USOO8222460B2

(12) United States Patent (10) Patent No.: US 8,222,460 B2

Sawrey (45) Date of Patent: Jul. 17, 2012
(54) PROCESS FOR THE PRODUCTION OF MIBC (58) Field of Classification Search .................. 568/388,
AND FOR IBHKPLUS TMN USING 568/881
COPPER-BASED CATALYSTS See application file for complete search history.
(56) References Cited
(75) Inventor: Jeffrey Scott Sawrey, Westford, MA
(US) U.S. PATENT DOCUMENTS
(73) Assignee: Dow Global Technologies LLC, 2,137,407 A 11/1938 Lazier
3.657,351 A 4, 1972 Araki et al.
Midland, MI (US) 5,925,796 A 7/1999 Bassett et al.
6,518.462 B2 2/2003 Saayman et al.
(*) Notice: Subject to any disclaimer, the term of this 6,706,928 B2 3/2004 Kelly
patent is extended or adjusted under 35 6,762,328 B2 7/2004 Saayman et al.
U.S.C. 154(b) by 154 days. 6,977.314 B2 12/2005 Vandersall et al.
FOREIGN PATENT DOCUMENTS
(21) Appl. No.: 12/670,195 WO 2007/038440 A1 4/2007

(22) PCT Fled: Jul. 17, 2008 OTHER PUBLICATIONS

Torres, et al., “One-step methl isobutyl ketone (MIBK) synthesis
(86) PCT NO.: PCT/US2O08/07O262 from 2-propanol: Catalyst and reaction condition optimization'.
S371 (c)(1), Applied Catalysis A: General, vol. 317, 2007 (pp. 161-170).
(2), (4) Date: Jun. 25, 2010 Primary Examiner — Sikarl Witherspoon
(87) PCT Pub. No.: WO2009/017970 (74) Attorney, Agent, or Firm — Whyte Hirschboeck Dudek
SC
PCT Pub. Date: Feb. 5, 2009
(57) ABSTRACT
(65) Prior Publication Data MIBC and/or a mixture of IBHK and TMN is produced from
US 2010/0317897 A1 Dec. 16, 2010 MIBK by a process comprising the step of contacting MIBK
with hydrogen under condensation/hydrogenation/dehydra
Related U.S. Application Data tion reactive conditions and in the presence of a catalytic
amount of a Cu-based condensation/hydrogenation/dehydra
(60) Provisional application No. 60/952.322, filed on Jul. tion catalyst. The relative amounts of MIBC and the mixture
27, 2007. of IBHK and TMN are controlled by the reaction tempera
(51) Int. C. ture, a lower temperature, e.g., 130 C., favoring MIBC alone,
C07C 45/73 (2006.01) and a higher temperature, e.g., 200 C., favoring a mixture of
C07C 29/145 (2006.01) MIBC and IBHK plus TMN.
(52) U.S. Cl. ........................................ 568/388: 568/881 10 Claims, 4 Drawing Sheets
U.S. Patent Jul. 17, 2012 Sheet 1 of 4 US 8,222.460 B2

ERE

Rehydrogenation

- \ ".H. .
us
A K
Condensationitehydration

--
act -->
\' sale
y AA

iycirogenation

-se - "2. --
S. 3K

iydrogenation
+h pH
------ H. ---
K SC

leavier redicts

Dig - E - - -
-N-N--
--
---
BK

2 MSK . O
() MK - 8K oc
|-
F - usu
- -N1 -
3K
U.S. Patent Jul. 17, 2012 Sheet 2 of 4 US 8,222.460 B2

Cu Catalyst i & Cui Catalyst 2 's N Catalyst

8were Yperature is g {}

c. Cucatalyst 2 NCatalyst - Equilibrium

|--|--
3 {{ 's 18 70 180 3& 28).

---------.
Over angerature sieg : . . . . . . . . . . . . . . . . . . . . . . ------------------- * r *

6, 2
U.S. Patent Jul. 17, 2012 Sheet 3 of 4 US 8,222.460 B2

Cu Catalyst 1 3 cu catalyst 2

:38 as: 8.

yen ferrera tire (deg C} ·

Cucatalyst C. Cata lyst 2

13 $$$3. so S. 383
{ver eigeratase sieg C.
(16
U.S. Patent Jul. 17, 2012 Sheet 4 of 4 US 8,222.460 B2

Fié. (a
YYYYYYYYYYYYYYYYYYY-----------axx-xx-aa-arrara-Arrivaarawaxaaaaaaa-ra-a-a-a-a-Naa... ------. . . . . . . . . . . . . . . . . . .
3 Catalyst & Cu Catalyst 2 's N. Catalyst

8.
- R... ." ... . . w ..
narraxxxx-x-xx-xxssssssssssssssssssssssss,
30, 430 53) OC O. Q00 : 00 200
time thrsv-s-s-s-s-sixxxxx-xx-SSSSSSSSSSNYSSSSSSSSSSSSWNYW N-SSSS-YYYYYYYYYY-\---------a-a-a---------------- * * * * * * * ... . .

ww-aww.a.a.a.

Cu Catalyst 1 Cu Catalyst 2

4.

f2
1

s8
R
R
R
R
&
Rw
,
R
23: 388 383 SR 88: 8:8; 8:8; 8.38 E3 iii)& 3)
firing firs} w
R

6, 7
 US 8,222,460 B2
1. 2
PROCESS FOR THE PRODUCTION OF MIBC mately derived from the dehydrogenation of IPA), thus pro
AND FOR IBHKPLUS TMN USING ducing a near equilibrium mixture of IBHK and TMN.
COPPER-BASED CATALYSTS Of continuing interest is a process to increase the IBHK
plus TMN capacity while eliminating the need for separate,
CROSS-REFERENCE TO RELATED labor intensive campaigns. Also of interest is a process that
APPLICATION has a lower conversion cost and fewer hydrocarbon impuri
ties, and eliminates concerns associated with the convention
This application which claims the benefit of U.S. Provi ally used, more expensive Ni-catalysts.
sional Application No. 60/952.322 filed Jul. 27, 2007, the 10 SUMMARY OF THE INVENTION
teachings and disclosures of which are incorporated herein by
reference.
MIBC is produced and/or simultaneously co-produced
FIELD OF THE INVENTION with IBHK plus TMN by feeding MIBK and hydrogen over a
Cu-based hydrogenation or multifunctional catalyst at low
This invention relates to a process for the production of
15 temperature conditions similar to those used with a Ni-based
Solvents. In one aspect, the invention relates to a process for hydrogenation catalyst. In contrast to the process in which
producing methyl isobutyl carbinol (MIBC) and a mixture of MIBC is produced in a converter using a nickel-based cata
isobutylheptyl ketone (IBHK) and trimethylnonanol (TMN) lyst, the process of this invention allows for a dramatic
increase the IBHK plus TMN capacity, eliminates the need
while in another aspect, the invention relates to a process for for separate labor intensive campaigns to Supplement IBHK
making these solvents using a copper-based catalyst. In still plus TMN production, utilizes a much less expensive catalyst,
another aspect, the invention relates to a process for making lowers conversion costs and produces fewer hydrocarbon
MIBC alone or in combination with a mixture of IBHK and impurities.
TMN. In one embodiment. MIBC and/or a mixture of IBHK and
25 TMN is produced from MIBK by a process comprising the
BACKGROUND OF THE INVENTION step of contacting MIBK with hydrogen under condensation/
hydrogenation/dehydration reactive conditions and in the
The condensation of acetone and/or isopropanol to higher presence of a catalytic amount of a Cu-based condensation/
ketones is well known. For example, U.S. Pat. No. 6,977.314 hydrogenation/dehydration catalyst. The relative amounts of
discloses the condensation of acetone to methyl isobutyl 30 MIBC and the mixture of IBHK and TMN are controlled by
ketone (MIBK) with a catalyst consisting of a polysulfonated the reaction temperature, a lower temperature, e.g., 130 C.
ion exchange resin containing metalions. U.S. Pat. No. 6,762, favoring MIBC alone, and a higher temperature, e.g., 200 C.
328 and U.S. Pat. No. 6,518.462 disclose a process to make favoring a mixture of MIBC and IBHK plus TMN.
MIBK by reactive distillation. In a first step acetone is con One hallmark of this invention is to pass MIBK over a
densed to mesityl oxide (MSO). In a second step MSO is 35 copper-based condensation/hydrogenation/dehydration cata
hydrogenated to MIBK and small amounts of MIBC (also lyst and, depending on the temperature, make MIBC or a
known as methylamyl alcohol). U.S. Pat. No. 6,706.928 dis mixture of MIBC and IBHK plus TMN. So rather than two
closes a vapor condensation process to convert acetone to independent operations to manufacture MIBC and supple
MSO followed by hydrogenation of MSO to MIBK. This mental IBHK plus TMN, it can now be completed in a single
patent also discloses a single step condensation/hydrogena 40 step in which control of the process temperature is the means
tion process of acetone to MIBK. U.S. Pat. No. 5,925,796 for controlling the product mix. The process uses a catalyst
discloses feeding MIBC and/or MSO with acetone and/or that is less expensive than the current nickel-based catalyst,
isopropanol to a multifunctional condensation/hydrogena and generates fewer impurities.
tion/dehydration catalyst in order to adjust the MIBK to
DIBK (diisobutyl ketone) ratio in the product. 45 BRIEF DESCRIPTION OF THE DRAWINGS
In one known process, MIBK, MIBC, DLBK and IBHK
are co-produced in parallel, mixed ketone converters. Isopro FIG. 1 is a series of reaction equations describing the
panol and hydrogen are fed to the reaction system and through manufacturing steps for DMK (dimethylketone), DAA (diac
a series of condensation/hydrogenation/dehydration steps, etone alcohol), MSO, MIBK, MIBC, DIBK, i-DIBK (methyl
the various products are generated. These condensation/hy 50 heptyl ketone) and IBHK.
drogenation/dehydration reactions can be carried out using a FIG. 2 is a graph reporting the weight percent (wt %) of
single multifunctional catalyst comprising copper, chromium MIBK in the reactor output as a function of the oven tempera
and calcium carried on an aluminum oxide Support. These ture in degrees C.
products can be produced in specified amounts on a continu FIG.3 is a graph reporting the wt % of MIBC in the reactor
ous basis. The ratio of products can be adjusted to a limited 55 output as a function of the oven temperature in degrees C.
extent by altering the reaction conditions. The reaction chem FIG. 4 is a graph reporting the wt % of total C which
istry for making these products is shown in FIG. 1. equals IBHK plus TMN in the reactor output as a function of
Additional MIBC is produced by feeding refined MIBK the oven temperature in degrees C.
produced in the mixed-ketone converters to a separate single FIG.5 is a graph reporting the ratio of IBHK to TMN in the
hydrogenation converter containing a nickel-based catalyst. 60 reactor output as a function of the oventemperature in degrees
IBHK is made in parallel by reaction 6 schematically C.
shown in FIG. 1. Optionally, IBHK can be made in isolated FIG. 6 is a graph reporting a comparison in the production
campaigns. This is done by feeding MIBK and MIBC at high of MIBC overtime in hours using two different copper-based
temperature (24.0 C) over a single multifunctional catalyst catalysts and a nickel-based catalyst.
comprising copper, chromium and calcium carried on an 65 FIG. 7 is a graph reporting a comparison in the production
aluminum oxide Support. IBHK is partially hydrogenated in of total C, i.e., IBHK plus TMN, over time in hours using
situ to its corresponding alcohol TMN (the hydrogen is ulti two different copper-based catalysts.
 US 8,222,460 B2
3 4
DESCRIPTION OF THE PREFERRED While bi-functional, copper-based aldol condensation
EMBODIMENT catalysts capable of carrying out hydrogenation/dehydroge
nation chemistry are the preferred catalysts for use in the
The numerical ranges in this disclosure are approximate, process of this invention, other copper-based catalysts can
and thus may include values outside of the range unless also be used. Accordingly, any catalyst useful for the produc
otherwise indicated. Numerical ranges include all values tion of MIBK and/or DIBK from IPA and/or DMK can be
from and including the lower and the upper values, in incre used in the practice of this invention. Such catalysts often
ments of one unit, provided that there is a separation of at least have one or more base metals (e.g., Na, Ca, Mg, Li, and the
two units between any lower value and any higher value. As like) for the condensation chemistry, in combination with one
an example, if a compositional, physical or other property, 10 or more metals such as Cr, Ni, Pd or Zn, and the like, for the
Such as, for example, molecular weight, Viscosity, melt index, hydrogenation/dehydrogenation chemistry. The dehydration
etc., is from 100 to 1,000, it is intended that all individual chemistry is promoted by heat and base metals (as described
values, such as 100, 101, 102, etc., and Sub ranges, such as above) and potentially by the catalyst Support, e.g., alumina.
100 to 144, 155 to 170, 197 to 200, etc., are expressly enu The preferred catalysts comprise 10% Cu. 1% Ca and 0.5%
merated. For ranges containing values which are less than one 15 Crby weight of the metal, the remainder being the support,
or containing fractional numbers greater than one (e.g., 1.1, preferably alumina. For purposes of the present invention, the
1.5, etc.), one unit is considered to be 0.0001, 0.001, 0.01 or composition of the catalyst is not believed to be narrowly
0.1, as appropriate. For ranges containing single digit num critical. For example, the Cu concentration of the hydrogena
bers less than ten (e.g., 1 to 5), one unit is typically considered tion catalyst may be 5 to 15% by weight, while the concen
to be 0.1. These are only examples of what is specifically tration of the base metal (e.g., Ca,Na, Mg, etc.) may be in the
intended, and all possible combinations of numerical values range of 0.5 to 3% by weight. With respect to the preferred
between the lowest value and the highest value enumerated, catalyst composition, Cr is optional and may range from 0 to
are to be considered to be expressly stated in this disclosure. 1% by weight.
Numerical ranges are provided within this disclosure for, Except as is discussed below in connection with the change
among other things, relative amounts of components in a 25 oftemperature to enhance control over the MIBC and IBHK/
mixture and various temperature and other process parameter TMN ratio, choice of reaction temperature, within the tem
ranges. perature operating envelope of the chosen catalyst, can be
"Catalytic amount’ means an amount necessary to pro varied to convenience, and can typically range from 90 to
mote the reaction of two components at a detectable level, 260° C., preferably 100 to 240° C., more preferably 120 to
preferably at a commercially acceptable level. 30 200° C. Temperatures above 240° C., depending upon the
"Condensation/hydrogenation/dehydration reactive con thermal stability of the specific catalyst in use, are preferably
ditions' and like terms means reactive conditions in which avoided in order to minimize deactivation of the catalyst.
one or more reactants undergo condensation and/or hydroge Obviously, lower temperatures are preferred for that reason.
nation and/or dehydration. Condensation is the combination Also, as temperature increases, equilibrium begins to favor
of two molecules or moieties to form a single molecule with 35 the ketone thus driving the IBHK/TMN and MIBK/MIBC
the loss of a small molecule, e.g., two MIBK joining to form ratios up. Generally, a temperature below 200°C., e.g., 90 to
IBHK plus water. Hydrogenation is the addition of hydrogen 150° C., favors MIBC production from both kinetic (e.g.,
to an unsaturated organic compound, e.g., converting MIMIC limits condensation to C) and thermodynamic perspectives.
to MIBC. Dehydration is a chemical reaction that involves the Temperatures above 200° C. e.g., 200 to 240° C., increase
loss of water from one a molecule (it is a subset of elimination 40 both the total C production and the IBHK/TMN ratio.
reactions), e.g., the conversion of DAA to MSO. In the con Choice of reaction pressure is not narrowly critical. Opera
text of this invention, these conditions typically include a tion in the range of 0.1 to 0.3 MPa is preferred. Similarly, flow
temperature between 90 and 300 C. and a pressure between rate through the reactor is not narrowly critical, and may
0.1 and 1 megapascals (MPa). typically range from 0.1 to at least 5 LHSV, preferably from
“Condensation/hydrogenation/dehydration catalyst” and 45 0.1 to at least 1.0 LHSV.“LHSV” means liquid hourly space
like terms means a catalyst that will promote simultaneously Velocity, a commonly used measure which equals the Volu
condensation, hydrogenation and dehydration reactions metric rate of feed in the liquid state per volume of catalyst,
within a given reaction mass under given condensation/hy typically measured at atmospheric pressure and in the liquid
drogenation/dehydration reactive conditions. state. Preferably, the flow rate is in the range of 0.15 to 0.5
“Cu-based condensation/hydrogenation/dehydration cata 50 LHSV, and more preferably in the range of 0.2 to 0.3 LHSV.
lyst” and like terms means a condensation/hydrogenation/ As is apparent from the reaction chemistry outlined above,
dehydration catalyst comprising copper. hydrogen is both a product and a reactant in the system.
The production of MIBC and/or a mixture of IBHK and Preferably an excess of hydrogen is maintained throughout.
TMN from IPA (isopropyl alcohol) and/or DMK can, in one This condition is conveniently referred to as the hydrogen
embodiment, proceed according to the reactions Schemati 55 balance. As will be recognized by those skilled in the art, the
cally described in FIG. 1. Isomers of MSO, DIBK and other desired hydrogen level can be achieved by Such process
compounds identified in these reaction schemes exist and are means as feeding fresh hydrogen, or recycling unused or
probably present in the chemical mix; however, these isomers produced hydrogen. Typically, hydrogen is present in a molar
are not believed to be significant to the instant invention and ratio to MIBK of at least 7:1, more typically of at least 8:1.
for purposes of this invention, are considered as normal MSO, 60 In addition, the system has a certainability to remove heat.
DIBK, etc., respectively. This condition is known as the heat balance. If an excessive
The first three reaction schemes of FIG. 1 describe the amount of MIBK is fed to the system, the exothermic reaction
conventional preparation of MIBK from IPA and/or DMK. between MIBK and hydrogen will give off an excessive
The fourth reaction scheme describes the conventional con amount of heat, more IBHK plus TMN is produced as a result,
version of MIBK to MIBC that occurs in the mixed ketones 65 deactivation of the catalyst may occur, and the consumption
converter. This production of MIBC is supplemented with a of hydrogen will be excessive. Thus, typically, a manufactur
Ni-based catalyst using MIBK plus hydrogen as the feed. ing unit is limited in how much MIBK can be fed without
 US 8,222,460 B2
5 6
disrupting the hydrogen balance and/or the heat balance to The catalysts used for the screening study are samples
Such an extent that the result is unacceptable. produced by Sud-Chemie Inc. Table 1 compares the Cu-based
Better control of the reaction is achieved if the overall catalysts to the current Ni-based catalyst.
system is kept within an acceptable heat balance. Thus, the
stoichiometry of the reactions, as well as the relevant heats of 5 TABLE 1
reaction, needs to be taken into account. For a system which Catalyst Composition and Properties
has only MIBK as a raw material, the general rule for an ideal,
adiabatic system is that a pound of MIBK can be fed for about Cu Cu Cu N
every pound of MIBC that is made by the system. This is Catalyst 1 Catalyst 1* Catalyst 2 Catalyst
because the heat for the production of MIBC is about the same 10
N >2O
amount endothermic as the hydrogenation of MIBK to MIBC Cu 35-50 35-50 10
is exothermic. This also maintains the hydrogen in excess (as oxide) (as oxide)
because one pound/hour of MIBC production consumes Zn 40-5S 40-5S
about 0.02 pound/hour hydrogen. Most systems are not ideal, (as oxide) (as oxide)
of course, so it may be possible to Successfully feed more 15 Cr 0.4
Ca 1.2
MIBK than would be suggested by this analysis. Graphite <5 <5
As earlier noted, both the MIBC and IBHK/TMN mixture Al2O3 balance balance
ratio can be controlled by increasing or decreasing the tem SA (mig) 30-60 30-60 >2OO >75
Particle size A" x 1/4" /4" x 1/4" 5 x 8 mesh 3 x 8 mesh
perature in combination with the use of a Cu-based catalyst. Bulk density 80-95 80-95 SOS 605
As a theoretical example, if the system is under typical oper (Ibs/ft)
ating conditions and feed composition using a Ni-based cata Crush strength >7 >7 >15 15
lyst, then the system would produce 90-95% MIBC and little, (Ibs)
Shape cylindrical cylindrical sphere sphere
if any, IBHK plus TMN mixture. The same performance is tablets tablets
achieved if the Ni-based catalyst is replaced with a Cu-based
catalyst and the system is operated at 130 C. Operate the 25 *Cu Catalyst 1* (Cu-1*) is identical to Cu Catalyst 1 (Cu-1) except that Cu-1* has 5-15%
calcium aluminate as a binder to help maintain its structural strength,
Cu-based system at 200 C, however, and the system might
now produce 50% MIBC and 20% IBHK plus TMN mixture. The screening tests are completed over a relatively short
Historically, to run a Ni-based catalyst system at 200° C.; time frame to gain a basic understanding of performance
would limit MIBC production to less than 60 wt % and potential (1100 hr for the Cu-1 and Cu-1 catalysts, and 650
produce minimal to nil IBHK plus TMN mixture. Moreover, 30
hr for the Cu Catalyst 2 (Cu-2)), so life cycle is not deter
the side reaction impurities would increase dramatically. To mined. The catalysts can be regenerated as needed. In a first
produce the equivalent 20 wt % IBHK plus TMN mixture run Cu-1* is charged to the inlet half of the reactor and Cu-1
would have required a separate campaign. is charged in the outlet half of the reactor. The total amount of
The ability to produce MIBC, and simultaneously co-pro catalyst charged to the reactor is 20 cc, and the ratio of Cu-1
duce IBHK and TMN using Cu-based condensation/hydro 35
to Cu-1* is 1:1 by volume. In the next run, the total amount of
genation/dehydration catalysts instead of Ni-based catalysts catalyst charged is also 20 cc but in this instance, all of the
under similar process conditions is demonstrated in the fol catalyst is Cu-2.
lowing examples. The process of this invention increases the Procedures and Results
C, i.e., the IBHK plus TMN, capacity, eliminates the need Although a range of temperatures are tested to determine
for separate labor intensive campaigns to Supplement IBHK 40
the hydrogenation activity of the catalysts, condensation
plus TMN production, utilizes a less expensive catalyst, low potential and product mix flexibility, and efficiency of con
ers conversion cost, and generates fewer hydrocarbon impu verting MIBK to MIBC and/or IBHK plus TMN, most all of
rities as compared with a Ni-catalyst based process similar in the other parameters are held constant.
essentially all other aspects.
The following examples further illustrate the invention. 45
TABLE 2
Unless otherwise stated, all parts and percentages are by
weight. Reaction Parameters

SPECIFIC EMBODIMENTS Parameter Quantity

50
Pressure 20 psig
Materials and Equipment MIBK Rate 4 cc/hr, 0.2 hr' LHSV
A fixed bed, single-pass, vapor phase reaction system H2:MIBK 8:1 molar
(nominal/2 inch diameter tubing by 10-12 inchbed length) is Molar ratios of 4:1 and 2:1 are also tested for Cu-2.
used to study the condensation/hydrogenation/dehydration of LHSV = Liquid Hourly Space Velocity measured in the gas phase and at pressure.
MIBK to MIBC and IBHK plus TMN. All the MIBK feed is 55
from the same source, i.e., plant-generated product recovered FIG. 2 shows that the high hydrogen ratio (8: 1) pushes the
from the distillation columns. Ultra-high purity (99.99%) equilibrium conversion to the alcohol as well as prevents
hydrogen from Air-Gas Inc. is co-fed to the reactor. The capillary condensation which can lead to excessive catalyst
catalyst bed temperature is within a few (+ or -5) degrees C. deactivation. The results at similar process conditions for the
of the reported oven temperature. The reactor vapor product is 60 Ni-based catalyst are obtained from a previous study, and are
condensed, and liquid samples are taken each working day used for comparison purposes.
morning and analyzed with an HP 6890 gas chromatograph. The major components in the reactor outlet composition
Samples are water-titrated, and all are less than 2 wt %. The are shown in FIGS. 2-5 as a function of the furnace bed
chromatogram method uses a flame ionization detector, is temperature. In addition to the results for all three catalysts is
calibrated with a standard, and the results are normalized to 65 the theoretical thermodynamic prediction for MIBC (FIG. 3)
100% using the water factor as determined by a Karl Fisher when considering only the ketone to alcohol balance (i.e.
type titrator. without condensation). The screening results clearly indicate
 US 8,222,460 B2
7 8
equilibrium conversion at typical commercial conditions tion upon the following appended claims. All U.S. patents,
down to 130 C. At the higher temperatures where condensa allowed U.S. patent applications and U.S. patent application
tion activity is much greater, MIBC is less than predicted due Publications are incorporated herein by reference.
to MIBK consumption to IBHK plus TMN production. Also What is claimed is:
the MIBK to MIBC balance is shifted as expected with lower 5 1. A method of increasing the amount of methyl isobutyl
H:MIBK ratios as is screened with only the Cu-2 catalyst carbinol product relative to isobutyl heptyl ketone plus trim
(see FIG. 2) at 160 C. The 8:1 ratio has been historically ethyl nonanol product, both products made from contacting
preferred to prevent capillary condensation which can lead to methyl isobutyl ketone with hydrogen and a Cu-based con
irreversible structural damage and premature deactivation of densation/hydrogenation/dehydration catalyst under conden
the catalyst. 10
sation/hydrogenation/dehydration reactive conditions which
FIG. 4 indicates how sensitive IBHK plus TMN production includes a reaction temperature, the method comprising the
is to temperature. At the lower boundary of 130°C., the total step of using a reaction temperature of less than 200° C. and
IBHK plus TMN production is about 0.1 wt %. The IBHK the increase measured against a method identical to the
plus TMN potential at 200 C is 33% for Cu-1 and Cu-1* and method described except that the catalyst is Ni-based rather
19% for Cu-2. The Cu-1 and Cu-1 catalysts are more pro 15
than Cu-based catalyst.
ductive as expected compared to the Cu-2 catalyst given that 2. The method of claim 1 in which the reaction temperature
is between 90 and 150° C.
the latter is supported with a lower metal composition (wt % 3. The method of claim 2 in which the catalyst is a bi
of copper on the catalyst). Also important to note is the ratio functional copper-based aldol condensation catalyst.
of IBHK to TMN as the temperature changes as shown in 4. The method of claim 3 in which the catalyst comprises
FIG. 5. In the art, heavier product is comprised mostly of one or more of Na, Ca, Mg and Li.
IBHK so the alcohol balance that is obtained by the inventive 5. The method of claim 4 in which the catalyst further
process is both much greater and more dependent upon the comprises Cr.
temperature of operation. This balance can be shifted by 6. The method of claim 1 in which the catalyst is carried on
limiting the hydrogen feed. a Support comprising an aluminum oxide.
The selectivity to product MIBC, IBHK and TMN is typi 25
7. The method of claim 6 in which the support further
cally greater than 98%. Three main impurities are indicated in comprises calcium aluminate.
the gas chromatographic results, i.e., 2-methyl pentane and 8. The method of claim 6 in which the copper is present in
two other components that are not identified but are likely an amount of 5 to 15% based on the weight of the catalyst.
hydrocarbons. FIGS. 6-7 show typical product range varia 9. The method of claim 1 in which the reactive conditions
tion of MIBC and IBHK plus TMN as the temperature is 30
include liquid hourly space velocity of 0.5 to 1.5.
varied between 130° C. and 200° C.
Although the invention has been described in considerable 10. The method of claim 1 in which the hydrogen is present
detail by the preceding specification, this detail is for the in a molar excess relative to the methyl isobutyl ketone.
purpose of illustration and is not to be construed as a limita k k k k k