USOO92281.

56B2

(12) United States Patent (10) Patent No.: US 9.228,156 B2

Wild et al. (45) Date of Patent: Jan. 5, 2016

(54) PROCESS FOR THE PRODUCTION OF (56) References Cited

FATTY ACIDESTERS
U.S. PATENT DOCUMENTS
(71) Applicant: Johnson Matthey Davy Technologies
Limited, London (GB) 5,157,168 A 10, 1992 Wilmott et al.
5,536,856 A 7/1996 Harrison et al.
(72) Inventors: Robert Wild, Thornaby (GB); Rickard
Umberto Andersson, London (GB) FOREIGN PATENT DOCUMENTS
(73) Assignee: Davy Process Technology Limited, CN 10 1244857 8, 2008 ................ CO2F 1/58
London (GB) CN 101318750 12/2008 ................ CO1F 1704
EP 2348009 A2 T 2011
(*) Notice: Subject to any disclaimer, the term of this WO 2005O21697 A1 3, 2005
patent is extended or adjusted under 35 OTHER PUBLICATIONS
U.S.C. 154(b) by 0 days.
CN 101244857, Dingliang Chen, Alkaldeweighting wastewater pro
(21) Appl. No.: 14/.407,862 cessing method and device, 2008, English translation (14 pages).
(22) PCT Filed: May 23, 2013 CN 101318750, Baixiong Dai, et al., Method for treating wastewater
from acetic acid mercapto-isoctyl ester, 2008, English translation (4
pages).
(86). PCT No.: PCT/GB2O13/O51351 International Search Report dated Sep. 5, 2013.
S371 (c)(1), * cited by examiner
(2) Date: Dec. 12, 2014
Primary Examiner – Yate K Cutliff
(87) PCT Pub. No.: WO2013/186526 (74) Attorney, Agent, or Firm — Armstrong Teasdale LLP
PCT Pub. Date: Dec. 19, 2013 (57) ABSTRACT
(65) Prior Publication Data In a process for producing fatty acid esters, a fatty acid or fatty
acid mixture is subjected to esterification with a lower alkanol
US 2015/O152353 A1 Jun. 4, 2015 in an esterification reactor maintained under esterification
conditions to form a stream comprising the corresponding
(30) Foreign Application Priority Data lower alkyl ester(s). An overhead stream comprising unre
acted lower alkanol, water and a heavy organic content of one
Jun. 15, 2012 (GB) ................................... 1210655.5 or more of lower alkyl ester and/or acids is recovered from the
(51) Int. Cl. reactor. The overhead stream is subjected to distillation in a
first distillation column to separate a portion of the lower
CIIC3/00 (2006.01) alkanol from a stream comprising the water, the remaining
CIIC I/00 (2006.01) lower alkanol and the heavy organic content. This stream is
(52) U.S. Cl. recovered and subjected to distillation in a second distillation
CPC. CIIC3/003 (2013.01); CIIC I/00 (2013.01); column to provide an overhead stream comprising lower
Y02E 50/13 (2013.01) alkanol and at least a major portion of the heavy organic
(58) Field of Classification Search content and a water stream having a reduced heavy organic
None and alkanol content.
See application file for complete search history. 17 Claims, 2 Drawing Sheets
U.S. Patent Jan. 5, 2016 Sheet 1 of 2 US 9.228,156 B2

Figsfe 3
U.S. Patent Jan. 5, 2016 Sheet 2 of 2 US 9.228,156 B2

Fige 3
 US 9.228,156 B2
1. 2
PROCESS FOR THE PRODUCTION OF is followed by refining of any resulting ester-containing
FATTY ACIDESTERS hydrogenation product to produce a substantially ester free
fatty alcohol.
The present invention relates to a process for the produc Whatever process is used for the esterification an excess of
tion of fatty acid esters. More particularly, it relates to a alkanol is generally used. Since water is produced during the
process for the production of detergent fatty acid esters. In a esterification reaction and it is desirable to separate the excess
further arrangement the present invention relates to a process alkanol from the water generated in the esterification.
for the production of fatty alcohols. One prior art process for achieving this separation is illus
Fatty alcohols, or higher alcohols as they are sometimes trated schematically in FIG.1. Fatty acid is fed in line 1 to the
designated, are monohydricaliphatic alcohols containing six 10
esterification reactor 2. In the reactor 2 the downflowing acid
or more carbon atoms which are derived either from natural
Sources or are synthesised from petroleum feedstocks. They is reacted with upflowing alkanol which has been added to the
are often classified by their market usage. As the primary end reactor 2 in line 6. The ester product is removed from the
reactor 2 in line 3.
use of primary alcohols containing between about 6 and about
11 carbon atoms is the production of plasticiser esters, such 15 The excess alkanol removes most of the water present as a
alcohols are often termed plasticiser alcohols. For higher gaseous overhead stream 4. This is then fed to an alkanol
alcohols containing, for example, from about 11 up to about recovery distillation column 5 where the water and alkanol
20 carbon atoms, the major use is the production of synthetic are separated. Reflux is returned to the distillation column 5 in
detergents, hence Such alcohols are often termed detergent line 9 and lights are purged in line 8. Alkanol is removed in
alcohols. The distinction between plasticiser alcohols and line 6 and returned to the esterification reactor 2. Fresh
detergent alcohols is somewhat arbitrary and detergent alco alkanol is added in line 7.
hols may have from 10 carbon atoms. In addition, there is Waste water is removed in line 10. This waste water stream
some production of phthalate esters from a C“oxo' alcohol will always also contain some or all of residual alkanol, alkyl
and also some production of for example, non-ionic Surfac ester and fatty acid. The bulk of the fatty acid and methyl
tants from Cs to Co alcohols. 25 esters can be recovered in a simple separation as they are
Although there are some natural products which contain immiscible with water. However, even after this separation,
esters which can be hydrogenated to produce alcohols in the the water stream will still contain residual organic content
plasticiser range, these are more usually produced syntheti that requires the stream to be treated by a waste effluent
cally from petroleum feedstocks by, for example, the so treatment unit.
called “oxo' process, a process which is also termed oXona 30
This process does Suffer from various disadvantages and
tion or hydroformylation. Detergent range alcohols, on the drawbacks. First, useful feedstocks and products such as
other hand, are typically produced by hydrogenation of low alkanol, fatty acids and esters are lost to the process thereby
molecular alkyl esters of fatty acids. Such esters can be pro reducing the economics of the system. However, the main
duced by transesterification of natural triglycerides or by problem is that water treatment processes are required to
esterification of the fatty acids obtained by hydrolysis of the 35
triglycerides. Examples of triglycerides which can be used as reduce the chemical oxygen demand (COD) of the effluent
Stream.
raw materials include natural oils, such as coconut oil, rape
seed oil, and palm oils, and animal fats such as lard, tallow, COD is commonly used to indirectly measure the amount
and fish oils. As such natural raw materials contain mixtures of organic compounds in water. The basis for the COD test is
of triglycerides, the alcohol products obtained upon hydro 40 that nearly all organic compounds can be fully oxidized to
genation are also mixtures of n-alkanols of differing molecu carbon dioxide with a strong oxidizing agent under acidic
lar weight. Such mixtures of alkanols are acceptable for pro conditions. The International Organization for Standardiza
duction of detergents without prior separation of the alkanols tion describes a standard method for measuring COD in ISO
one from another. 6060. Many governments impose regulations regarding the
One process for carrying out the esterification is described 45 maximum COD allowed in wastewater before it can be
in U.S. Pat. No. 5,536,856 the contents of which are incorpo returned to the environment. As environmental concerns
rated herein by reference. In this process, the esterification of increase, the requirement to reduce the COD further makes
the fatty acid is carried out in a column reactor having a treatment plants for effluent streams increasingly costly to
plurality of esterification trays, each having a predetermined construct and operate.
liquidhold-up and containing a charge of a solid esterification 50 The growth in demand for naturally derived detergent
catalyst. The fatty acid flows down the column reactoragainst range alcohols such as that derived from coconut or palm
an upflowing lower alkyl alcohol vapour stream Such as kernel has driven a desire to provide an improved process for
methanol. The supplied alcohol is relatively dry and water of manufacturing the alcohols and for handling the effluents
esterification is removed from the top of the column in the produced.
vapour stream. The product ester is recovered from the Sump 55 The problem associated with the prior art process Such as
of the reactor. As the liquid flows down the trays it encounters that illustrated in FIG. 1 has been solved by the surprising
progressively drier alcohol which drives the ester reaction finding that when the wastewater stream is subjected to a
towards 100% conversion. The ester may then be fed to a second distillation step, the heavy fatty acid and alkyl ester
polishing reactor operated under liquid phase conditions. components are removed as part of the overhead stream giv
Once produced, these esters can be utilised as biodiesel or 60 ing a waste water stream having a lower COD.
they can be hydrogenated to the desired alcohols. Thus according to the present invention there is provided a
An alternative process for the production of fatty alcohols process for the production of fatty acid esters comprising:
is described in U.S. Pat. No. 5,157,168. In this process the (a) Subjecting a fatty acid or fatty acid mixture to esterifi
fatty alcohols are produced by hydrogenation of lower alkyl cation with a lower alkanol in an esterification reactor
esters, particularly methyl esters, offatty acids derived from 65 maintained under esterification conditions to form a
natural triglycerides, under conditions which minimize for stream comprising the corresponding lower alkyl ester
mation of by-product alkanes and ethers. The hydrogenation or esters and recovering same;
 US 9.228,156 B2
3 4
(b) recovering an overhead stream from the esterification acids, or to remove both lower and higher boiling acids and
reactor comprising unreacted lower alkanol, water, and a thus produce a “topped and tailed mixture of acids.
heavy organic content comprising one or more of lower In a preferred process of the present invention esterification
alkyl ester and/or acids; of the fatty acid or fatty acid mixture with the lower alkanol
(c) subjecting the recovered overhead stream to distillation (e.g. methanol) is effected by a procedure in which the fatty
in a first distillation column operating under first distil acid or fatty acid mixture and lower alkanol are passed in
lation conditions to separate a portion of the lower countercurrent flow through a column reactor provided with a
alkanol from a stream comprising the water, the remain plurality of esterification trays mounted one above another,
ing lower alkanol and the heavy organic content; each adapted to hold a predetermined liquid Volume and a
(d) recovering the stream comprising the water, the remain 10 charge of Solid esterification catalyst thereon, liquid down
ing lower alkanol and the heavy organic content; and comer means associated with eachesterification tray adapted
(e) Subjecting the stream comprising the water, the remain to allow liquid phase to pass down the column reactor from
ing lower alkanol and the heavy organic content to dis that esterification tray but to retain solid esterification catalyst
thereon, and vapour upcomer means associated with each
tillation in a second distillation column operating under 15 esterification tray adapted to allow vapour to enter that esteri
second distillation conditions to provide an overhead fication tray from below and to agitate the mixture of liquid
stream comprising lower alkanol and at least a major and solid esterification catalyst on that tray, in which the fatty
portion of the heavy organic content and a water stream acid or fatty acid mixture is Supplied in liquid phase to the
having a reduced heavy organic and alkanol content. uppermost one of said plurality of esterification trays whilst
Without wishing to be bound by any theory it is believed the lower alkanol is supplied in vapour form beneath the
that an azeotrope may be formed between the alkanol and the lowermost one of said plurality of esterification trays, in
heavy organic content in the second distillation Zone thereby which vapour comprising lower alkanol and water of esteri
allowing at least a majorportion of the heavy organic content fication is recovered from an upperpart of the column reactor,
to be separated from the water. This is surprising in view of and in which a lower alkyl fatty acid ester or ester mixture is
the high boiling points of the components of the heavy 25 recovered from a lower part of the column reactor.
organic content. In such a procedure the water content of the lower alkanol
The presence of the second distillation column and the vapour Supplied to the column reactor should be less than
separation that occurs therein, provides various advantages. about 5 mole% and the number of esterification trays and the
One benefit is that there is an optimal recovery of alkanol. reaction conditions should be selected so that the stream of
Another benefit is the greater recovery offatty material. More 30 lower alkyl fatty acid ester or esters has a low acid content of
importantly the removal of the COD value from the waste less than about 1 mole %, calculated on a lower alkanol free
water effluent is optimised. basis, and an ester content, also expressed on an alkanol free
The waste water recovered may be of sufficient purity to basis, of at least about 99 mole %.
enable the water to be recycled. Where the process of the Any suitable reaction conditions can be used for the esteri
present invention is carried out on the same site where the raw 35 fication in the esterification Zone. The esterification condi
oil or fat is split, some or all of the waste water may be tions used in the column reactor will normally include use of
recycled to the reactor in which the splitting occurs. elevated temperatures up to about 160° C., for example a
The term “lower alkyl means C- to C-alkyl, including temperature in the range of from about 80°C. to about 140°
methyl, ethyl, n-propyl, iso-propyl. n-butyl, iso-butyl and C., preferably in the range of from about 100° C. to about
sec-butyl. The preferred lower alkyl radical is methyl. Simi 40 125° C. Such operating temperatures will be determined by
larly the term “lower alkanol' means C- to C-alkanols, factors such as the thermal stability of the esterification cata
including methanol, ethanol, n-propanol, iso-propanol, n-bu lyst, the kinetics of the esterification reaction and the vapour
tanol, iso-butanol, and sec-butanol. Methanol is the preferred temperature of the lower alkanol fed to the base of the column
lower alkanol. reactor at the relevant inlet pressure. Typical operating pres
The term “fatty acids’ means linear saturated, unsaturated 45 Sures at the vapour inlet of the column reactor range from
or polyunsaturated aliphatic acids, such as linear alkyl, alk about 0.1 bara to about 25 bara. A liquid hourly space velocity
enyl, or hydroxyalkenyl carboxylic acids containing from through the column reactor in the range of from about 0.1 hr'
about 6 to about 26 carbon atoms, preferably about 10 to to about 10 hr', typically from about 0.2 hr' to about 2 hr',
about 20 carbon atoms. Examples of such fatty acids are may be used.
decanoic acid (capric acid), dodecanoic acid (lauric acid), 50 The column reactor has a plurality of esterification trays.
tetradecanoic acid (myristic acid), pentadecanoic acid, hexa Although two or three trays may suffice in some cases, it will
decanoic acid (palmitic acid), heptadecanoic acid (margaric typically be necessary to provide at least about 5 up to about
acid), octadecanoic acid (Stearic acid or isostearic acid), octa 20 or more esterification trays in the column reactor. Typi
decenoic acids (oleic acid, linoleic acid or linolenic acid), cally each esterification tray is designed to provide a resi
hydroxyoctadecenoic acid (ricinoleic acid), eicosanoic acid 55 dence time for liquid on each tray of from about 1 minute up
(arachidic acid) and docosanoic acid (behenic acid). Mixtures to about 120 minutes, preferably from about 5 minutes to
offatty acids are of especial importance as raw materials from about 60 minutes.
which the lower alkyl fatty acid esters used as starting mate The fatty acid or fatty acid mixture is supplied in liquid
rial in the hydrogenation step are prepared. Such mixtures of form to an upper part of the column reactor or in admixture
acids can be obtained by hydrolysis of naturally occurring 60 with lower alkanol, in Solution in recycled ester product, or in
triglycerides such as coconut oil, rape seed oil, palm oils, solution in an inert solvent or diluent therefor. It is possible to
tallow, lard and fish oils. If desired, such mixtures of acids can pre-react the lower alkanol and the fatty acid or fatty acid
be subjected to distillation to remove lower boiling acids mixture prior to introduction to the column reactor. The
having a lower boiling point than a chosen temperature and resulting reaction mixture contains a mixture of lower alkyl
thus produce a “topped mixture of acids, or to remove higher 65 fatty acid ester or ester mixture, water, and lower alkanol.
boiling acids having a boiling point higher than a second The Solid esterification catalyst may be a granular ion
chosen temperature and thus produce a “tailed mixture of exchange resin containing SOH and/or COOH groups. Mac
 US 9.228,156 B2
5 6
roreticular resins of this type are preferred. Examples of vary from lower alkanol to lower alkanol and will depend
suitable resins are those sold under the trade marks upon the interaction between water and lower alkanol (e.g.
“Amberlyst”, “Dowex”, “Dow” and “Purolite', such as azeotrope formation) and its effect upon alkanol/water sepa
Amberlyst 13, Amberlyst 66, Dow C351 and Purolite C150. ration. As discussed above, where an alkanol/water azeotrope
Different solid esterification catalysts may be used on dif is present it may be necessary to provide an additional column
ferent trays of the column reactor. Moreover different con to split the azeotrope by the use of for example, pressure
centrations of Solid esterification catalyst can be used on Swing distillation or a membrane system in order to attain an
different trays. alkanol stream of Suitable dryness. In any case, the water
The charge of Solid particulate or granular esterification content of the lower alkanol vapour supplied to the reactor is
catalyst on each tray is typically Sufficient to provide a cata 10
less than about 5 mole %, and even more preferably is less
lyst liquid ratio on that tray corresponding to a resin concen than about 1 mole 96.
tration of at least about 0.2% w/v for example, a resin con The first distillation column may be of any suitable con
centration in the range of from about 2% w/v to about 20% figuration. In one arrangement the distillation column will
w/v., preferably 5% w/v to 10% w/v, calculated as dry resin.
Sufficient catalyst should be used to enable equilibrium or 15 operate at a pressure of from about 0.1 to about 5 bara. The top
near equilibrium conditions to be established on the tray temperature may be in the region of about 40° to about 110°
within the selected residence time at the relevant operating C. and may be about 70 to about 80°C. The reboiler tempera
conditions. On the other hand not so much catalyst should be ture may be in the region of about 80° to about 150° C. and
used on each tray that it becomes difficult to maintain the may be about 110 to about 120° C. In one arrangement the
catalyst in Suspension in the liquid on the tray by the agitation distillation column may be fabricated from stainless steel. It
produced by the upflowing vapour entering the tray from will generally have a plurality of trays or a structured packing.
below. For a typical resin catalyst a resin concentration in the A shell and tube condenser may be used for the overheads.
range of from about 2% v/v to about 20% V/V, preferably 5% The overhead stream will comprise non-condensable dialky
V/v to 10% V/v may be used. lether, nitrogen and lower alkanol.
The particle size of the catalyst should be large enough to 25 Generally the amount of lower alkanol separated in the first
facilitate retention of the catalyst on each tray by means of a distillation column for recycle to the esterification reaction
screen or similar device. However, as larger catalyst particle will be in the region of about 95 wt % to about 99.8 wt %.
sizes are more difficult to maintain in Suspension and have The lower alkanol may be taken from any suitable point in
lower geometrical Surface area per gram, it is expedient to use the first distillation column.
not too large a catalyst particle size. A Suitable catalyst par 30 In one arrangement, it may be taken as a side draw.
ticle size is in the range of from about 0.1 mm to about 5 mm. The column will generally include a reflux. A purge of
In an alternative arrangement, the reaction may be autoca lights, which may be mostly dialkyl ether, may also be taken.
talysed. A stream will be recovered fromator towards the bottom of
One or more wash trays may be provided above the esteri the first distillation column. This stream will contain water,
fication trays in order to prevent loss of product, Solvent 35 the remaining lower alkanol and the heavy organic content.
and/or reagents from the column reactor. The amount of lower alkanol present in this stream will
The process of the invention utilises the vaporous stream of depend on the amount of lower alkanol removed for return to
the lower alkanol to carry away water of esterification pro the esterification Zone.
duced in the esterification reactor but without carrying with it Where a lower alkanol/water azeotrope is present, the
significant quantities of the fatty acid or acids or of the lower 40 stream may be subjected to a process to break the azeotrope.
alkyl fatty acid ester or esters. The carryover of fatty acid or This process may be the application of pressure Swing distil
acids or of the lower alkyl fatty acid ester or esters may be lation or by application of membrane to remove any residual
greater with a shorter alkyl chain length of the fatty acid or Water.
acids. The overhead stream may include lower alkanol dialkyl This stream can then be passed to the second distillation
ether. In general the overhead stream recovered from the 45 column. The second distillation column may be of any Suit
esterification will include: from about 5 to about 40 wt % able configuration. It may be of the same or different configu
water, preferably from about 15 to about 30 wt %; from about ration to the first distillation column.
50 to about 90 wt % alkanol, preferably from about 60 to In one arrangement, the second distillation column may be
about 85 wt % alkanol, from about 0.5 to about 20 wt % operated to have a top temperature of about 40° C. to about
dialkyl ether, preferably from about 1 to about 10 wt % dialkyl 50 110° C. and may be about 60° C. to about 100° C. and a
ether; from about 0.01 wt % to about 1 wt % of fatty acid; and reboiler temperature of about 80°C. to about 150° C. and may
from about 0.01 wt % to about 1 wt % of fatty ester. be about 90° C. to about 120° C.
The overhead stream is passed to a first distillation column The first and second distillation columns will generally be
where a portion of the alkanol is separated. The separated separate columns. However, it is possible that these may be
alkanol portion is preferably recycled to the esterification 55 configured as separate Zones in the same shell.
reactor. The lower the water content of the lower alkanol The lower alkanol and heavy organic content separated
vapour that is Supplied to the esterification column, the fur from the water will be removed from the second distillation
ther towards 100% conversion to ester the esterification equi column in the overhead stream. The water will be removed
librium reaction can be driven and the lower the residual from the bottom of the second distillation column. The over
acidity of the ester containing product recovered from the 60 head stream may be returned to the esterification reactor.
bottom of the column reactor will be. However, a balance may It will be understood that it is desirable that the amount of
often have to be struck between the cost of providing, for alkanol and heavy content be reduced as much as possible
example, a Substantially dry lower alkanol for vaporisation however, the water received may still contain some alkanol
into the column reactor, on the one hand, and the cost of and/or heavy organic content. Thus the reference to the water
providing and operating any additional downstream process 65 having a reduced heavy organic content means that the water
ing facilities that may be required to upgrade the esterproduct stream contains less alkanol and/or heavy organic content
to the required quality if a less dry alkanol is used. This will than the stream entering the second distillation column. In
 US 9.228,156 B2
7 8
one arrangement it will be reduced from about 0.55 wt % total The water stream, which comprises water, remaining
organics to about 0.06 wt % or less. alkanol and the heavy organic content is removed from the
It will be understood that references to an overhead stream bottom of the first distillation column 15 and passed in line 20
means a stream taken from the top of the column or from an to the second distillation column 21. In this column at least a
upper area thereof. Similarly the reference to a stream being major portion of the remaining alkanol and heavy organic
taken from the bottom of the column means a stream taken content is removed as overheads in line 22 and the water,
from the base of the column or from a lower area thereof. which has a reduced content of alkanol and heavy organics, is
Steam may be supplied to the second distillation column to removed in line 23. In an alternative arrangement, the alkanol
strip the alkanol and fatty components. This can be freshly and heavy organic content removed as overheads in line 22
added stream or stream generated from within the process. 10
may be returned to the esterification reactor 12.
The water stream having the reduced heavy organic and An alternative arrangement for the second distillation col
alkanol may be recycled to a fat splitting section. umn 21 is illustrated in FIG. 3, The bottom stream from the
The present invention will now be described by way of first distillation column is fed to the second distillation col
example with reference to the accompanying figures in umn 21 via line 20. Steam is added in line 25 to assist the
which: 15
FIG. 1 is a schematic representation of a process according stripping of the remaining alkanol and heavy organic content
to the prior art; which leaves the second distillation column in line 22. A
FIG. 2 is a schematic representation of the process of the reflux system 24 will generally be located at the top of the
present invention; and column 21. The water having a reduce content of alkanol and
FIG. 3 is a schematic representation of the process in a heavy organics is removed in line 23.
second distillation column in which stream stripping is used. The present invention will now be described with reference
It will be understood by those skilled in the art that the to the following examples.
drawings are diagrammatic and that further items of equip
ment such as reflux drums, pumps, vacuum pumps, tempera EXAMPLE 1.
ture sensors, pressure sensors, pressure relief valves, control 25
valves, flow controllers, level controllers, holding tanks, stor The experiment was carried out using a laboratory scale 1
age tanks, and the like may be required in a commercial plant. inch glass distillation column. The feed point was located in
The provision of Such ancillary items of equipment forms no the middle of the column with four pieces of structured pack
part of the present invention and is in accordance with con ing located above and below. A three litre three necked round
ventional chemical engineering practice. 30 bottomed flask heated via an isomantle was used as the
A simplified version of a flow scheme of the present inven reboiler, with the temperature of the isomantle controlled by
tion is illustrated schematically in FIG. 2. A fatty acid or the skin temperature of the flask. Two thermocouples were
mixture of fatty acid is supplied in line 11 before being attached to the top and bottom Surface sections of the column
subjected to esterification in the reactor 12. The acid is reacted and the column was insulated to minimise any heat losses. A
with upflowing alkanol added to the esterification reacts in 35
vapour travelling up the column was condensed and then
lines 16 and 17. The product of the esterification reaction is collected as a liquid in the reflux drum. Off take and reflux
withdrawn in line 13. The product of the esterification may be return rates were then adjusted to maintain a liquid level.
Subjected to any Subsequent treatment, polishing and the like.
The excess alkanol removes most of the water present as a 2013 g of a feed comprising 96.85 wt % water, 3.00 wt %
gaseous overhead stream 14. This is then fed to a first distil 40 methanol, 0.10 wt & methyl laurate and 0.05 wt % lauric acid
lation column 15 where a proportion of the alkanol is sepa was charged to the round bottomed flask and then heated to
rated and removed from the first distillation column 15 in line 100° C. to generate vapour traffic. The reflux back to the
16 and returned to the esterification reactor 12. Fresh alkanol column was set at approximately ten times that of the over
is added in line 17. Reflux from the top of the first distillation heads take off. Ten overhead fractions ranging between 20
column 15 is returned in line 19 and lights are purged in line 45 and 25 g were taken.
18. The results are set out in Table 1.
TABLE 1.
Reflux Analysis (wt %
Temperatures (°C.) Ratio C12 Acid by
Time Skin Pot OH's Ratio Comments MeOH Ester Water Titre

O 199 97 63 10.0 Starting to

take off
25 195 98 63 12.0 Fraction 1 96.584 O.087 3.329
130 19S 100 63 10.0 Fraction 2 99.970 O.O30 OO61
230 19S 100 64 10.0 Fraction 3 99.977 O.O23 O.064
420. 19S 1 OO 96 8.0 Fraction 4 62.74O O.271 36.974 O.036
455 200 100 99 9.0 Fraction 5 1S.S84 O.O21 84.395
SSO 200 100 99 9.0 Fraction 6 3.175 0.006 96.819
715 200 99 99 11.0 Fraction 7 O.S3O O.O19 99.451
815, 200 99 99 11.0 Fraction 8 O.231 O.046 99.723
935 200 99 99 10.0 Fraction 9 O.228 O.O09 99.762
1055 200 99 99 10.0 Fraction 10 O.172 O.O21 99.807
 US 9.228,156 B2
9 10
EXAMPLE 2 mined by Gas Chromatography (GC), using flame ionisation
detection and a constant injection Volume. For the methanol,
Example 1 was repeated, but pot samples were also methyl laurate and water test work all streams were analysed
removed. The final pot sample was also analysed for chemical by GC for methanol and methyl laurate and also by titration
oxygen demand (COD). for lauric acid using 0.01 molar potassium hydroxide Solution
For the methanol water test work the overheads stream was
analysed for water using a Karl Fischer Coulometric Analy and phenolphthalein indicator.
ser. The methanol content in the bottoms stream was deter The results are set out in Table 2.
TABLE 2
Reflux Overheads Analysis (wt %)
Temperatures (C.) Ratio C12 Acid by
Time Skin Pot OHS Ratio Comments MeOH Ester Water Titre

O 200 98 63 1O.O Starting to

take off
40 200 98 63 Fraction 1 89.701 1.532 7.956 2.312
90 200 99 66 Fraction 2 99.617 O.OSO O.233 O.100
195 200 99 96 Fraction 3 51.926 O.154 47.852 O.OOO
26O 200 100 98 Fraction 4 7.864 O.O14 92.063 O.OOO
345 200 100 99 9.0 Fraction 5 1.925 O.OO1 98.OSO
400 200 100 99 1O.O Fraction 6 O404 O.OOO 99.596
46S 200 100 99 14.O Fraction 7 O.637 O.O11 99.351
S4O 200 100 99 11.O Fraction 8 O.313 O.019 99.570
610 200 100 99 9.0 Fraction 9 O.O14 99.986
7SO 200 100 99 9.0 Fraction 10 O.OO6 99.994

Time Pot Analysis (wt %)

O MeOH C12 Ester Water

40 98.24
90 99.08
195 99.91
260 99.99
345 100
99.99
465 99.98
100
99.99
750 100
COD of final pot contents 13 mgL-1 O2

40
EXAMPLE 3

A COD model was used to predict the reduction of cod

values for the present invention. The results are illustrated in
Table 3.
TABLE 3
molsO2.
Decanter feed composition: Feed mol O2 req. mol

kmoh feed kmoh

MeOH CH3OH O.OO88 1.5 O.O132 32.042

C10 acid C10H2OO2 O.OOO8 14 O.0114 172.27
C12 acid C12H24O2 O.O115 17 O.1961 2OO.324
C14 acid C14H28O2 O.OO12 2O O.O247 228.37
C16 acid C16H32O2 O.OOO2 23 O.OOS1 256.43
C18 acid C18H36O2 O.OOO1 26 O.OO26 284.48
C10 ester C11H22O2 O.OOO8 15.5 O.O117 186.297
C12 ester C13H26O2 O.O108 18.5 O.1994 214.351
C14 ester C15H3OO2 O.OO12 21.5 O.O2SO 242.405
C16 ester C17H34O2 O.OOO2 24.5 O.OOS1 270.459
C18 ester C19H38O2 O.OOO1 27.5 O.OO26 298.514
Water H2O 62.2271 18.016
O4968

Mass flow = 1127 kg/h

Density = 950 kg/m3
Wol flow = 1.18632 m3/h
1186.32 h
 US 9.228,156 B2
11 12
TABLE 3-continued
Total O2 required = O4968 kmoh
15.8981 kg/h
COD = 134012 mg/l

Assumed Decanter water

product composition mol mol
wt % kmoh feed kmoh Wt

MeOH O.O2S CH3OH O.OO88 1.5 O.O132 32.042

C10 acid O.O12S C10H2OO2 O.OOO8 14 O.O114 172.27
C12 acid O.O3 C12H24O2 O.OO17 17 O.O287 200.324
C14 acid O C14H28O2 O.OOOO 20 OOOOO 228.37
C16 acid O C16H32O2 O.OOOO 23 OOOOO 256.43
C18 acid O C18H36O2 O.OOOO 26 OOOOO 284.48
C10 ester O.O12S C11H22O2 O.OOO8 15.5 O.O117 18.6.297
C12 ester O.O3 C13H26O2 O.OO16 18.5 O.O292 214.351
C14 ester O C15H3OO2 O.OOOO 21S OOOOO 242.405
C16 ester O C17H34O2 O.OOOO 24.5 OOOOO 270.459
C18 ester O C19H38O2 O.OOOO 27.5 OOOOO 298.514
Water 99.89 H2O 62.4867 18.016
O.0942

Total O2 required = O.O942 kmoh

3.01541 kg/h
COD = 2541.83 mg/l

25
The following Table 4 compared the measured results with It can be seen from the above examples that the overhead
the predicted results confirming that the prediction is reason include high boiling C. ester which has a boiling point of
able.
TABLE 4
261° C. and C acid which has a boiling point of 299° C. even
30 though the pot temperature in the batch distillation does not
% MeOH Predicted COD
Measured Measured Predicted COD (MeOH + 0.03%C12 go above 100°C. Thus, as distillation proceeds, not only is the
analytically COD (MeOH only) Acid + 0.12% C12 Ester) alkanol removed but the organic levels are reduced to low
O.O2 41SO 285 42O7 COD values which are acceptable in wastewater.
1.09 23300 15512 19435 35
1.02 11490 14516 18438
O3S 1368O 4981 8903
0.72 16900 10247 14169 The following Tables 5 to 8 exemplify the use of alkanols
2.17 34800 3O882 34804
other than methanol and show the removal of a partial of the
heavy organics as well as the alkanol from the water.
TABLE 5

Summary of ethanol, water, ethyl laurate and lauric acid distillation

Overheads Overheads Analysis/wt %

temperature 3.SS Ethyl Lauric

Fraction fo C. fg EtOH Laurate Acid Water

Overheads

1 79 26.6 56.537 O.149 38.813

2 95 21.54 61.953 O. 110 36.809
3 96 28.55 44.145 O.230 0.103 53.538
4 97 24.95 10.645 O.091 88.984
5 97 33.72 0.857 0.077 98.697
6 97 37.75 O.209 O.123 97.889
7 97 20.19 O.093 O.O84 99.705
8 97 127.96 O.O38 O.O73 99.351
9 97 120.71 O.O70 99.831
10 97 72 O.O72 99.68O
11 97 SO.45 O.O63 99.800
Pot sample

Feed 3.02O O.100 O.OSO 96.830

 US 9.228,156 B2
13
TABLE 6
Summary of ethanol, water, ethyl palmitate and palmitic acid distillation
Overheads Overheads Analysis/wt %
temperature 3.SS Ethyl Palmitic
Fraction fo C. fg EtOH Palmitate Acid Water
Overheads

1 75 34.76 57.960 O.223 40.057

2 95 24.99 S3.940 O.O2O 45.592
3 96 17.45 42,086 O.O17 S7.182
4 97 33.58 6.276 O.OO9 93.615
5 97 58.91 O.323 O.O24 99.588
6 97 34.21 0.137 99.823
7 97 1242 O.048 99.918
8 97 58.4 O.O22 99.936
8 97 45.7 O.O13 99.942
10 97 26.2 O.O12 99.945
Pot sample
Feed 3.OOO O.120 O.OSO 96.830

TABLE 7
Summary ofbutanol, water, butyl laurate and lauric acid distillation
Overheads Overheads Analysis/wt %
temperature 3.SS 1- Butyl Lauric
Fraction fo C. fg BuOH Laurate Acid Water
Overheads

1 - top layer 90 41.08 62.877 O.384 35.889

1 - bottom layer 7.563 O.O16 92.221
2 - top layer 90 1529 62.868 O.O2S 36.997
2 - bottom layer 6.906 O.OO8 93.017
3- top layer 89 20.36 64.748 O.O2S 35.153
3 - bottom layer 6.915 O.OOS 93.033
4- top layer 97 21.49 62.331 O.128 0.02O 36.657
4 - bottom layer 6.477 O.OO6 93.490
5 97 23.49 1.437 O.O17 98.504
6 97 64.5 O112 99.874
7 97 12O.S O.O39 99.950
8 97 834 O.O16 OO15 99.958
9 97 44.5 O.O09 O.139 99.653
10 97 37.67 O.O09 O.335 99.584
11 97 68.1 O.O09 OOO6 99.968
12 97 4O.S O.O11 O.OO6 99.953
Pot Sample
Feed 3.OOO O.1OO O.OSO 96.840

TABLE 8
Summary of propanol, water, propyl palmitate and palmitic acid distillation
Overheads Overheads Analysis/wt %
temperature 3.SS 1- Propyl Palmitic
Fraction fo C. fg Propanol Palmitate Acid Water
Overheads

1 84 16.04 58.347 O.O32 O490 38.618

2 84 15.56 71.245 O.O13 O.O87 28.122
3 84 22.56 73.576 O.OO6 26.2SS
4 84 2O.S6 67.009 32.932
5 96 17.89 71.396 O.O41 27.889
6 96 37.33 2.295 O.O37 97.624
 US 9.228,156 B2
15 16
TABLE 8-continued
Summary of propanol, water, propyl palmitate and palmitic acid distillation
Overheads Overheads Analysis/wt %
temperature 3.SS 1- Propyl Palmitic
Fraction fo C. fg Propanol Palmitate Acid Water
7 96 74.61 O.183 O.O33 99.784
8 97 24.86 O112 O.O43 99.845
9 97 57.97 O.066 O.232 O.O90 98.391
10 97 41.4 O.O37 O.O33 99.896
11 96 239.8 O.066 O. 113 O.O18 99.433
12 96 58.6 O.O16 O.O1O 99.956
13 96 36.07 O.O15 O.OO6 O.O16 99.931
14 96 28.1 O.O17 O.OOS O.O17 99.926
Pot Sample
Feed 2.96 1830 O.7OO 94.510

The invention claimed is: 5. A process according to claim 1 wherein the esterification
1. A process for the production of fatty acid esters com reaction is carried out a pressure from about 0.1 bara to about
prising: 25 bara.
(a) Subjecting a fatty acid or fatty acid mixture to esterifi 6. A process according to claim 1 wherein the esterification
cation with a lower alkanol in an esterification reactor is carried out with a liquid hourly space Velocity through the
maintained under esterification conditions to form a 25 column reactor in one of a range of from about 0.1 hr' to
stream comprising the corresponding lower alkyl ester about 10 hr', and a range of from about 0.2 hr' to about 2
or esters and recovering same; hr.
(b) recovering an overhead stream from the esterification 7. A process according to claim 1 wherein the esterification
reactor comprising unreacted lower alkanol, water, and a is carried out in the presence of a solid esterification catalyst
heavy organic content comprising one or more of lower 30 which is a granularion exchange resin containing at least one
alkyl ester and/or acids; of SO3H groups and COOH groups.
(c) subjecting the recovered overhead stream to distillation 8. A process according to claim 1 wherein the esterification
in a first distillation column operating under first distil is autocatalysed.
lation conditions to separate a portion of the lower
alkanol from a stream comprising the water, the remain 35
9. A process according to claim 1 wherein the first distil
ing lower alkanol and the heavy organic content; lation column is operated at a pressure of from about 0.1 bara
(d) recovering the stream comprising the water, the remain to about 5 bara.
ing lower alkanol and the heavy organic content; and 10. A process according to claim 1 wherein the first distil
(e) Subjecting the stream comprising the water, the remain lation column has a top temperature in the region of about 40
ing lower alkanol and the heavy organic content to dis 40
to about 110° C.
tillation in a second distillation column operating under 11. A process according to claim 1 wherein the first distil
second distillation conditions to provide an overhead lation column has a reboiler temperature in the region of
stream comprising lower alkanol and at least a major about 80 to about 150° C.
portion of the heavy organic content and a water stream 12. A process according to claim 1 additionally comprising
having a reduced heavy organic and alkanol content. 45 a step of breaking any lower alkanol/water azeotrope present
2. A process according to claim 1 wherein the esterification after step (c).
of the fatty acid or fatty acid mixture with the lower alkanol is 13. A process according to claim 12 wherein the azeotrope
effected in a column reactor in which the fatty acid or fatty is broken by the application of pressure Swing distillation or
acid mixture and lower alkanol are passed in countercurrent a membrane to remove any residual water.
flow. 50
3. A process according to claim 1 wherein the water content 14. A process according to claim 1 wherein the second
of the lower alkanol supplied in the esterification reaction is distillation column has a top temperature of from about 40°C.
less than about 5 mole % and the reaction conditions are to about 110° C.
selected so that the stream of lower alkyl fatty acid ester or 15. A process according to claim 1 wherein the second
esters has a low acid content of less than about 1 mole %, 55 distillation column has a reboiler temperature of about 80°C.
calculated on a lower alkanol free basis, and an ester content, to about 150° C.
also expressed on an alkanol free basis, of at least about 99 16. A process according to claim 1 whereinsteam is added
mole 96. to the second distillation column.
4. A process according to claim 1 wherein the esterification 17. A process according to claim 1 wherein the water
reaction is carried out in one of a temperature up to about 160° 60 stream having the reduced heavy organic and alkanol content
C., a temperature in the range of from about 80°C. to about is recycled to a fat splitting section.
140°C., and a temperature of from about 100° C. to about
125o C. k k k k k
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 9,228,156 B2 Page 1 of 1
APPLICATION NO. : 14/4O7862
DATED : January 5, 2016
INVENTOR(S) : Wild et al.

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

On the title page item (72), add -- Simon Nicholas Tilley, Thornaby, (GB) --

Signed and Sealed this

Nineteenth Day of July, 2016
74-4-04- 2% 4 Michelle K. Lee
Director of the United States Patent and Trademark Office