US 8,183,417 B2
19
20
TABLE 4
Ultra?ltration operation
tate ?oW Was ratioed, via the concentrate ?oW control valve
ratioed to 5% of the inlet feed ?oW. Temperature Was held
intial
Stage #1
Stage #2
1.49
2.94
3896
1.52
Concentration Factor
F1uX(hterS/m2/hr)
?nal
Concentration2 Factor
avera
3C or
#3
Total
15.83 1583
3896
3274
369
3.16
16.10
16.1
2???
25-23
is;
29m
2735
2114
08
253
Separation characteristics
membrane
Total
Feed to
I
Ultra?ltrat1on
Non
Sugar
PDO
Rejection
(gram/L)
(gram/
L)
Nitrogen
(ppm)
Ammonia
(ppm)
Nitrogen
(ppm)
107.9
993.0
1048.0
133.6
8.7
Ammonia
Permeate
8.1
116.4
817.1
951.0
37.3
Retentate
23.0
109.3
2729.9
1459.1
1533.4
Rqi ?ction
7%
0%
13%
9%
72%
TABLE 6
20
Nano?ltrat1on operation
Stage #1
Stage #2
Stage #3
Total
Conc?nmmon Factor
Flux (11t6lS/IH2/hl)
1'72
68.1
4-3
20-2
20-2
56.8
30.3
51.7
Sulfate Phosphate
Rejection Rejection
UVi270
25
TABLE 7
Nano?ltrat1on separation characteristics
Feed to Nano?ltrat1on
Permeate
Retentate
Rejection
Divalent
Monovalent
PDO
Cations
(Ca + Mg)
Cations
(Na + K)
(gram/L)
(gram/L)
(ppm)
(ppm)
(ppm)
(ppm)
Hm
7.31
2.17
78.63
70%
111.84
112.92
106.57
0%
31.03
14.54
152.04
53%
247.62
198.45
821.33
20%
150
52
1480
65%
650
550
2060
15%
2.875
1.7628
Total
Sugars
39%
broth concentrations.As the PDO ultra?ltration feed concentrates through the system, the ?uxes decline With an increas-
more concentrated than the initial feed and the overall ?ux
performance is an average of the individual stages. With the
skid is ~15-fold more concentrated than the original feed the 45 demonstrated no fouling as the ?uxes and concentration fac
overall ?ux performance is averaged over the three stages
tors of the individual stages remained constant over the
experiment.
branes, therefore With ultra?ltration removing 72% of the 50 iZed impurities of the PDQ process are removed through
Example #5
rejected.
Ion Exchan e
Example #4
_
Nano?ltrat1on
60
US 8,183,417 B2
21
22
Emission Spectroscopy)
10
15
tration.
pH
TABLE 10
Feed to Ion Exchange
1.373
3400
90.0
7.59
Process
Process
Process
Process
Process
Sampling
Sampling
Sampling
Sampling
Sampling
Process Sampling
0.062
0.074
0.099
0.120
0.133
0.131
94.8
88.5
75.1
68
114.3
89.0
89.3
86.6
90.3
89.1
10.27
9.72
9.88
9.78
9.81
256
88.1
10.25
Process Sampling
0.143
44.9
89.5
10.45
Process Sampling
0.170
36.2
87.4
Process Sampling
0.288
23
93.6
9.9
Process Sampling
Composite Ion Exchange
1.047
0 069
21.4
95.7
94.8
92.7
9.4
10.22
Evaporation Rgsults
20
DS
(%)
UV_270 Hm
25 22
'
29.12
38 33
25
'
Product
Composite
0 224
'
0.230
0 234
'
59-86
82-91
0-245
0-214
85
0.264
TABLE 9
Ion Exchange Component Pro?les
Divalent
Cations
Monovalent
Cations
2826
38
8.05
4.25
Chloride
ppm (asiis)
Phosphate
ppm (asiis)
Ammonia
ppm (asiis)
55
405
2
702.3
2.3
176.5
27.38
270 nm) greater than 0.5 ABU. For this Example, break
through occurs as the result of the UV component eluting
from the second set of anion columns. The ion exchange cells
are siZed suf?ciently for ion removal as the overall ionic
species are still 98% removed. Capacity of the ion exchange
is dictated by the resins ability to absorb the UV contributor
45
50
Example #7
stream.
55
Example #6
Evaporation
60
65
base anion resin (DoWex 22) for the removal of residual salts
and color. The mixed bed is a 1 ft diameter by 5 ft high column
containing 6 ft3 of mixed bed resin that is fed at 1.5 gpm by a
cooled (80 F.) evaporated 3 G stream. Table 11 and 12
demonstrate the mixed beds polishing capacity.
US 8,183,417 B2
23
24
TABLE 11
Absorbance (nm)
210
230
250
270
2.529
1.634
1.810
1.191
1.063
0.457
0.957
0.373
290
310
0.587 0.296
0.231 0.085
treated product.
The distillation re?ning process of the invention requires
thermal treatment. A four distillation column process is pre
ferred. Column 1 is aimed primarily at the reduction of water,
which is removed in the overhead. Column 2 separates the
TABLE 12
Mixed Bed Polishing Ion Exchange
Conductivity
(uS/cm)
pH
23.7
7.73
8.38
Like the CACA ion exchange, the mixed bed has the capac
caramel color to a near water white solution, while the UV
25
30
Hydrogenation
The primary purpose of chemical reduction is to reduce the
35
able indicator of the PDO quality and the color of the ?nal
polymer. The UV spectra are normally collected at a 1:5
dilution ratio and reported as diluted numbers. It is believed
that a color metric of 270 nm UV below 0.1 will result in
products pH.
Example #8
45
General Protocol
50
sugars can remain in the broth and enter into the re?ning train.
TABLE 13
Unfermented sugars in light evaporated fermentation broth
Carbohydrates by HPAE-PAD
Iso-highers
(DP2-
Sample
Ugml
ID
Description
DP12)
Isomaltose Panose
73061
Light evap
6650
6470
4880
1050
500
6160
6340
4410
1010
505
Dextrose
Fructose
250
145
110
190
240
140
product
73329
Light evap
product
US 8,183,417 B2
25
26
TABLE 15
Retention Time
1.282
disappeared
1.306
1.439
Formed
Formed
Examples #(8)1-(8)8
In these examples, PDO described in Case A Was hydro
genated in a shaker tube With RANEY 2400 Nickel slurry
25
30
Was kept shaking for the speci?ed time, then cooled and
depressuriZed. The quality of the hydrogenated product Was
determined With GC and UV/VIS as described above. Table
14 shoWs the reduction in the UV absorption at 280 nm.
Change
2.246
disappeared
3 .253
disappeared
4.191
disappeared
4.270
Formed
5.285
disappeared
5 .674
unchanged
5 .760
5 .902
Increased
Reduced
6.104
6.900
7.333
unchanged
unchanged
unchanged
7.490
Formed
8.05 8
disappeared
8.567
8.828
9.206
9.278
disappeared
disappeared
unchanged
unchanged
9.616
9.743
Formed
Reduced
9.847
unchanged
10.257
Increased
10.386
unchanged
10.620
10.669
10.827
Formed
11.395
disappeared
Reduced
Increased
35
TABLE 14
Example #(8)9
Example#
Temp.
C.
Pressure
Psia
Cat.
Wt %
Time
hr.
UV-280
A.U.
1.58
80
400
0.05
0.64
100
400
0.05
0.65
80
800
0.05
0.99
100
800
0.05
0.46
100
100
0.125
0.25
1.28
1200 C. for 4 h. The process Was repeated three times and the
products Were combined and distilled in tWo pilot scale dis
tillation columns to remove the lights and heavies. The ?nal
product had a UV-270 beloW 0.3 AU. This puri?ed PDO Was
100
100
0.125
1.08
120
400
0.125
0.53
140
400
0.125
0.42
to 6.8.
55
Distillation)
65
US 8,183,417 B2
27
Example #(8)10
28
eral purity aspects, to tWo separate, commercially-obtained
TABLE 17
Bio - PDO
Unlts
Soum A
Source B
Ppm
570
695
Blo'PDo
80
AU
0'25
1'15
0'12
AU
0.123
0.427
0.017
UVAbS 275 nm
AU
0068
0151
0036
UVAbs 350 nm
AU
0.013
0.007
0.001
PeroXiii?i *
P1211
67
147'411
43
175'03
1'1
pp
Unlts
l,3_propan?diol
GC mao?,
pH, neat
UVAbS-@270nm,115 dilution
pH
AU
L*a*b*
Water
b*
ppm
Uvabs 220 nm at
UV abs 250 nm mat
AU
AU
g, _
Color APHA
0.10
115
0-144
0'017
AU
0.036
AU
0001
Peroxide
ppm
Metals
ppm
<1
ppm
<1
0-01
3
Sulfur
99992
8.22
3r Ony
pm
temperature and increased contact time or reduced space 40 other than 1,3-propanediol, as measured by a gas chromato
TABLE 16
Example
Feed
11
12
13
14
15
16
17
18
19
20
Catalyst
LHSV, l/h
HZ/PDO,
Press. Product
scc/g Temp. C. psig
UV
RANEY Ni
RANEY Ni
Ru/C
Ni/SiO2iAl2O3
4
4
4
4
21.3
21.3
21.3
21.3
120
120
120
80
400
650
400
400
Ni/SiO2iAl2O3
Ni/SiO2iAl2O3
Ni/SiO2iAl2O3
Ni/SiO2iAl2O3
Ni/SiO2iAl2O3
Ni/SiO2iAl2O3
4
4
4
3.8
1.9
1.27
21.3
21.3
21.3
22.4
22.4
22.4
100
60
40
120
120
120
400
400
400
400
400
400
1.52
0.35
0.32
0.33
0.55
0.47
0.74
0.87
0.32
0.35
0.15
S ppm
pH
13
5.7
0
0
7.5
6.7
60
Example #9
P
ur1ty
Ch
carbon.
aracter1Zat1ons
65
US 8,183,417 B2
29
30
removed;
(c) subjecting the product of step (b) to chemical reduction;
and
exchange procedure.
hydroboration.
3. The process of claim 2, Wherein said chemical reduction
is hydrogenation.
4. The process of claim 1, further comprising Wherein the
fermentation broth is subjected to an evaporation step.
5. The process of claim 4, Wherein said evaporation step is
20
30