US 2010.009.

4027A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2010/0094.027 A1
Coleman et al. (43) Pub. Date: Apr. 15, 2010
(54) PROCESS FOR THE PREPARATION OF Related U.S. Application Data
GLYCEROL FORMAL
(60) Provisional application No. 61/090.281, filed on Aug.
(76) Inventors: Todd Coleman, Batesville, AR 20, 2008.
She ship Publication Classification
(51) Int. Cl.
Correspondence Address: C07D 35/00 (2006.01)
LEWIS,BOX
ATTN RICEIP&DEPT.
FINGERSH, LC (52) U.S. Cl. ........................................................ 549/416
500 NORTH BROADWAY, SUITE 2000 (57) ABSTRACT
ST LOUIS, MO 63102 (US)
A process for the preparation of glycerol formal, from a
(21) Appl. No.: 12/544,785 paraformaldehyde and crude glycerin in a condensation reac
tion without the use of a secondary distilling agent for the
(22) Filed: Aug. 20, 2009 removal of the water.

OH
O

OH OH
(CH2O), F- r ON-0
to C)
Patent Application Publication Apr. 15, 2010 Sheet 1 of 7 US 2010/0094,027 A1
Patent Application Publication Apr. 15, 2010 Sheet 2 of 7 US 2010/0094.027 A1

CRUDE GLYCERNIS
CHARGED TO AFLASK
F- 11
A CONDENSATION REACTION
CATALYST AND PARAFORMALDEHYDE
REMOVED WATERCUT issOATED
| GLYCERINTO
ARE CHARGEDCREATEAMIXTURE
TO THE CRUDE 12
UNTILAWATER PRODUCT CUT
CAN BESOLATED COLLECTED

MIXTURE IS INCREASED AND 13

'4 PRESSURES MAINTAINED
FOR TWO TO
lm....T. ...
FOURHOURS
Tour
TO APOINTAT WHICHA1ST
PRODUCT CUTISCOLLECTED

PRESSURE IS MAINTAINED TO A - 14
POINTAT WHICHASECOND
PRODUCTCUTISCOLLECTED
WEIGHT OF CRUDE REACTION .15
AFRACTIONING COLUMN MIXTURE ISOBTAINED
SATTACHED

MIXTURES HEATED TOA

9 5.
TEMPERATUREAT WHICH FINAL PRODUCT YELD
WATER WILLBEREMOVED SCALCULATED
Patent Application Publication Apr. 15, 2010 Sheet 3 of 7
ARGED WITH
270.5g CRUDEGLYCERIN
-103
0.5m SULFURICACID
FLASKISCHARGED WITH
60 GRAMSPARAFORMALDEHYDE
MIXTURESHEATED TO orc
MIXTURES HELDAT 100°CUNTIL
ALPARAFORMALDEHYDES
DISSOLVEDANDTIMESRECORDED
1-m SAMPLE OF CRUDE REACTION
MIXTURE IS TAKENAND SUBMITTED
FOR COMPOUNDANALYSIS
(GAS-LIQUID CHROMOTOGRAPHY)
MIXTURESHELDAT1COC
FOR2 HOURS
SAMPLE OF CRUDE REACTION
MIXTURE IS TAKENAND
SUBMITTED FOR GAS-LIQUID
CRUDE REACTION MIXTURES
COOLED TO < 50°C
US 2010/0094.027 A1
10
102
TEFLON6BOILING CHIPS
AREADDED TOMIXTURE
104
105
106
WATER CUTS SOLATED AND
107 WEIGHTS RECORDED
PRESSUREISREDUCED
TO 10-20mm Hg AND
108 WATER PRODUCTIS COLLECTED
ONCE OO'CSOBTANED AND
10-20mm Hg ISMAINTAINED THE
109 WATER PRODUCTCUTISISOLATED, 119
TSWEIGHTS RECORDED ANDA
SAMPLE ISSUBMITTED FOR
GAS-LIQUID CHROMOTOGRAPHY
AND KRTITRATION
—
TEMPERATURES INCREASED TO
125°C AND PRESSURES 12O
MAINTAINEDAT 10-20mm HgTO
COLLECT THE 1ST PRODUCT CUT
TO FIG, 3B
Patent Application Publication Apr. 15, 2010 Sheet 4 of 7 US 2010/0094,027 A1

FROMFG, 3A
— —
1ST PRODUCTCUTISSOLATED,
TSWEIGHTS RECORDED ANDA
SAMPLE ISSUBMITTED FOR 121
GAS-LIQUID CHROMOTOGRAPHY
ANALYSIS, KRTITRATION AND
FORMALDEHYDETESTING

140°C WHILE PRESSURES 122

MAINTAINEDAT 10-20mm HgTO
COLLECT2ND PRODUCT

2ND PRODUCTCUTISISOLATED,
TSWEIGHTS RECORDED ANDA
SAMPLESSUBMITTED FOR 123
GAS-LIQUID CHROMOTOGRAPHY
ANALYSSKRTITRATION AND
FORMALDEHYDETESTING
WEIGHT OF CRUDEMIXTURE 124
RESIDUE ISOBTAINED
CRUDE MIXTURERESIDUES
SAMPLED AND SUBMITTED FOR 125
GAS-LIQUID CHROMOTOGRAPHY
ANALYSIS AND DIFFERENTAL
SCANNING CALORMETRY ANALYSIS
- -
CRUDE MIXTURE RESIDUESSAVED 126
FOR RECYCLINGTONEXTBATCH

PRODUCTYELDISCALCULATED -112
Patent Application Publication Apr. 15, 2010 Sheet 5 of 7
FLASKIS CHARGED WITH
100g DISTILLATERESIDUE
FLASKIS CHARGED WITH
184g CRUDEGLYCERIN
5mlSULFURICACDIS -204
CHARGED TOFLASK
60g OF PARAFORMALDEHYDE
SCHARGED TOFLASK
MIXTURES HEATED TO 100°C
MIXTURE IS HELDAT 1 OOC
UNTILALL PARAFORMALDEHYDE
SDSSOLVED
SAMPLE OF CRUDE REACTION
MIXTURE IS TAKENAND
| CHROMOTOGRAPHYANALYSIS
SUBMITED FORGASLIQUID
MIXTURES HELD FOR
TWOHOURSAT 100°C
A 1-m SAMPLE OF CRUDE
REACTION MIXTURES
SUBMITTED FOR GAS-LIQUID
CHROMOTOGRAPHYANALYSIS
TCRUDEMIXTUREST
COOLEDTO<50C
FIG. 4A
US 2010/0094.027 A1
CRUDEMIXTUREISNEUTRALIZED -212
WITH 1ml OF50% CAUSTIC
STIRSHAFTAND BRUSHINGS
AREREMOVED
TEFLON3BOLING CHIPS
AREADDED TOMIXTURE
Y
205 1st VIGREUXCOLUMNISATACHED1
PRESSURE IS REDUCED
206 TO 100mm Hg
MIXTURE IS HEATED
TO 100°CTOREMOVEWATER
208
PRESSURE IS REDUCED 219
TO 10-20mm Hg AND PRODUCTI
WATERCUTISCOLLECTED
WATER PRODUCTCUTISISOLATED,
TSWEIGHTS RECORDED ANDA 220
SAMPLE ISSUBMITTED FOR
GAS-LIQUID CHROMOTOGRAPHY
INCREASED TO 125°C AND PRESSURE 221
ISMAINTAINEDAT 10-20mm Hg
TO COLLECT1ST PRODUCT CUT
TO FIG.4B
Patent Application Publication Apr. 15, 2010 Sheet 6 of 7 US 2010/0094,027 A1

FROM FIG, 4A

1ST PRODUCTCUTIS SOLATED,

TSWEIGHTS RECORDED ANDA
SAMPLE ISSUBMITTED FOR 222
GAS-LIQUID CHROMOTOGRAPHY,
KRTITRATIONAND
FORMALDEHYDETESTING

CREASED TO 140°C WHILE PRESSURE-223

SMAINTAINEDAT 10-20mm
Hg TOCOLLECT2ND PRODUCTCUI
SECOND PRODUCTCUTISSOLATED,
TSWEIGHTS RECORDED ANDA
SAMPLE ISSUBMITTED FOR 224
GAS-LIQUID CHROMOTOGRAPHY
ANALYSIS, KRTITRATION AND
FORMALDEHYDETESTING

WEIGHT OF MIXTURE 225

RESIDUE ISOBTAINED
MXTURERESIDUES
SAMPLED AND SUBMITTED FOR 226
GAS-LIQUID CHROMOTOGRAPHY
AND DIFFERENTIAL SCANNING
CALORMETRY ANALYSIS

TMIXTURERESIDUESSAVED 227
FOR RECYCLINGTONEXTBATCH
228

FG. 4B
Patent Application Publication Apr. 15, 2010 Sheet 7 of 7 US 2010/0094.027 A1

PM
NUMBER COMPOUND AMOUNT MOLES SOURCE

3O338
PSR
DISTILLATERESIDUE,
CRUDE GLYCERN
2 to LBGENERATE
BH8OOO2.85%
O 60 2O
SULFURICACD LAB SUPPLY
50%. CAUSTIC LABSUPPLY
US 2010/0094.027 A1
PROCESS FOR THE PREPARATION OF
GLYCEROL FORMAL
CROSS REFERENCE TO RELATED
APPLICATION(S)
0001. This application claims benefit of U.S. Provisional
Patent Application Ser. No. 61/090.281 filed Aug. 20, 2008,
the entire disclosure of which is herein incorporated by ref
CCC.
BACKGROUND
0002 1. Field of the Invention
0003. This disclosure relates to the field of processes for
the creation of glycerol formal. In particular, to the process of
creating glycerol formal from paraformaldehyde and crude
glycerin.
0004 2. Description of the Related Art
0005. A condensation reaction is a chemical reaction in
which two molecules or moieties (functional groups) com
bine to form one single molecule, together with the loss of a
small molecule. When this small molecule is water, the reac
tion is known to those skilled in the art as a dehydration
reaction.
0006 Examples of condensation reactions known to those
skilled in the art include, but are not limited to, esterfication of
organic acids, preparation of amides from an amine and an
organic acid, and preparation of acetals/ketals from alde
hydes/ketones and diols. These reactions are typically cata
lyzed by a strong acid, such as Sulfuric acid, or a strongly
acidic ion-exchange resin.
0007 Condensation reactions are equilibrium reactions
(i.e., two opposing reactions occurring simultaneously at the
same rate, so that the concentration of each reactant and
product remains constant). Those skilled in the art, however,
know that a higher conversion of product can be obtained by
shifting the equilibrium by the removal of water. This is
typically done by using an azeotropic distilling agent Such as
heptane, benzene, or toluene and a water trap Such as a Dean
Stark trap. Another method to remove water, known to those
skilled in the art, is by distillation under vacuum without the
use of a distillation aid or water trap.
0008 Generally, condensation reactions are used as the
basis for making many important polymers. Examples of
Such polymers include, but are not limited to, nylon, polyester
and other condensation polymers and various epoxies.
0009 Paraformaldehyde is the smallest polyoxymethyl
ene. Further, it is the condensation product of formaldehyde
with a typical degree of polymerization generally around
8-100 units.
0010 Glycerin is a colorless, odorless, and viscous liquid
that is widely used in pharmaceutical formulations. Glycerin
has three hydrophilic hydroxyl groups that are generally
responsible for its solubility in water and it hygroscopic
nature. This particular Substructure is a central component of
many lipids. In fact, since glycerin generally forms the back
bone of triglycerides, it is produced during saponification
processes (such as soap making) and transeterfication pro
cesses (such as biodiesel production). Thus, glycerin is a
common by-product of biodiesel production (via the trans
esterfication of vegetable oils or animal fats).
0011. As use of and the production of biofuels increases as
the demands for replacements for traditional petroleum fuels
gain funding and clout in the “green revolution, the amount
Apr. 15, 2010
of the crude glycerin by-product of these reactions will only
increase. Historically, disposal of the crude glycerin by-prod
uct of biodiesel production has been by incineration; the
by-product has not historically been used as a raw material for
secondary reactions. As such, processes that utilize crude
glycerin in an efficient and cost-effective manner to create
value-added molecules from the crude glycerin by-product of
biodiesel production would be valuable and resourceful in the
emerging green economy.
0012. Although glycerol formal is not readily available on
the chemical commercial market, generally processes for the
production of glycerol formal, with the removal of the reac
tion water, are commonly known in the art. Examples of some
such known processes include the following. First, Patent No.
ES475962 (Spain, Gimeno 1979) describes a process to pre
pare glycerol formal from pure glycerin and paraformalde
hyde by using a packed column and low pressure to remove
the water produced from the condensation reaction. Second,
Patent RO78145 (Romania, Burghelea, 1982) describes a
process to prepare glycerol formal using technical grade glyc
erin (90%) and 37% formaldehyde with benzene as an aid to
remove water. Third, Patent DE 19648960 (German, BASF,
1996) describes both a continuous and batch process. In the
continuous process, an alcohol and excess ketone are heated
to reflux. After a period of time, the ketone is allowed to be
removed by distillation, with fresh ketone being added to
maintain a constant Volume. In a batch process, glycerin and
excess acetone are allowed to react in the presence of petro
leum ether, with water being collected in a trap. In both these
examples, the ketone is utilized in a 4-fold excess with respect
to the alcohol.
0013 While the above cited references demonstrate that
processes for the production of glycerol formal, with the
removal of the reaction water, are generally commonly
known in the art, there are several distinct problems with the
known processes. Generally, all of the known processes uti
lize an inert distilling agent in order to remove the water in the
condensation reaction. This adds to both the cost and com
plexity of the production process. For example, the processes
of the prior art use a distilling agent, such as benzene, to
remove the water (this creates a complex product purification
process) and a packed distillation column and vacuum source
are required (this increases the equipment costs of the pro
duction process). This complexity of the purification process
and high cost make the processes of the prior art difficult to
manufacture.
SUMMARY
0014. The following is a summary of the invention in order
to provide a basic understanding of some aspects of the inven
tion. This summary is not intended to identify key or critical
elements of the invention or to delineate the scope of the
invention. The sole purpose of this section is to present some
concepts of the invention in a simplified form as a prelude to
the more detailed description that is presented later.
00.15 Because of these and other problems in the art,
described herein are, among other things, processes for the
preparation glycerol formal without the use of a secondary
distilling agent to remove the water, in one embodiment from
paraformaldehyde and PM 30338 (crude glycerin) with a
distillate residue recycle.
0016. In one embodiment, the method is comprised of the
steps of: (1) reacting paraformaldehyde and crude glycerin in
a condensation reaction without the use of a secondary dis
US 2010/0094.027 A1
tilling agent for the removal of water. This method can also be
performed with a distillate residue recycle.
0017. Also provided in the present disclosure, is a glycerol
formal formed by the process of: (1) providing a paraformal
dehyde and a crude glycerin; (2) reacting said paraformalde
hyde and said crude glycerin in a condensation reaction with
out the use of a secondary distilling agent for the removal of
water, and (3) segregating said glycerol formal. It is also
contemplated that this process for the formation of glycerol
formal can be performed with a distillate residue recycle.
0018. Also disclosed herein is a method for the production
of glycerol formal, without a distillate residue recycle, the
method comprising the steps of: (1) charging crude glycerin,
a condensation reaction catalyst, and paraformaldehyde
together to create a mixture; (2) heating the mixture to a
temperature at which the paraformaldehyde will dissolve; (3)
holding the temperature of the mixture until all of the
paraformaldehyde is dissolved; (4) holding the temperature
of the mixture for another two hours after all of the paraform
aldehyde has dissolved; (5) cooling the mixture; (6) neutral
izing the mixture; (7) attaching a fractioning column to the
mixture; (8) reducing the pressure of the mixture for a first
time; (8) heating the mixture to a temperature to remove
water; (9) reducing the pressure of the mixture for a second
time; (10) increasing the temperature of the mixture and
maintaining the pressure of the mixture to collect a first prod
uct cut; and (11) increasing the temperature of the mixture
and maintaining the temperature of the mixture to collect a
second product cut.
0019. In am embodiment of this method, 270.5 grams of
crude glycerin are charged in the step of charging.
0020. In another embodiment of this method, 0.5-ml of
Sulfuric acid are charged as said condensation reaction cata
lyst in the step of charging.
0021. In yet another embodiment of this method, 60 grams
of paraformaldehyde are charged in the step of charging.
0022. In yet another embodiment of this method, the mix
ture is heated to a temperature of about 100° C. in the step of
heating the mixture to a temperature at which the paraform
aldehyde will dissolve.
0023. In yet another embodiment of this method, the mix
ture is held at a temperature of about 100° C. in the step of
holding the temperature of the mixture for another two hours
after all of the paraformaldehyde has dissolved.
0024. In yet another embodiment of this method, the mix
ture is cooled to less than 50° C. in the step of cooling the
mixture.
0025. In yet another embodiment of this method, the mix
ture is neutralized by adding about 1.0 ml of 50% caustic.
0026. In still yet another embodiment of this method, the
method further comprises the step of adding boiling agents to
the mixture after the step of neutralizing the mixture.
0027. In yet another embodiment of this method, the frac
tioning column is a 15" Vigreux column.
0028. In still yet another embodiment of this method, the
mixture is reduced to a pressure of around 100 mm Hg in the
step of reducing the pressure of the mixture for a first time.
0029. In yet another embodiment of this method, the mix
ture is heated to a temperature of 100° C. in the step of heating
the mixture to a temperature to remove water.
0030. In yet another embodiment of this method, the mix
ture is reduced to a pressure of about 10-20 mm Hg in the step
of reducing the pressure of the mixture for a second time.
Apr. 15, 2010
0031. In still yet another embodiment of this method, the
temperature is increased to about 125°C. while maintaining
a pressure of about 10-20 mm Hg in the step of increasing the
temperature of the mixture and maintaining the pressure of
the mixture to collect a first product cut.
0032. In yet another embodiment of this method, the tem
perature is increased to about 140° C. while maintaining a
pressure of about 10-20 mm Hg in the step of increasing the
temperature of the mixture and maintaining said pressure of
the mixture to collect a second product cut.
0033. Also disclosed herein is a method for the production
of glycerol formal with a distillate residue recycle, the
method comprising the steps of: (1) charging distillate resi
due, crude glycerin, a condensation reaction catalyst, and
paraformaldehyde together to create a mixture; (2) heating
the mixture to a temperature at which the paraformaldehyde
will dissolve; (3) holding the temperature of the mixture until
all of the paraformaldehyde is dissolved; (4) holding the
temperature of the mixture for another two hours after all of
the paraformaldehyde has dissolved; (5) cooling the mixture;
(6) neutralizing the mixture; (7) attaching a fractioning col
umn to the mixture; (8) reducing the pressure of the mixture;
(9) heating the mixture to a temperature to remove water; (10)
reducing the pressure of the mixture; (11) increasing the
temperature of the mixture and maintaining the pressure of
the mixture to collect a first product cut; (12) increasing the
temperature of the mixture and maintaining the temperature
of the mixture to collect a second product cut; and (13) saving
the crude mixture reside for recycling to the next batch.
BRIEF DESCRIPTION OF THE DRAWINGS
0034 FIG. 1 provides an embodiment of a flowchart of a
process for the preparation of glycerol formal and provides
molecular diagrams of the molecules.
0035 FIG.2 provides an embodiment of a flow chart of the
process for the preparation of glycerol formal from paraform
aldehyde and crude glycerin.
0036 FIG.3 provides an embodiment of a flow chart of an
exemplary step-by-step bench process for the preparation of
glycerol formal from paraformaldehyde and crude glycerin,
without a distillate residue recycle.
0037 FIG. 4 provides an embodiment of a flow chart of an
exemplary step-by-step bench process for the preparation of
glycerol formal from paraformaldehyde and crude glycerin,
with a distillate residue recycle.
0038 FIG.5 provides an embodiment of a chart of the raw
materials needed in the preparation of glycerol formal, in the
process of FIG. 1.
DESCRIPTION OF THE PREFERRED
EMBODIMENT(S)
0039. The following detailed description illustrates by
way of example and not by way of limitation. Described
herein, among other things, is a new process for the prepara
tion glycerol formal, from paraformaldehyde and crude glyc
erin, in one embodiment with a distillate residue recycle.
0040. This process, in its simplified form, comprises:
using a condensation reaction with the raw materials of
paraformaldehyde and crude glycerin, and not using a sec
ondary distilling agent for the removal of water, to produce
glycerol formal. One embodiment of this process for the
preparation of glycerol formal is shown in the process
molecular diagram flow chart of FIG. 1.
US 2010/0094.027 A1
0041. Before the process of this disclosure is more fully
described herein, it is important to note that additional steps
may be performed in certain embodiments, for example in
one embodiment the disclosed process will be performed
without a distillate residue recycle whereas in another
embodiment the disclosed process will be performed with a
distillate residue recycle.
0042 FIG. 5 provides a table of an embodiment of the raw
materials used in the preparation of glycerol formal from
crude glycerin and paraformaldehyde. It is important to note
that is contemplated that any comparable, analogous or Suf
ficient strong acid or strongly-acidic ion-exchange resin
known to those of skill in the art now or in the future to
catalyze a condensation reaction may be used in place of
Sulfuric acid. Further, any caustic or other neutralization
method or process known to those of skill in the art now or in
the future that can be used to neutralize the batch may be used
in place of 50% caustic. Identification of these particular
chemicals in the chart of FIG. 5 is in no way determinative.
Further, the disclosed MW, amounts, and moles are not deter
minative, and any MW, amounts or moles known to those of
skill in the art that would effectively function in the disclosed
processes are contemplated.
0043. An embodiment of the disclosed process for the
preparation glycerol formal, from paraformaldehyde and
crude glycerin is shown in the flow chart of FIG. 2. As a
preliminary matter, it is noted that at any point in this process
a sample of the mixture may be taken and submitted for
testing or procedures known to those of skill in the art to have
utility in Such a reaction. Examples of such tests and/or pro
cedures include, but are not limited to, gas-liquid chromatog
raphy analysis, KF water titration, and formaldehyde testing.
0044. In the first step (1) of this embodiment of the dis
closed process, crude glycerin is charged to a flask (or similar
reaction container/equipment known to those of skill in the
art). The amount of crude glycerin charged in this first step is
dependant upon whether or not it is the first batch of the series.
0045. Next, in step (2), a condensation reaction catalyst
known to those of skill in the art and paraformaldehyde is
charged to the crude glycerin to create a mixture. In one
embodiment of the disclosed process, the condensation reac
tion catalyst utilized is Sulfuric acid.
0046. Then, in step (3), the mixture is heated until gener
ally all of the paraformaldehyde is dissolved. One embodi
ment of the process disclosed in FIG. 2, in this step, the time
required to reach the point at which all of the paraformalde
hyde had dissolved from the mixture is recorded.
0047. After all of the paraformaldehyde is dissolved, in
step (4), the crude reaction mixture is held for around two
hours at a temperature higher than room temperature.
0048 Next, in step (5), the crude reaction mixture is
cooled.
0049 Post-cooling, the crude reaction mixture is neutral
ized in step (6) by a neutralization method or agent known to
those of skill in the art. In one embodiment of the disclosed
process, the crude reaction mixture is neutralized by adding a
50% caustic.
0050. Next, in step (7), a boiling agent known to those of
skill in the art is added to the mixture. Generally, any boiling
agent known to those of skill in the artis contemplated in this
disclosure. In one embodiment of the disclosed process of
FIG. 2, the boiling agent utilized is Teflon R) boiling chips.
Apr. 15, 2010
However, it should be noted that this step is not required and
the process of FIG. 2 can be performed without inclusion of
this step.
0051. After addition of the boiling agent, a fractioning
column or condenser known to those of skill in the art is
attached in step (8). In one embodiment of the process of FIG.
2, the fractioning column or condenser utilized is a 15"
Vigreux column.
0052. After column attachment, in step (9) the pressure of
the crude reaction mixture is reduced.
0053. After reducing the pressure, in step (10), the crude
reaction mixture is generally heated to a temperature at which
water will be removed.
0054 Then, in step (11), the removed water cut from the
crude reaction mixture is isolated. In an embodiment of this
step, the weight of the removed water cut is also recorded.
0055 Next, in step (12), the pressure of the crude reaction
mixture is generally reduced until a water/product cut can be
collected. In an embodiment of this step, after collection of
the water/product cut, the water/product cut is isolated and
the weight is recorded. Further, the sample of the water/
product cut is Submitted for compound analysis and water
titration. Generally, any method of compound analysis (e.g.,
gas-liquid chromatography), water titration (e.g., KF water
titration) known to those of skill in the art are contemplated in
this step of the disclosed process.
0056. Then, in step (13), the temperature of the crude
reaction mixture is generally increased to a temperature and
the pressure is maintained to the point at which a first product
cut can be collected. In an embodiment of this step, after the
first product cut is collected, the cut is isolated and its weight
is recorded. Further, the first product sample is submitted for
compound analysis, water titration and formaldehyde testing.
Generally, any method of compound analysis (e.g., gas-liquid
chromatography), water titration (e.g., KF water titration) or
formaldehyde testing known to those of skill in the art are
contemplated in this step of the disclosed process.
0057. After the first product cut is collected, in step (14),
the temperature of the crude reaction mixture is generally
increased and the pressure is maintained to such a tempera
ture and level that a second product cut can be collected. In an
embodiment of this step, after the second product cut has been
collected, the second cut is isolated and its weight is recorded.
Then, the second product sample is Submitted for compound
analysis, water titration and formaldehyde testing. Generally,
any method of compound analysis (e.g., gas-liquid chroma
tography), water titration (e.g., KF water titration) or formal
dehyde testing known to those of skill in the art are contem
plated in this step of the disclosed process.
0058. In an embodiment of the disclosed process of FIG.
2, following isolation of the second product cut, the weight of
the crude reaction mixture residue is obtained in step (15). In
one embodiment, the weight of the crude reaction mixture
residue is obtained by weighing the flask, pot or equipment
that was utilized minus the weight of the utilized fractioning
column.
0059. In an embodiment of the disclosed process of FIG.
2, after obtaining the weight of the crude reaction mixture
residue, in step (16) the crude reaction mixture residue (i.e.,
the excess glycerin) is saved for recycling to the next batch.
0060. Further, in an embodiment of the disclosed process
of FIG. 2, in a final step (17), the final product yield is
calculated using a calculation method or formula known to
those of skill in the art.
US 2010/0094.027 A1
0061 The disclosed process of FIG. 2 can be performed
either with or without a distillate residue recycle. In the
embodiment of the process of FIG. 2 in which the process is
performed with a distillate residue recycle, prior to step (1) in
which the crude glycerin is charged, distillate residue from
the previous batch is charged and the crude glycerin is added
thereto.
0062. It is noted that the problems of the prior art (i.e., the
complexity of the purification process and high cost) are not
problems of the disclosed processes of the present applica
tion. In the present procedure, glycerol formal is prepared in
good yield and high purity using crude glycerin obtained
from biodiesel and paraformaldehyde without the removal of
the reaction water of condensation. The fact that the reaction
water does not need to be removed from the reaction mixture
in order to obtain a good yield is advantageous for several
reasons: (1) a distillation aid, such as benzene, to remove the
water is not required, thus simplifying the process of purifi
cation; and (2) a packed distillation column and vacuum
Source are not required, thus reducing the burden of equip
ment COStS.
0063. Other advantages of the disclosed processes are the
ability to use the crude glycerin by-product of the biodiesel
process as a raw material. As noted previously, this is essen
tially a low cost and abundant raw material. Due to the low
costand abundance of glycerin, the reaction can use an excess
of alcohol (glycerin) rather than excess formaldehyde (alde
hyde/ketone). This allows for a recycle of the reaction residue
to increase product yield from formaldehyde and minimizes
the likelihood of the formation of high boiling polymers. This
results in a safer and more efficient manufacturing process for
the production of glycerol formal than those disclosed in the
prior art.
0064. The following examples provide for embodiments
of the processes disclosed here-in. The example depicted in
FIG. 3 is an exemplary process without a distillate residue
recycle. The example depicted in FIG. 4 is an exemplary
process with a distillate residue recycle. These processes are
generally bench procedures and therefore are exemplary of
what may be performed in production. It would be understood
by one of ordinary skill in the art that these examples can be
adapted to standard commercial operating processes. Further,
for the purpose of this disclosure, it is noted that distillation
and Volume conditions discussed in this embodiment are not
determinative, and any functional distillation or Volume con
ditions known to those of skill in the art is contemplated in the
processes of this disclosure. Moreover, it is inherent that any
specifically identified flask, distillation column or other
equipment is not determinative. Any piece of equipment
known to those of skill in the art that can properly and effec
tively function in the given step of the disclosed processes is
also contemplated.
Example 1
0065. To begin, in step (101), a flask is tared. In the
embodiment of the process depicted in FIG. 3, the flask is a
500-gram flask.
0066. Then, in step (102), the tared flask is charged with
about 270.5 grams of crude glycerin.
0067. Following the charging, in step (103), around 0.5-ml
of PM23 (sulfuric acid) is added to the flask.
0068. Then, in step (104), about 60 grams paraformalde
hyde is charged to the reaction flask (6).
Apr. 15, 2010
0069. After charging the 60 grams of paraformaldehyde,
in step (105), the mixture is heated to about 100° C.
(0070. In step (106), the mixture is held at about 100° C.
until generally all of the parafromaldehyde is dissolved. Step
(106) also consists of recording the time required to reach this
point (106) at which all of the parafromaldehyde is dissolved.
0071. After recording the time, in step (107), a sample of
the crude reaction mixture is taken and then submitted for
gas-liquid chromotography analysis using the advance work
sheet. In the embodiment of the process depicted in FIG.3 the
sample is a 1-mL sample.
0072 Then, in step (108), the contents of the pot are held
for around an additional two hours, generally at 100° C.
0073. Then, in step (109), a sample of the crude reaction
mixture is taken and Submitted for gas-liquid chromotogra
phy analysis using the advance worksheet (109). In the
embodiment of the process depicted in FIG.3 the sample is a
1-mL sample.
0074. After the sample is taken, in step (110), the pot
contents are cooled to around <50° C.
(0075) Next, in step (111), the batch is neutralized. In this
embodiment, the neutralization occurs by adding 1.0-ml of
PM 16 (50% caustic) with a plastic pipette. In other embodi
ments, the batch will be neutralized by other neutralization
methods known to those of skill in the art now or in the future.
0076) Post-neutralization, in step (112), the stir shaft and
bushings are removed.
0077. Then, after removing the shaft and bushings, in step
(113), several Teflon R boiling chips (or comparable boiling
chips known to those of skill in the art) are added to the
mixture.
(0078 Next, in step (114), a 15" Vigreux column is
attached.
0079. After column attachment, in step (115), the pressure
is reduced to around 100 mm Hg.
0080. After reducing the pressure, in step (116), the pot is
generally heated to around 100° C. to remove water.
I0081 Following the step in which the temperature is
increased, in step (117), the water cut is isolated and the
weight of the water is recorded.
I0082 Next, in step (118), the pressure is slowly reduced to
generally within the range of 10-20 mm Hg, and the water/
product cut is collected.
I0083. In step (119), after collection, the water/product cut
is isolated and the weight is recorded once the conditions of
generally 100° C. and 10-20 mm Hg have been obtained and
stabilized. Further, in step (119), the sample of the water/
product cut is Submitted for gas-liquid chromotography
analysis and Karl Fischer water titration.
I0084. Then, in step (120), the pottemperature is generally
increased to around 125°C., while the pressure is maintained
at around 10-20 mm Hg to collect the first product cut.
I0085. After increasing the temperature, in step (121), the
cut is isolated and the weight is recorded when distillation
ceases at around 125° C. and 10-20 mm Hg. In addition, in
this step (121), the first product cut sample is submitted
gas-liquid chromotography analysis, Karl Fischer water titra
tion, and formaldehyde testing.
I0086. In step (122), the pot temperature is generally
increased to around 140°C. while the pressure is maintained
at around 10-20 mm Hg to collect the second product cut.
I0087 Post-collection, in step (123), the second product
cut is isolated and the weight is recorded when distillation
ceases at around 140°C. and 10-20 mm Hg and the sample is
US 2010/0094.027 A1
Submitted for gas-liquid chromotography analysis, Karl Fis
cher water titration and formaldehyde testing.
0088. Then, in step (124), the weight of the pot residue is
obtained by weighing the pot minus the 15"Vigreux column.
0089. After obtaining the weight of the pot, in step (125),
the pot residue is sampled and Submitted for gas-liquid chro
motography analysis. Also, a second sample is taken and
Submitted for differential scanning calorimetry analysis.
0090. In step (126), the pot residue (excess glycerin) is
saved for recycling to the next batch.
0091 Finally, in step (127), the yield is calculated using
the following equation:
Yield=(Batch weightxassay)-(Batch weightx%
water)/208.
0092. While the expectant yield of the exemplary process
depicted in FIG.3 varies, in one embodiment it is expected to
be between 145 and 185 grams.
Example 2
0093. To begin, in step (201), a flask is tared. In the
embodiment of the process depicted in FIG. 3, the flask is a
500-gram flask.
0094. Then, in step (202), the tared flask is charged with
about 100 grams of distillate residue from the previous batch.
Generally the typical assay of this distillate is around 75%
glycerin.
0095. Then, in step (203), a 500-ml flask is charged with
184 grams of crude glycerin. Generally the typical assay of
this glycerin is around 85%.
0096. Following the charging, in step (204), around 0.5-ml
of PM23 (sulfuric acid) is added to the flask.
0097. Then, in step (205), about 60 grams paraformalde
hyde is charged to the reaction flask.
0098. After charging the 60 grams of paraformaldehyde,
in step (206), the mixture is heated to about 100° C.
0099. In step (207), the mixture is held at about 100° C.
until generally all of the paraformaldehyde is dissolved. Step
(207) also consists of recording the time required to reach this
point (207) at which all of the paraformaldehyde is dissolved.
0100. After recording the time, in step (208), a sample of
the crude reaction mixture is taken and then submitted for
gas-liquid chromotography analysis using the advance work
sheet. In the embodiment of the process depicted in FIG.3 the
sample is a 1-mL sample.
0101 Then, in step (209), the contents of the pot are held
for around an additional two hours, generally at 100° C.
0102 Then, in step (210), a sample of the crude reaction
mixture is taken and Submitted for gas-liquid chromotogra
phy analysis using the advance worksheet (210). In the
embodiment of the process depicted in FIG.3 the sample is a
1-mL sample.
0103. After the sample is taken, in step (211), the pot
contents are cooled to around <50° C.
0104. Next, in step (212), the batch is neutralized. In this
embodiment, the neutralization occurs by adding 1.0-ml of
PM 16 (50% caustic) with a plastic pipette. In other embodi
ments, the batch will be neutralized by other neutralization
methods knownto those of skill in the art now or in the future.
0105 Post-neutralization, in step (213), the stir shaft and
bushings are removed.
Apr. 15, 2010
0106 Then, after removing the shaft and bushings, in step
(214), several Teflon R) boiling chips (or comparable boiling
chips known to those of skill in the art) are added to the
mixture.
0107 Next, in step (215), a 15" Vigreux column is
attached.
0108. After column attachment, in step (216), the pressure
is reduced to around 100 mm Hg.
0109. After reducing the pressure, in step (217), the pot is
generally heated to around 100° C. to remove water.
0110. Following the step in which the temperature is
increased, in step (218), the water cut is isolated and the
weight of the water is recorded.
0111. Next, in step (219), the pressure is slowly reduced to
generally within the range of 10-20 mm Hg, and the water/
product cut is collected.
0112. In step (220), after collection, the water/product cut
is isolated and the weight is recorded once the conditions of
generally 100° C. and 10-20 mm Hg have been obtained and
stabilized. Further, in step (220), the sample of the water/
product cut is Submitted for gas-liquid chromotography
analysis and Karl Fischer water titration.
0113. Then, in step (221), the pottemperature is generally
increased to around 125°C., while the pressure is maintained
at around 10-20 mm Hg to collect the first product cut.
0114. After increasing the temperature, in step (222), the
cut is isolated and the weight is recorded when distillation
ceases at around 125° C. and 10-20 mm Hg. In addition, in
this step (222), the first product cut sample is submitted
gas-liquid chromotography analysis, Karl Fischer water titra
tion, and formaldehyde testing.
0.115. In step (223), the pot temperature is generally
increased to around 140°C. while the pressure is maintained
at around 10-20 mm Hg to collect the second product cut.
0116. Post-collection, in step (224), the second product
cut is isolated and the weight is recorded when distillation
ceases at around 140°C. and 10-20 mm Hg and the sample is
Submitted for gas-liquid chromotography analysis, Karl Fis
cher water titration and formaldehyde testing.
0117 Then, in step (225), the weight of the pot residue is
obtained by weighing the pot minus the 15"Vigreux column.
0118. After obtaining the weight of the pot, in step (226),
the pot residue is sampled and Submitted for gas-liquid chro
motography analysis. Also, a second sample is taken and
Submitted for differential scanning calorimetry analysis.
0119. In step (227), the pot residue (excess glycerin) is
saved for recycling to the next batch.
I0120 Finally, in step (228), the yield is calculated using
the following equation:
Yield=(Batch weightxassay)-(Batch weightx%
water)/208.
I0121 While the expectant yield of the exemplary process
depicted in FIG. 3 varies, in one embodiment it is expected to
be between 145 and 185 grams.
0.122 While the invention has been disclosed in connec
tion with certain preferred embodiments, this should not be
taken as a limitation to all of the provided details. Modifica
tions and variations of the described embodiments may be
made without departing from the spirit and scope of the
invention, and other embodiments should be understood to be
encompassed in the present disclosure as would be under
stood by those of ordinary skill in the art.
US 2010/0094.027 A1
1. A method for the preparation of glycerol formal, the
method comprising the steps of
providing a paraformaldehyde and a crude glycerin; and
reacting said paraformaldehyde and said crude glycerin in
a condensation reaction without the use of a secondary
distilling agent for the removal of water.
2. The method for the preparation of glycerol formal of
claim 1, wherein said condensation reaction is performed
with a distillate residue recycle.
3. A glycerol formal formed by the process of:
providing a paraformaldehyde and a crude glycerin;
reacting said paraformaldehyde and said crude glycerin in
a condensation reaction without the use of a secondary
distilling agent for the removal of water; and
segregating said glycerol formal.
4. The process for the formation of glycerol formal of claim
3, wherein said condensation reaction is performed with a
distillate residue recycle.
5. A method for the production of glycerol formal, without
a distillate residue recycle, the method comprising the steps
of:
charging crude glycerin, a condensation reaction catalyst,
and paraformaldehyde together to create a mixture;
heating said mixture to a temperature at which said
paraformaldehyde will dissolve:
holding said temperature of said mixture until all of said
paraformaldehyde is dissolved;
holding said temperature of said mixture for 2 to 4 hours
after all of said paraformaldehyde has dissolved;
cooling said mixture;
neutralizing said mixture;
attaching a fractioning column to said mixture;
reducing the pressure of said mixture for a first time;
heating said mixture to a temperature to remove water;
reducing the pressure of said mixture for a second time;
increasing said temperature of said mixture and maintain
ing said pressure of said mixture to collect a first product
cut; and
increasing said temperature of said mixture and maintain
ing said temperature of said mixture to collect a second
product cut.
6. The method of claim 5, wherein 270.5 grams of crude
glycerin are charged in said step of charging.
7. The method of claim 5, wherein 0.5-ml of sulfuric acid
are charged as said condensation reaction catalyst in said step
of charging.
8. The method of claim 5, wherein 60 grams of paraform
aldehyde are charged in said step of charging.
9. The method of claim 5, wherein said mixture is heated to
a temperature of about 100° C. in said step of heating said
mixture to a temperature at which said paraformaldehyde will
dissolve.
10. The method of claim 5, wherein said mixture is held at
a temperature of about 100° C. in said step of holding said
temperature of said mixture for another two hours after all of
said paraformaldehyde has dissolved.
Apr. 15, 2010
11. The method of claim 5, wherein said mixture is cooled
to less than 50° C. in said step of cooling said mixture.
12. The method of claim 5, wherein said mixture is neu
tralized by adding about 1.0 ml of 50% caustic.
13. The method of claim 5, further comprising the step of
adding boiling agents to said mixture after the step of neu
tralizing said mixture.
14. The method of claim 5, wherein said fractioning col
umn is a 15" Vigreux column.
15. The method of claim 5, wherein said mixture is reduced
to a pressure of around 100 mm Hg in said step of reducing
said pressure of said mixture for a first time.
16. The method of claim 5, wherein said mixture is heated
to a temperature of 100°C. in said step of heating said mixture
to a temperature to remove water.
17. The method of claim 5, wherein said mixture is reduced
to a pressure of about 10-20 mm Hg in said step of reducing
the pressure of said mixture for a second time.
18. The method of claim 5, wherein said temperature is
increased to about 125°C. while maintaining a temperature of
about 10-20 mm Hg in said step of increasing said tempera
ture of said mixture and maintaining said pressure of said
mixture to collect a first product cut.
19. The method of claim 5, wherein said temperature is
increased to about 140°C. while maintaining a temperature of
about 10-20 mm Hg in said step of increasing said tempera
ture of said mixture and maintaining said pressure of said
mixture to collect a second product cut.
20. A method for the production of glycerol formal with a
distillate residue recycle, the method comprising the steps of
charging distillate residue, crude glycerin, a condensation
reaction catalyst, and paraformaldehyde together to cre
ate a mixture;
heating said mixture to a temperature at which the
paraformaldehyde will dissolve:
holding said temperature of said mixture until all of said
paraformaldehyde is dissolved;
holding said temperature of said mixture for another two
hours after all of said paraformaldehyde has dissolved;
cooling said mixture;
neutralizing said mixture;
attaching a fractioning column to said mixture;
reducing the pressure of said mixture;
heating said mixture to a temperature to remove water,
reducing the pressure of said mixture;
increasing said temperature of said mixture and maintain
ing said pressure of said mixture to collect a first product
cut,
increasing said temperature of said mixture and maintain
ing said temperature of said mixture to collect a second
product cut; and
saving the crude mixture reside for recycling to the next
batch.