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Harrison et al.
[45]
476,453
Mar. 3, 1992
Date of Patent:
5,093,535
1002372
1362071
8/1965
7/1974
United Kingdom .
[57]
ABSTRACT
PCT No.:
PCT/GB88/01027
371 Date:
Jun. 4, 1990
102(e) Date:
Jun. 4, 1990
[30]
[52]
[56]
References Cited
U.S. PATENT DOCUMENTS
3,880,940
9/1975
568/874
4,451,677
568/881
4,510,092
4/1985
260/409
4,626,604 12/1986
4,960,960 10/1990
Rosen ............ ..
product.
23 Claims, 10 Drawing Sheets
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Mar. 3, 1992
Sheet 1 of 10
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Mar. 3, 1992
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5,093,535
hydrogenation catalyst.
thereof).
There have been various pn'or proposals to operate
hydrogenation processes in several catalytic stages con
nected in series. For example, a vapour phase aldehyde
hydrogenation process is described in U.S. Pat. No.
nected in series.
'
benzyl cyanide is an example of hydrogenation of a 45 whilst the aldehyde feed rate corresponds to a space
nitrile. As examples of hydrogenation of sugars to
velocity of from 0.3 to 2.5 hr-, preferably 0.75 to 1.1
polyhydroxyalcohols there can be mentioned hydroge
hr-l. An excess of hydrogen is recirculated from the V
nation of ketose and aldose sugars to hexahydroxyal
exit end of the second hydrogenation stage to the inlet
cohols, for example hydrogenation of D-glucose to
end of the first hydrogenation stage.
sorbitol and of D-mannose to mannitol.
50
GB-A-784359 is concerned with preferential hydro
An important route to C3 and higher alkanols in
genation of aldehydes in a mixture of aldehydes and
volves hydroformylation of alpha-olefms, such as ethyl
olefms, water being added to inhibit ole?n hydrogena
ene, propylene, and butene-l, to yield the correspond
tion. Multi-bed co-current hydrogenation is used, with
ing aldehyde having one more carbon atom than the
injection of hydrogen between beds. Hydrogen recycle
is envisaged.
5,093,535
(ISCRE 8);
65
5,093,535
!0 182;
15. Catalyst Effectiveness Factor in Trickle-Bed Reac
tors" by M. P. Dudukovic and P. L. Mills, Chemical
1104;
17. Analysis of Three-Phase Packed-Bed Reactors by
S. Goto and J. M. Smith, AIChE Journal, Vol. 24,
No. 2, pages 295 to 302;
18. "Performance of Slurry and Trickle-Bed Reactors
to 163;
1261;
188;
30. Kinetics of Hydrodesulfurization by C. G. Frye
and J. F. Mosby, Chemical Engineering Progress,
Vol. 63, No. 9, September 1967, pages 66 to 70; and
5,093,535
uct.
Care must accordingly be taken, in designing a plant to 20 Another example of a hydrogenation reaction to
which the present invention can be applied is the pro
operate according to the invention, that it is ensured
duction of butane-1,4-diol by hydrogenation of but-2
that at the bottom of the catalyst bed the crushing
yn-l,4-diol This can be carried out using a catalyst
strength of the catalyst is not equalled or exceeded. If
which is a granular nickel-copper-manganese on silica
there is any risk of this occurring, then it is necessary to
gel at a pressure of from about 200 bar to about 300 bar
utilise two or more catalyst beds of appropriate depth in
in the hydrogenation zone. A typical inlet temperature
place of a single large catalyst bed; in this case gas and
to the hydrogenation zone is about 40' C., when the
liquid must be uniformly distributed into each bed.
catalyst is freshly reduced
The selection of catalyst particle size and of the su
A further example of a hydrogenation reaction to
per?cial liquid velocity are features which are crucial to
the process of the invention. These features ensure that 30 which the process of the invention can be applied is the
production of stearic acid by hydrogenation of linoleic
the catalyst surface is completely wetted, that a large
acid, of linolenic acid, or of a mixture thereof This can
catalyst super?cial surface area is presented for reaction
'
catalyst,
according
to
the
equation:
R-CH=Cl-l1 + Hz + CO>R-CH2-CH2'CHO + R~CH(
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10
lysts are those with a particle size range of from about 65 organic feedstock dissolved in a compatible diluent
1 mm to about 2 mm.
5,093,535
11
12
hydrogenation product.
many cases the hydrogenation product itself can be 30 obtained. Generally, however, when an adiabatic tem
perature rise across the catalyst bed of from about 20'
used as the compatible diluent or as a part of the com
C. to about 30' C. can be accepted, a simple hydrogena
patible diluent. Hence, when hydrogenating an alde
tion reactor consisting of one or more beds of catalyst in
hyde for example, the diluent can be the product alco
a cylindrical vessel with its axis arranged vertically can
he] obtained upon hydrogenation of the aldehyde. In
be used with good results. When two or more beds are
this case the process of the invention includes the fur
used in such a reactor the space between adjacent beds
ther step of recycling a part of the liquid hydrogenation
will be largely occupied by the gas phase. The liquid
product for admixture with make up unsaturated or
emerging from one bed may with advantage be col
ganic compound or other organic feedstock to form the
lected and passed over a distributor of conventional
feed solution to the hydrogenation zone. Alternatively
aldehyde condensation product, such as the dimers, 40 design before entering the next bed.
The hydrogen containing gas is generally admixed
trimers and high condensation products of the type
with the feed solution upstream from the hydrogenation
disclosed in GB-A-l338237, can be used as diluent. If
zone and is partly dissolved therein. At the upper end of
the unsaturated organic compound or other organic
the hydrogenation zone the concentration of unsatu
feedstock used as starting material is a solid or if the
hydrogenation product or an intermediate product is a 45 rated organic compound or other organic feedstock is at
tity of hydrogen is used in the process of the invention 60 hydrogen is consumed by the chemical reactions taking
place in the hydrogenation zone. Hence at the lower
and there is at most only a small excess of hydrogen
end of the hydrogenation zone the driving force for the
used, the liquid phase hydrogenation of even relatively
hydrogenation reaction can be relatively low. The reac
volatile unsaturated organic compounds to similarly
tion product exiting the lower end of the hydrogenation
volatile products, such as n-butyraldehyde to n-butanol,
or benzene to cyclohexane, can be effected with essen 65 zone accordingly usually still contains a minor amount
13
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14
ganic material.
20
thereof.
15
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16
that supplied to the first-mentioned hydrogenation 5 steady state conditions, the composition of the gas
(whether dissolved in the liquid phase or present in the
gaseous state) exhibits a significant variation between
ally in lesser amounts than the amount of hydrogen-con
different parts of the plant. Thus, for example, the par
taining gas supplied to the ?rst-mentioned hydrogena
tial pressure of hydrogen is highest in the, or in each,
tion zone. Generally speaking, it should be fed to the
further hydrogenation zone in an amount sufficient to 20 hydrogenation zone at the respective gas inlet end
ally it will be preferred to supply hydrogen-containing 25 highest at the exit end for gaseous effluent therefrom. It
is thus possible to discharge from the hydrogenation
gas to the further hydrogenation zone at a rate sufficient
to supply not more than about 115% (e.g. up to about
in hydrogen than that fed to the ?rst-mentioned hydro 35 N2, Ar, CH4 etc). In this case the effluent gas stream or
genation zone. Hence the gas fed to the first-mentioned
hydrogenation zone may be, for example, a 3:1 molar
counter-current flow regime. Hence the driving f 45 from the hydrogenation zone, the inert gases being
purged in the course of work up of the hydrogenation
towards the desired hydrogenation product is maxi
product.
mised in the further hydrogenation zone and essentially
Because any inert gases present are automatically
all of the remaining unsaturated material in the liquid
concentrated in any gaseous effluent stream or streams,
phase exiting the first-mentioned hydrogenation zone is
'
17
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18
the bed.
reactor 1.