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Us 7126032
Us 7126032
TABLE 1.
Crude Tank 1 Recovered Stripping Recovered Column
Glycerin Effluent Methanol Column Feed Glycerin Bottoms
Mass Mass Mass Mass Mass Mass
Component bjr. Wt. 90 bhir. Wt. 90 bhir. Wt. 90 bir. Wt. 90 bhir. Wt. 90 bir. Wt. 90
Water 83 1.OO 39 O.S3 46 4.67 409 S.32 26.0 O416 O O.OO
CHOH 996 12.OO 79 1.08 917 93.10 30 O.39 O.1 O.OO2 O O.OO
Glycerin 71.96 86.70 7167 98 22 2.23 7190 93.6O 6224.O. 99.576 1102 87.46
FAME 21 O.25 O O.OO O O.OO O O.OO O O.OO O O.OO
Heavies* 4 O.OS 30 O41 O O.OO 53 O.69 0.4 O.OO6 158 12.54
Total 83OO 100.00 731S 10O.OO 985 100.OO 7682 1 OOOO 62SO.S 10O.OO 1260 100.00
*Includes Glycerides
15
The crude glycerin stream used as the basis for the model tion unit as opposed to a short packed column, following
has a composition that is typical for crude glycerin streams completion of the batch stripping and conversion of FAME
coming from the production of fatty acid methyl ester to glycerides.
production for biodiesel. The crude glycerin stream is Approximately 1.5 gallons of glycerin byproduct was
approximately 86.7 weight percent glycerin, with most of obtained from a biodiesel pilot plant. This material is
the balance, about 12.0 percent, being methanol. Modeling believed to be typical of byproduct streams from biodiesel
the process according to the exemplary embodiment using production. A Small amount of biodiesel fuel floating on top
this typical feed results in a predicted effluent stream from of the glycerin byproduct was decanted away. The crude
the first tank containing essentially no FAME and a signifi 25 glycerin had an initial pH of approximately 11.6. After
cantly reduced content of methanol, approximately 1.08 adjusting the pH of a portion of the crude glycerin to
weight percent. This demonstrates that the transesterification approximately 5.8, approximately 1000 grams of the pH
of FAME in the first tank essentially goes to completion and adjusted material was charged to a 1.5 liter resin kettle. The
that methanol is efficiently removed from the glycerin crude glycerin was heated to about 153° C. with nitrogen
stream. The model also demonstrates that methanol can be 30 sparging for a period of approximately 1.5 hours. Over this
recovered overhead from the first tank with an acceptable time 63.2 grams of volatiles were collected overhead. The
distillate had a density of 0.83 g/mL, indicating that it was
water content of less than 5 weight percent. The feed to the mostly methanol. The cooled contents were charged to a
stripping column, coming from the second tank via the glass separatory funnel and allowed to phase separate over
decanter shows the glycerin stream having an adjusted water 35 night. On Separating 593.4 grams of a lower product phase
content and further reduced methanol content, obtained by was collected, and 272.6 grams of an upper phase was
addition of a wash water stream and further stripping of collected.
water and methanol in the second tank. The composition of Another batch was prepared in a similar manner, except
the wash water will depend on many factors, such as the that the pH was adjusted to only 6.8 this time and a phase
efficiency of the upstream phase separation, as well as 40 separation was performed prior to charging to the resin
catalyst and methanol concentrations used in the biodiesel kettle.
transesterification reaction. The wash water stream will most Water was added to both lower phases to a concentration
likely be the concentrated aqueous product from a counter of about 5 weight percent. The higher pH batch had to be
current multi-stage washing operation, whether done con filtered to remove solids that had precipitated. The lower
tinuously or batchwise, wherein the incoming organic 45 phases were then combined for the distillation.
stream first contacts the most concentrated water stream. For The continuous-mode distillation was performed using a
modeling purposes, the methanol and glycerin were both 4-inch diameter Pope wiped film evaporator to simulate the
assumed to be less than 2 weight percent in the wash water. vacuum conditions that are expected to be used in practice
In practice, conditions such as temperature and sparging rate and the vapor side draw. The upper Zone of the wiped film
in the second vessel would be adjusted as needed to have the 50 evaporator was maintained at 156 to 160° C. and the lower
water content close to 5 percent in its effluent. The model Zone was maintained at 173 to 176°C. The absolute pressure
further predicts a recovered glycerin stream from the flash in the system was maintained at 7 to 9 mm Hg. The crude
distillation having a purity of greater than 99.5 percent, with glycerin feed was pumped in continuously at rates ranging
most of the balance being water. The column bottoms, still from 3 to 10 mL/min over the course of more than 3 hours.
containing a significant amount of glycerin, can be continu 55 A first product cut, simulating the side product cut, was
ously or intermittently purged in part with most being collected in a receiver attached to the wiped film evaporator
recycled to the decanter. where product from the internal condenser is collected. A
second cut was obtained by condensing a vapor stream from
EXAMPLE the wiped film evaporator at a first condenser after the wiped
60 film evaporator, which was filled with hot water to condense
The process according to the current invention was mod out glycerin. This simulated the overhead glycerin fraction
eled experimentally on a bench scale. The only differences to be collected. Finally, water was condensed out of the
from the modeled process and the industrial scale process vapor stream using a cold trap condenser cooled with water
described above were that only a single reactor was used, ice. Some of the water vapor appeared to get carried over
batchwise, on the bench scale, as opposed to two in series 65 into the vacuum pump.
and continuous mode for the process described above, and The side product cut amounted to 194.5 grams of a lightly
that the distillation step was done in a wiped film evapora amber colored product, which had a density of 1.259. The
US 7,126,032 B1
9 10
overhead product cut was 220.7 grams of a water white glycerin effluent stream into a top layer comprising oil
product, which had a density of 1.256. The specific gravity and fatty acid and a bottom layer comprising glycerin,
for pure glycerin is 1.261. A total of 386.3 grams of water, and at least one glyceride,
evaporator bottoms were also collected. The total recovery wherein the bottom layer is the stream to be distilled.
represented by the side and overhead product cuts was only 5. The process according to claim 3, further comprising:
51%. This is likely due to too high a feed rate initially and removing a sidestream comprising glycerin vapor from
lower than desirable temperature during the distillation. the flash distillation column, and condensing the side
Also, it should be noted that the process design calls for Stream.
recycle of the distillation bottoms. 6. The process according to claim 1, wherein the first
The invention has thus been described with reference to 10 reactor is sparged with nitrogen at a rate of from about 3
exemplary drawings and a working example. The novel percent to about 20 percent by weight of the crude glycerin
process according to the current invention utilizes common, stream feed rate to the first reactor, and the second reactor is
simple equipment and allows for low energy recovery of a sparged with nitrogen at a rate of from about 2 percent to
purified glycerin stream. In addition, the process allows for about 15 percent by weight of the crude glycerin stream feed
recovery of greater than 90 percent of the low molecular 15 rate to the second reactor.
weight alcohol from the crude glycerin and process water 7. The process according to claim 1, further comprising,
streams, most of it as a relatively low-water material suitable preheating the second glycerin effluent stream prior to the
for recycle as is. distillation column to partially vaporize glycerin and water
What is claimed is: in the second effluent stream.
1. A process for purifying glycerin recovered from a fatty 8. The process according to claim 5, further comprising,
acid alkyl ester process, comprising: combining the condensed sidestream product and condensed
providing a crude glycerin stream recovered from fatty overhead glycerin fraction to form one liquid stream, and
acid alkyl ester production, the crude glycerin stream passing the one liquid stream over at least one bed of
comprising: glycerin, at least one low molecular weight sorbent.
alcohol, at least one glyceride, at least one fatty acid 25 9. The process according to claim 2, wherein the first
ester of a low molecular weight alcohol and water, glycerin effluent stream and water stream are mixed prior to
heating the crude glycerin stream to a temperature of from being fed to the second reactor.
about 125° C. to about 160° C., 10. The process according to claim 2, wherein
feeding the crude glycerin stream to a first reactor main in the second reactor a portion of the glycerides and fatty
tained at about 125° C. to about 160° C., wherein at 30 acid esters are hydrolyzed to produce additional glyc
least a portion of the at least one fatty acid alkyl ester erin and free fatty acids.
contained in the crude glycerin stream undergoes a 11. The process according to claim 1, further comprising
transesterification with glycerin to produce additional prior to heating the crude glycerin stream to a temperature
amounts of the at least one low molecular weight of from about 125° C. to about 160° C. in the first
alcohol and additional glyceride, 35 reactor, but after reducing the pH below 7, separating
in the first reactor, sparging the crude glycerin stream with the crude glycerin stream into a top layer comprising
nitrogen, thereby stripping a portion of the at least one oil and fatty acid and a bottom layer comprising
low molecular weight alcohol and water from the crude glycerin, at least one low molecular weight alcohol, at
glycerin stream, to produce a first glycerin effluent least one glyceride, at least one fatty acid ester of a low
Stream, 40 molecular weight alcohol and water, wherein
feeding the first glycerin effluent stream from the first the bottom layer is the stream to be heated to about 125°
reactor to a second reactor maintained at about 120° C. C. to about 160° C.
to about 160° C., 12. The process according to claim 3, wherein the distil
in the second reactor, sparging the first effluent stream lation bottoms are predominately recycled to an upstream
with nitrogen, thereby stripping the at least a portion of 45 step with a partial purge to prevent excessive accumulation
the at least one low molecular weight alcohol and a of salts and other impurities.
portion of the water, to produce a second effluent 13. A process for treating glycerin recovered from a fatty
stream comprising glycerin, at least one glyceride and acid alkyl ester process, comprising:
water; providing a crude glycerin stream recovered from fatty
distilling the second glycerin effluent stream in a flash 50 acid alkyl ester production, the crude glycerin stream
distillation column wherein water and glycerin are comprising: glycerin, at least one low molecular weight
vaporized and removed as an overhead stream. alcohol, at least one glyceride, at least one fatty acid
2. The process according to claim 1, further comprising, ester of a low molecular weight alcohol and water,
adding a water stream containing at least one low molecular heating the crude glycerin stream to a temperature of from
weight alcohol and glycerin, to the first glycerin effluent 55 about 125° C. to about 160° C. so that at least a portion
stream, wherein of the at least one fatty acid alkyl ester contained in the
additional amounts of the at least one low molecular crude glycerin stream undergoes a transesterification
weight alcohol and water are stripped out in the second with glycerin to produce additional amounts of the
reactOr. alcohol and additional glyceride;
3. The process according to claim 1, further comprising: 60 sparging the crude glycerin stream with nitrogen, thereby
condensing a glycerin fraction from the distillation over stripping a portion of the alcohol and water from the
head stream to separate purified glycerin from water, crude glycerin stream, to produce a glycerin effluent
and passing the remaining vapor thus separated to a stream comprising glycerin, at least one glyceride and
secondary condenser where it is recovered. water;
4. The process according to claim 1, further comprising 65 distilling the glycerin effluent stream in a flash distillation
prior to distilling the second glycerin effluent stream, but column wherein water and glycerin are vaporized and
after reducing the pH below 7, separating the second removed as an overhead stream.
US 7,126,032 B1
11 12
14. The process according to claim 13, further compris removing a sidestream comprising glycerin vapor from
ing, adding a water stream containing at least one alcohol the flash distillation column, and
and glycerin, to the crude glycerin stream; condensing the sidestream.
wherein additional amounts of the at least one low
molecular weight alcohol and water are stripped out. 5
19. The process according to claim 18, further compris
15. The process according to claim 13, further comprising ing, combining the condensed sidestream product and con
prior to distilling the glycerin effluent stream, but after densed overhead glycerin fraction to form one liquid stream,
reducing the pH below 7, separating the glycerin efflu and
ent stream into a top layer comprising oil and fatty acid passing the one liquid stream over at least one bed of
and a bottom layer comprising glycerin, water, and at 10 sorbent.
least one glyceride, 20. The process according to claim 13, further comprising
wherein the bottom layer is the stream to be distilled. prior to heating the crude glycerin stream to a temperature
16. The process according to claim 13, further compris of from about 125° C. to about 160° C., but after
ing, preheating the glycerin effluent stream prior to the reducing the pH below 7, separating the crude glycerin
distillation column to partially vaporize glycerin and water 15
stream into a top layer comprising oil and fatty acid and
in the effluent stream.
17. The process according to claim 13, further compris a bottom layer comprising glycerin, at least one low
1ng: molecular weight alcohol, at least one glyceride, at
condensing a glycerin fraction from the overhead stream least one fatty acid ester of a low molecular weight
to separate purified glycerin from water, and passing alcohol and water, wherein
the remaining vapor thus separated to a secondary the bottom layer is the stream to be heated to about 125°
condenser where it is recovered. C. to about 160° C.
18. The process according to claim 17, further compris
1ng: