Patent US4655879 - Low-Pressure, Low-Temperature, Continuous Processing Efficiency - Google Patents

5/14/2014 Patent US4655879 - Low-pressure, low-temperature, continuous processing; efficiency - Google Patents
http://www.google.com/patents/US4655879 1/8
Patents
Publication number US4655879 A
Publication type Grant
Application number US 06/664,902
Publication date Apr 7, 1987
Filing date Oct 26, 1984
Priority date Oct 28, 1983
Fee status Paid
Also published as DE3339051A1, EP0141358A1, EP0141358B1
Inventors Rolf Brockmann, 5 More
Original Assignee Henkel Kommanditgesellschaft Auf Aktien
Export Citation BiBTeX, EndNote, RefMan
Patent Citations (13), Non-Patent Citations (8), Referenced by (48),
Classifications (29), Legal Events (6)
External Links: USPTO, USPTO Assignment, Espacenet
CLAIMS (3)
We claim:
1. A process for the purification of crude glycerol derived from the
transesterification, hydrolysis, and saponification of naturally occurring fats and
oils, comprising
(a) alkalizing crude glycerol containing up to 10% by weight of water without
predrying and chemical prepurificaton by mixing with an aqueous alkali
hydroxide solution for about 1 hour at about 90-100 C., followed by the
addition of about 10 N/m
3
of air per cubic meter of said crude glycerol;
(b) distilling the alkalized mixture at about 165-180 C. and about 10-20
mbar and discharging high boiling constituents for additional distillation;
(c) passing the vapors generated by said distillation into a lower part of a
packing column and flowing said vapors upward through said column, said
column containing low-pressure-loss plates having a pressure loss of at most
1 mbar/theoretical separation stage at an air velocity of 2 m/s and having at
least seven theoretical separation stages;
(d) partially first condensing the vapors from said column at about 80-90 C.
under a head pressure of about 5-10 mbars, and second condensing the
remaining vapors at about 20-30 C., so that the second condensate
corresponds to approximately 1% of the quantity of crude glycerol;
(e) cooling the first condensate by about 30-50 C. and returning same to
the head of said column;
(f) continuously removing a main product from said column as a liquid
Low-pressure, low-temperature, continuous
processing; efficiency
US 4655879 A
ABSTRACT
An improved process for purification of glycerol obtained from natural sources
comprising alkalizing a glycerol-containing crude mixture in the presence of air for
oxidation, evaporating the mixture in a thin-layer evaporator with redistillation of
the residue, rectification and reevaporation in a packed column characterized by
low-pressure-loss plates with a falling-film evaporator designed for internal and
external partial condensation and to separate off unwanted constituents of the
mixture, bleaching the product with activated carbon and separating the bleach in
known manner.
DESCRIPTION
BACKGROUND OF THE INVENTION
1. Field of the Invention
The purification of glycerol obtained from naturally occurring fats and oils by an
improved distillation process.
2. Statement of the Relevant Art
Glycerol (propane-1,2,3-triol) is the most important of the trihydric alcohols. It is
present as its esters in all animal or vegetable fats and oils and is obtained from
them as a by-product of the saponification process during soap manufacture.
Although glycerol is also synthesized from petrochemicals, this invention is
concerned only with the purification of glycerol obtained from naturally occurring
fats and oils.
Glycerol is formed during the transesterification, splitting or saponification of
natural oils and fats, by saponification with alkali or by high pressure hydrolysis,
and--depending on the saponification process--contains relatively large quantities
of water, inorganic salts, fats, low molecular weight organic compounds and also
higher glycerol oligomers and polymers.
The organic impurities accumulating in the crude glycerol consist primarily of fats
and glycerol-like compounds formed by bacterial or chemical decomposition,
such as propane-1,2-diol and propane-1,3-diol or even other components, such as
glycerol methyl ethers which barely differ from glycerol in their physical properties
(boiling point, refractive index) and which interfere seriously with the purification
process because they are distilled together with glycerol in conventional columns
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IMAGES (1)

Sign in
sidestream at a point approximately 1/3 of the height of said column, and
returning a partial stream thereof to said column beneath the point of
removal;
(g) cooling the remaining non-returned portion of said main product to about
80-90 C.;
(h) adding about 0.1 to 0.3% by weight of activated charcoal to the said non-
returned portion as a bleaching agent and stirring under nitrogen for about 15
to 30 mintures while at about 80-90 C.; and then removing said bleaching
agent;
(i) drawing off bottom product from the column sump, evaporating said bottom
product at temperatures of about 150-180 C., and returning vapor generated
thereby to said sump,
(j) continuously removing a partial stream of about 1% of the quantity of
glycerol being processed from said bottom product before it is evaporated.
2. The process of claim 1 wherein in step (i) said evaporating is by
falling-film evaporation of said bottom product.
3. The process of claim 1 or 2 wherein about 2 to 4 kg of superheated
steam per 100 kg of glycerol being processed is introduced during the
evaporation of step (i).
having a small number of theoretical plates. Some of these impurities are
responsible for the undesirable discoloration and poor color stability of the crude
glycerol; accordingly, their separation is absolutely essential.
One feature common to all processes carried out on an industrial scale for
extracting purified glycerol obtained from natural fats and oils is that production of
high purity glycerol requires a crude mixture of which the organic impurity content
(mong content) amounts to 1% by weight and from which fat, soap and other
organic constituents have been removed. To this end, the fats are saponified with
calcium hydroxide solution or by the lime-soda (calcium-sodium hydroxide)
process in an elaborate chemical prepurification stage and are filtered off as far as
possible in the form of soaps. Further separation, particularly to remove inorganic
impurities, is carried out by distillation. Columns in which the plates produce a
high pressure loss are used in the rectification stage. In order to obtain adequate
separation of the various components, the sump temperatures have to be
correspondingly high. Limits are imposed on this process parameter by the fact
that glycerol begins to split off water and to decompose and polymerize at
temperatures of the order of 180 C. Crude glycerol is processed in various ways,
depending on its salt content. Crude glycerol of low salt content may be directly
purified using ion exchangers whereas crude glycerol of high salt content has to
be pretreated by distillation to remove the salt. To obtain pure glycerol of the
requisite commercial quality, distillation is followed by treatment with ion
exchangers, for which purpose the concentrated glycerol has to be rediluted. Both
processes are very expensive in terms of apparatus and energy consumption,
cannot always be carried out continuously and are accompanied by considerable
losses of glycerol. In order to separate glycerol by distillation from higher boiling
impurities as well, the mixture has to be additionally subjected to severe thermal stressing which produces further losses of
glycerol and more decomposition products.
SUMMARY OF THE INVENTION
The present invention provides an improved process for the non-degenerative distillation of glycerol, in which glycerol derived
from natural fats and oils is continuously separated from its impurities, particularly salts, water and organic contaminants
affecting its chemical and physical properties, without having to be subjected to intense thermal stressing. The yields amount
to 90% and higher and the quality of the glycerol is at least of a food and cosmetic standard. Preferably, the glycerol is
purified to pharmaceutical standards such as that set by the U.S. Pharmacopeia, Deutsche Industrienorm No. 55,967, or
Europharm III.
The present invention thus relates to a process for the improved purification by distillation of glycerol obtained by the
transesterification, splitting or saponification of natural fats and oils. The process comprises alkalizing a glycerol-containing
crude mixture in the presence of air for oxidation, evaporating the mixture in a thin-layer evaporator with redistillation of the
residue, rectification and reevaporation in a packed column having low-pressure-loss plates with a falling film evaporator
designed for internal and external partial condensation and to separate off unwanted constituents of the mixture, bleaching
the product with activated carbon and separating the carbon in known manner.
The process according to the invention enables high salt, low salt, or salt free crude glycerols to be purified continuously. It
may also be used for the purification of crude glycerols from alkaline saponification bottoms which contain a high percentage
of fatty compounds (mong content 3% by weight), have a high salt content (6% by weight) and contain up to 10% by
weight of water. There is no need for chemical pre-purification, even in the case of low quality crude glycerols and where even
the most stringent quality requirements have to be satisfied. In addition, predrying has only to be carried out down to 10% by
weight of water, which may still be done at normal pressure without having to apply vacuum. Through the application of new
technologies in the field of distillation and rectification, such as the combination of thin-layer and falling-film evaporators and
packed columns with low-pressure-loss plates, separation efficiency is high despite relatively low sump temperatures,
enabling the glycerol to be very carefully treated and losses through decomposition reactions to be avoided. Through the
integration of various process steps, such as the separation of main runnings, first runnings, residue and sump, into a unified
process, separation of the glycerol takes place under optimal conditions both with regard to apparatus and also to energy
consumption. The yields amount to between 90 and 95% of the glycerol processed. The quality of the product may be
regulated according to requirements, the yield even for high purity glycerol still exceeding 90%, depending on the quality of
the crude glycerol starting material.
The packed column used in the process according to the invention is equipped with two evaporators and gives a twice
distilled end product in one process step. The low-pressure-loss plates provide for a high number of separation stages in that
process step and lead to nondegenerative separation of the fats and the glycerol-like compounds (1,2- and 1,3-propane diol
and also glycerolmethyl ethers), which was not possible in conventional columns because of the inadequate number of
separation stages responsible for the high pressure loss per separation stage and the resulting severe thermal stressing of
the glycerol.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a flow chart of the process according to this invention, for the non-degenerative purification of glycerol by
distillation.
DETAILED DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or
reaction conditions used herein are to be understood as modified in all instances by the term "about".
The process of this invention provides an improved purification of crude glycerol by distillation. The crude glycerol may be
obtained by the transesterification, hydrolysis and saponification of natural fats and oils. The successive process steps are
evaporation, rectification, bleaching, and separation of the bleaching agent.
The specific steps of this process are as follows:
(a) crude glycerol containing up to 10% by weight of water--without predrying and chemical prepurification--is alkalized for 1
hour at 90 to 100 C. with an aqueous alkali hydroxide solution in a stirrer-equipped vessel, followed by the addition of 10
N/m
3
of air/m
3
of crude glycerol;
(b) the resulting mixture is optionally preheated, and then is distilled at 165-180 C./10-20 mbar in a thin-layer evaporator
comprising mechanically driven wiper blades, the high boiling constituents being discharged through a lock into a residue
receiver in which they undergo additional distillation;
(c) the vapors from the evaporator pass through a drop separator into the lower part of a packed column comprising low-
pressure-loss plates (i.e., with a pressure loss of at most 1 mbar/theoretical separation stage at a comparable air velocity of
2 m/s) and flow through that column, at least seven theoretical separation stages being present;
(d) the vapors of the column are partially deposited in a first condenser at 80 to 90 C. under a head pressure of 5 to 10
mbars, the rest being condensed at 20 to 30 C. in a second condenser, the condensate of the second condenser
corresponding to approximately 1% of the quantity of crude glycerol used;
(e) the condensate from the first condenser is cooled by 30 to 50 C. and returned to the head of the column, optionally first
passing through a reflux condenser;
(f) the main product runnings is continuously removed from the column as a liquid sidestream at a height of approximately 1/3
of the height of the column, a partial stream being returned to the column immediately beneath the point of removal either at
the same temperature or cooled by 20 to 40 C.;
(g) the rest of the main product runnings is cooled to 80 to 90 C. optionally by passing through a third condenser and after
the addition of activated carbon bleaching agent in a quantity of 0.1 to 0.3% by weight, is stirred under nitrogen in a vessel for
15 to 30 minutes at 80 to 90 C. and passed through a frame filter press to separate the bleaching agent;
(h) bottom runnings are drawn off from the bottom of the sump and are evaporated in a falling-film evaporator at temperatures
in the range about 150 to 180 C. after which the vapors are returned to the sump of the column;
(i) a small partial stream of approximately 1% of the quantity of crude glycerol used is continuously removed from the sump of
the column and
(j) the vapors deposited in the second condenser, optionally together with the sump discharge of the column, are further
processed or partly recycled in another run.
Variant embodiments of the foregoing process include:
(1) introducing 2 to 4 kg of superheated steam per 100 kg of crude glycerol into the column through the falling-film evaporator
to react with and decolor the bottom runnings; and
(2) using salt free and/or salt containing crude glycerols as starting materials.
It should be understood that in the foregoing and following description, no particular apparatus limitations are intended, other
than in the characterization of the low-pressure-loss plates of the packed column. Thus, the first, second, third, and reflux
condensers may be any known condensing means. The first and second stirrer equipped vessels may be any known stirring
and container means. The thin-layer evaporator may be any known thin-layer evaporator means and the falling-film evaporator
may be any known falling-film evaporator means. Any known power or mechanical means may be utilized for introducing or
discharging reactants or products, where needed. Heat energy, where required, may be obtained from any known energy
source, although it is preferred to conserve heat energy removed during some process steps by recycling it to energy
consuming steps. Any known filtering means may be used for separation of the activated carbon bleaching agent, although
frame filter presses are preferred. The column itself may be any known column means which is adapted to contain the
required low-pressure-loss plates and thereby provide at least seven theoretical separation stages with the indicated minimal
pressure loss.
Referring more specifically to the drawing FIGURE, the crude glycerol mixture is introduced at 1 into a first stirrer equipped
vessel 2 in which 50% sodium hydroxide or potassium hydroxide is added at 3 to saponify the fats and fatty acids, followed
by alkalization at 90 C. for at least one hour, during which air is introduced with stirring at 4 to oxidize reducing components
of the mixture.
The reaction mixture thus treated passes through a preheater 5, in which it is heated to approximately 140 C., into a thin
layer evaporator 6 in which the glycerol is carefully concentrated by evaporation in vacuo (max. 15 mbars) with mechanical
stirring.
The residue containing the soaps formed during alkalization, salts and polymeric glycerols is discharged through a heated
upper ballcock 7 at the lower end of the thin-layer evaporator into a similarly heated receiver 8 in which the residue undergoes
additional "squeezing out" under the effect of higher temperatures. The receiver 8 is continuously emptied through the
similarly heated lower ballcock 7a after the upper ballcock 7 has been shut off and the receiver vented. The receiver is then
preevacuated by a ring pump and the connection between the evaporator 6 and the heated receiver 8 reestablished.
The vapors from the thin-layer evaporator 6 pass through a heated vapor tube 9 into the sump 27 of the packed column 11 at
10. The vapor tube 9 is fitted with separation aids to prevent droplets of liquid from the evaporator 6 from being entrained.
The vapors are rectified as they ascend through the packed column 11. The column is fitted with low-pressure-loss plates so
that a high number of separation stages is obtained without the glycerol being decomposed by severe temperature stressing
in the sump 27. For a comparable air velocity of at least 2 m/s, the low-pressure-loss plates lead to a pressure loss of at
most 1 mbar/theoretical separation stage, at least seven theoretical separation stages being present.
The vapors of the upper separation zone are partly deposited in the first condenser 13 at approximately 85 C. and under a
head pressure of at most 10 mbar (dephlegmator). The liquid phase formed is cooled in the reflux condenser 15 and returned
to the head 12 of the column 11 (i.e., internal and external partial condensation). The lower boiling components of the vapors
leaving the column at its head 12 condense in a second condenser 14 and are run off as first runnings at 16. In addition to
glycerol, the first runnings mainly contain esters, fats and glycerol-like compounds. Vapors which are not condensible under
the preveiling conditions of pressure and temperature, mainly water, pass uncondensed into a vacuum unit at 17.
Higher boiling components, such as dimeric glycerol and colored constituents, may be separated off from the ascending
vapors by at least two theoretical separation stages in the lower third of the column. At the upper end of this part of the
column, the entire column reflux is laterally run off at 18 as the main product runnings. Part of the main product runnings
passes back into the column at about the same point 18 either with the same temperature or even slightly cooled. This
fraction may be regulated and serves to remove the high boiling and colored constituents from the vapor containing good
product.
A small quantity of the liquid mixture is continuously removed from the sump 27 at the lower end of the column 11 to
counteract an excessive concentration of colored components. The contents of the sump 27 of the column 11 are carefully
evaporated in the sump falling-film evaporator 19 at a maximum temperature of 165 C. (second evaporation), the vapors being
returned to the sump 27 at point 20 while the residue is collected as sump discharge at 21 and may be recycled, optionally
together with the first runnings 16, in another run, shown in the FIGURE in dotted lines. The falling-film evaporator 19 is
preferably designed for internal and external partial condensation and to separate off unwanted constituents of the crude
glycerol.
The greater part of the main product runnings removed at 18 is cooled in a main condenser 22 and then continuously
bleached by adding activated carbon 28 in a second stirrer equipped vessel 23. Bleaching is carried out for 30 minutes at 80
C. with from 0.1 to 0.3% by weight of activated carbon, depending on the quality of the crude glycerol, the glycerol/carbon
mixture being placed under a nitrogen blanket. The carbon is removed by means of frame filter presses 24.
The heat removed from the main product runnings in the third condenser 22 for cooling to 80 C. is used to heat the crude
product after alkalization in the preheater 5 preceding the thin layer evaporator 6.
Since the stream of condensed first runnings removed at 16 still contains considerable quantities of glycerol, the entire
process may be rerun, although without a further alkalization step, optionally together with the sump discharge 21. Any
resulting deterioration in color in the main product runnings of the column may be corrected by slightly increasing the quantity
of activated carbon used in the bleaching stage. Alternatively, none of the condensed first runnings 16 may be returned to the
alkalization vessel.
In cases where the crude glycerol contains less than 5% by weight of water, an improvement in the color of the main product
runnings removed at 18 may optionally be obtained by introducing superheated steam at 26 into the head of the falling-film
evaporator 19.
The bleached process products which are run off as final runnings and which are obtained at 25 are of excellent quality. The
glycerol content amounts to between 99.8 and 99.9%. After bleaching, the products are colorless and clear and have Hazen
numbers of from 5 to 10. The product does not contain any salt residues and has a water content of less than 0.1%. With
product qualities such as these, a glycerol yield of from 90 to 95% is obtained.
The invention is illustrated by the following Examples, which were carried out with glycerols of various origin.
EXAMPLE 1
Crude glycerol mixture of high salt content from the transesterification of coconut oil; water content 2 to 10%, salt content 4
to 6%, mong content 2 to 3%, was used as the starting material.
EXAMPLE 2
Highly colored, strong-smelling crude glycerol mixture of high salt content from the splitting of a residue accumulating during
the splitting of coconut oil; water content 2 to 10%, salt content 6%, mong content 1.5%, was used as the starting material.
Using the crude glycerol mixtures of Examples 1 and 2 in the inventive process, the following values were obtained after
bleaching with 0.2% and 0.3% of two types of active carbon.
______________________________________Tested Value Example 1 Example
2______________________________________n
D
(20 C.): 1.4737 1.4737Glycerin content 99.8-99.9 99.8-99.9(% by
weight):Hazen No.: 5 5-10S.V. (% Na
2
O): 0.006 0.006S. No.: 0.11 0.11E. No. (ml N-10 HCl): 9.2 9.2A. No.: 0.1 0.1Red
substances1st stage: colorless clear colorless clear2nd stage: yellowish gray yellow-grayMiscibility colorless clear colorless
clearwater:Water content 0.07 0.07(% by weight):Cl
-
: -- --SO
4

--
: -- --Yield (%) 95
90______________________________________
PATENT CITATIONS
Cited Patent Filing date Publication date Applicant Title
US1357138 * Nov 3, 1919 Oct 26, 1920 Bassett Harry P Process of treating distillers' slops
US1474750 * Sep 20, 1919 Nov 20, 1923 Us Ind Alcohol Co Process of recovering glycerine
US1936497 * Oct 11, 1930 Nov 21, 1933 Du Pont Method of manufacturing fermentation glycerol
US2578816 * Mar 7, 1949 Dec 18, 1951 Swift & Co Glycerin refining
US2960447 * Jul 15, 1957 Nov 15, 1960 Shell Oil Co Purification of synthetic glycerol
US4009188 * Feb 19, 1975 Feb 22, 1977
Deutsche Gold- Und Silber-
Scheideanstalt Vormals Roessler
Distillation
US4225394 * Apr 14, 1976 Sep 30, 1980 Ppg Industries, Inc.
Reclamation of spent glycol by treatment with alkali
metal hydroxide and distillation
AU246932A * Title not available
AU278651A * Title not available
CA674001A * Nov 12, 1963 Olin Mathieson Glycerol manufacture
FR1138886A * Title not available
GB278703A * Title not available
GB737570A * Title not available
* Cited by examiner
NON-PATENT CITATIONS
Reference
1 Chemical Abstract 72:1970 42752p "Preparation of Alpha-Diamines from Epoxides".
2 * Chemical Abstract 72:1970 42752p Preparation of Alpha Diamines from Epoxides .
3 * D Souza, The Importance of Glycerol in the Fatty Acid Industry , Journal of the American Oil Chemists Society, vol. 56, pp. 812A 819A (1979).
4 D'Souza, "The Importance of Glycerol in the Fatty Acid Industry", Journal of the American Oil Chemists Society, vol. 56, pp. 812A-819A (1979).
5 Stromquist et al., "C. P. Glycerol by Ion Exchange", Industrial and Engineering Chemistry, vol. 53, pp. 1065-1070 (1951).
6 * Stromquist et al., C. P. Glycerol by Ion Exchange , Industrial and Engineering Chemistry, vol. 53, pp. 1065 1070 (1951).
7 Ziels, "Recovery and Purification of Glycerol", The Journal of the American Oil Chemists Society, vol. 33, pp. 556-565 (1956).
8 * Ziels, Recovery and Purification of Glycerol , The Journal of the American Oil Chemists Society, vol. 33, pp. 556 565 (1956).
* Cited by examiner
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US4935555 * Nov 25, 1988 Jun 19, 1990 Elias Carole L Purification of neopentyl glycol
US4936955 * Aug 12, 1988 Jun 26, 1990
Alameda
Instruments, Inc.
Hydrofluoric acid reprocessing for semiconductor standards
US4975158 * Apr 6, 1990 Dec 4, 1990 Lloyd Bert Recovery of glycerine from polyols by azeotropic distillation
US4980032 * Aug 12, 1988 Dec 25, 1990
Alameda
Instruments, Inc.
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retard loss of acid by reflux; wate acid from semiconductor processing
US4980033 * Sep 4, 1990 Dec 25, 1990 Lloyd Berg Recovery of triethylene glycol from triols by azeotropic distillation
US5061348 * Feb 15, 1990 Oct 29, 1991
Alameda
Instruments
Waste piranha from semiconductor processing
US5080761 * Sep 1, 1989 Jan 14, 1992
Krupp Koppers
Gmbh
Method of optimizing the operation of a distillation column provided
with a side heating device
US5271811 * Feb 8, 1993 Dec 21, 1993
Hoechst Celanese
Corporation
Process for purifying 2-(4-isobutylphenyl)-propionic acid by vacuum
distillation
US5421965 * Aug 1, 1994 Jun 6, 1995 Lloyd Berg
Separation of glycerine from bis(hydroxymethyl)tetrahydrofuran by
azeotropic distillation
US7045100 * Sep 28, 2001 May 16, 2006
Energea
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Gmbh
Method for producing fatty acid methyl ester and equipment for
realizing the same
US7094917 * Aug 13, 2002 Aug 22, 2006
Cognis
Deutschland
Gmbh & Co., Kg
Processes for refining compositions containing dialkyl carbonates
US7169946 Mar 2, 2005 Jan 30, 2007
Twin Rivers
Technologies, L.P.
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and rubbers
US7256301 Oct 12, 2004 Aug 14, 2007
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US7875153 * Jul 19, 2007 Jan 25, 2011
Purac Biochem
B.V.
Purification of aqueous solutions of organic acids
US7879197 Apr 16, 2008 Feb 1, 2011
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US7906691 May 19, 2006 Mar 15, 2011
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US7906692 May 19, 2006 Mar 15, 2011
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products and there is at least one treatment intended to remove at
least part of the halogenated ketones formed.
US7939696 Nov 8, 2006 May 10, 2011
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Process for the manufacture of dichloropropanol by chlorination of
glycerol
US7998317 * Sep 5, 2008 Aug 16, 2011 Wei Ming Chang
thin film evaporation and molecular distillation; making potassium
phosphate fertilizer as by-product as well, from biodiesel
transesterification process yielding glycerol which is upgraded; higher
value end products
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US8415509 Nov 18, 2004 Apr 9, 2013
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US8507643 Mar 31, 2009 Aug 13, 2013 Solvay S.A.
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US8536381 Sep 11, 2009 Sep 17, 2013 Solvay Sa Process for purifying hydrogen chloride
US8591766 Sep 21, 2012 Nov 26, 2013
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EP2241544A1 * Nov 17, 2009 Oct 20, 2010 Lurgi GmbH
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glycerol containing potassium sulfate
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EP2366660A1 * Mar 1, 2011 Sep 21, 2011
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WO2010075616A1 * Dec 28, 2009 Jul 8, 2010
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WO2010118716A1 * Jan 20, 2010 Oct 21, 2010 Lurgi Gmbh
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WO2011000976A2 * Jul 1, 2009 Jan 6, 2011
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E Especialidades
Ltda
Process for the purification of crude glycerol
WO2012034904A1 Sep 7, 2011 Mar 22, 2012 Rhodia Operations Process for purifying crude glycerol
* Cited by examiner
CLASSIFICATIONS
U.S. Classification
203/37, 159/5, 203/89, 202/186, 203/87, 202/205, 568/869, 202/236, 203/49, 203/99, 203/DIG.19, 203/98, 568/854, 203/80,
159/49
International
Classification
B01D3/32, C07C67/00, C07C27/00, C07C29/80, C07C31/22, B01D3/14, C07C29/88
Cooperative Classification Y10S203/20, B01D3/148, B01D3/322, C07C29/80
European Classification C07C29/80, B01D3/14B4, B01D3/32B
LEGAL EVENTS
Date Code Event Description
Oct 28, 2003 AS Assignment
Owner name: COGNIS DEUTSCHLAND GMBH & CO. KG, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HENKEL
KOMMANDITGESELLSCHAFT AUF AKTIEN;REEL/FRAME:014083/0112
Effective date: 20031001
Owner name: COGNIS DEUTSCHLAND GMBH & CO. KG HENKELSTRASSE 67D
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HENKEL
KOMMANDITGESELLSCHAFT AUF AKTIEN /AR;REEL/FRAME:014083/0112
Oct 27, 1998 REMI
Maintenance fee
reminder mailed
Oct 2, 1998 FPAY Fee payment
Year of fee payment: 12
Oct 26, 1984 AS Assignment
Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN (HENKEL KG
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BROCKMANN,
ROLF;JEROMIN, LUTZ;JOHANNISBAUER, WILHELM;AND OTHERS;REEL/FRAME:004330/0508
Effective date: 19841009
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