Enantioselectivity of tartaric acid-modified Ni-Al2O3 catalysts

Applied Catalysis, 30 (1987) 141-149 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

ENANTIOSELECTIVITY

Yuriko

NITTA,

Department

OF TARTARIC

Masayuki

KAWABE

of Chemical

Toyonaka,

Osaka

(Received

1 July

ACID-MODIFIED

Ni-A1203

and Toshinobu

CATALYSTS

IMANAKA

Faculty

Engineering,

141

of Engineering

Science,

Osaka University,

560, Japan.

accepted

1986,

6 November

1986)

ABSTRACT Effects of the preparation conditions on the properties of precipitated Ni-Al203 (1:l) catalysts precursors were studied using thermogravimetric analysis (TGA). The larger part of the nickel species on alumina, having no interaction with the support, is readily reduced and yields large nickel crystallites, while the remaining smaller part of the nickel species, having strong interactions with the support, has a lower reducibility and yields smaller crystallites. The reducibility of only the latter species is affected by the preparation conditions. The resulting bimodai size distribution of nickel crystallites on alumina explains the low activitv and enantioselectivitv of modified Ni-A1702 catalvsts oreoared with sodium carbonate. A small amount of Fe salt precipitatedLo; the support prior to the precipitation of the Ni salt increases the enantioselectivity of the catalyst, probably as a result of blocking the sites having strong metal-support interactions.

INTRODUCTION The asymmetric attracted

hydrogenation

3-hydroxybutyrate reactions

structure

[6-81, we reported

on the mean

catalysts

catalysts

prepared

active

use.

methyl

to the understanding

of the catalyst

the reaction

of the

surface

is

is known to be highly

which

because

selective

of precipitation

0166-9834/87/$03.50

size of nickel

size distribution

affect

of changes Ni-Si02

(CSD) of nickel

method

the composition

leads to variable

and reduction.

0 1987 Elsevier Science Publishers B.V.

sodium

carbonate,

and the reducibility

activity

were

plays an

of the catalyst.

with

and selectivity

in the CSD of nickel

catalysts

of modified

and that, with supported

of the enantioselectivity

by a precipitation

variables

precursors,

and satisfactorily conditions

synthesis

for the enantio-

that the enantioselectivity

crystallite

the crystallite

all preparation

the catalyst H2-reduced

has been devoted

although

role in the determination

With Ni-SiO2 almost

for asymmetric

(MAA) to optically

[2-51. The morphology

has long

but also for industrial

Raney Ni catalysts

acetoacetate

of much debate,

papers

depends

catalysts,

important

catalysts

using enzymes

sensitive.

In previous catalysts

modified

of methyl

catalysts

without

not only scientifically

(MHB), much effort

on metal

still the subject

products

on heterogeneous

importance,

Izumi et al. [I] developed

selective

nickel

of natural

Studies

attention.

are of particular Since

synthesis

prepared

[9,10].

Highly

under optimal

of

of the active

1

0 0 75 90 90

NOH-1

NOH-2

NOH-3

NOH-4

NOH-5

to NCO-5 are samples

50

90

NCO-5

aNCO-l

20

90

NCO-4

48

24

24

24

72

with Na2C03

20.8

22.2

20.9

28.3

5

5

9

16

31

24

24

24

31

31

nm

Dc/

Ni-A1203

164

160

142

108

97

106

113

101

104

105

m2g-'

5a/

catalysts

SM/

6

5

6

12

11

IO

7

8

IO

14

nm

Ds/

with NaOH.

37.2

41.3

34.0

17.5

19.0

21.6

31.8

26.6

21.2

15.9

m2g-'

and NOH-1 to NOH-5 precipitated

3.27

2.09

1.60

1.11

23.7

0.62

0.49

15.8 28.6

0.86

48

24

18.3

0.98

precipitated

120

120

110

120

120

la.7

0.37

24

"/ 0

OY/

24

-1

13.2

50

NCO-3 110

0 75

NCO-2

r0'

0.37

72

20

time/h

0

temp./Y

temp./"C

Drying

NCO-1

Drying

Precipitation

of modified

mm01 g-'min

on the properties

conditions

conditions

Preparation

of preparation

Precursora

Effects

TABLE

144 Hydrogenation A 10 ml volume the modified

a glass autoclave activity

determined

MAA was hydrogenated

at 60°C under a starting

equipped

with a magnetic

(ro) of the catalyst

the initial

measure

of distilled

catalyst

from the optical

stirring

was determined

15 min of the reaction.

system.

yield

of the distilled

(IO ml) with -2 by using

of IO kg cm

The hydrogenation

from the pressure

The optical

rotation

of the enantioselectivity

in ethyl acetate

H2 pressure

decrease

during

(OY) of the product,

MHB,

product

as a

was employed

of the catalyst.

Analysis The thermogravimetric thermal

analyser.

experiments

A portion

were carried

out using a Shimadzu

(ca. 40 mg) of a freshly

prepared

precursors

heated

in a flow of N2 or H2 to 600°C at lO"C/min

unless

degree

of reduction

from the weight

measurement catalyst

broadening

surface

area

crystallite

from the half-width

in the XRD pattern

of instrumental and metal

was estimated

in a flow of H2. The mean

was calculated

nickel metal

-196°C

of the catalyst

by Warren's

and by H2 adsorption

stated

method

after correction

FIGURE

correspond

to the precursors

at

nl

3;o

100

500

500

Temperature/"C

1 DTG profiles measured precursors

(Sit)

I

300

Ni-Al203

area

by N2 adsorption

at 25"C, respectively.

Temperature/"C

various

in the

for the effects

[17]. The BET surface were measured

I

100

The

loss in a TG

sire (DC) of nickel

b)

I

was

otherwise.

of the peak on the (111) plane of

of the catalyst

(SM) of the catalysts

DT-30

in (a) a flow of N2 and (b) a flow of H2 for

prepared listed

by using Na2C03 in Table

1.

(--)

and NaOH (---). Numbers

145 RESULTS

AND DISCUSSION

Table

1 lists the catalytic

from various conditions

precursors.

did not affect

of nickel

catalysts

in the resulting

widely,

selectivity

depending

of the weight

carbonate

appear

reported

CatalyStS

the hydrogenation

(DTG) curves,

although

activity,

i.e., the first derivatives

for the various

Ni-Al203

of adsorbed at around

water

and the water

IOO-150°C

and ZOO"C,

precursors

to the weight

respectively.

These

each other when they are large. With

the precursors

using Na2C03,

the peak around

to the decarboxylation

temperature

much

shifted

[IO]. However,

of Ni-Al203

in the basic

nickel

losses

that A1203

carbonate

prepared

does not accelerate

nickel

two peaks around

hydroxide

interaction position

having

conditions,

The DTG profiles of the preparation A1203

ture, whereas

species,

be detected

the larger the support

of nickel

hydroxycarbonate,

catalysts

aluminate

C19,2D]

intensity with

Ni(OH)2

clearly

but also

that,

regardless

carbonate

has some

with the support, rate, which

[18]. The formation

and the decom-

at relatively

Ni(OH)2,

of

strong

the preparation

on

low tempera(mild or

(Figure

than Si02 with metal

was reported

NaOH

and A1203.

and has a low reducibility

of the very low reduction

to the formation

by using

to the decomposition

and is reduced

interaction

it seems

in the precursor

part of the basic nickel

interaction

very strong

nickel

coprecioitated

between

was

from the

Therefore,

prepared

slightly

part of the Ni species,

has a greater

by DTG because

aluminium

interaction

com-

than 50% even

and a relatively

The relative

peak increased

with the support

having

interaction

in a flow of H2 showed more

with

the remaining

interaction

is known that A1203 nickel

measured

corresponding

respectively.

increasing

conditions,

has no interaction

strong)

280 and 4OO"C,

of the latter

indicating

to Ni(OH),

in

of NiC03

were estimated

of NiC03

of the precursors

of NiC03

conditions

to be larger (NCO-5).

the change

increasing

percentages

conditions

no or only a weak

with the support,

temperature

precursors found

by of

in the chemical

The molar

and were

severe

with

in the preparation

in the Ni-A1203

under

prepared

in the percentage

of the variation

precursors.

as much as SiOp does. The DTG profiles exhibited

a decrease

with a change

in the range ZOO-500°C

for the precursors

to a lower temperature

the extent

precursors

less than that for the Ni-Si02

weight

corresponding

indicating

of preparation,

the precursor position

carbonate,

320°C,

in

of crystallization

peaks overlap

free basic nickel

the

the enantio-

la. The peaks corresponding

in Figure

losses due to the desorption

obtained

the preparation

constant.

were measured

loss curves,

catalysts

and the mean Cr'YStallite size

as with Ni-Si02

and hence

catalysts,

thermogravimetric

a flow of N2 and are shown

of nickel

as much

on the .preparation conditions,

was low and almost

The differential

Ni-Al203

hand, when NaOH was used as the precipitant

[IO]. On the other

DC of nickel varied

of modified

used as the precipitant,

the enantioselectivity

in the Ni-Al203

previously

properties

When Na2C03was

lb). It

species.

however,

The

may not

is probably

of the Feitknecht

not only in the preparation

in the deposition-precipitation

due

compound, of method

146 using Y-Al203

activated

of this compound preparation patterns

conditions,

although

and the degrees

examined. latter

at a high pH [Zl]. In our case also,

could occur at the alumina

The strength

smaller

surface,

no corresponding

of reduction

were

of the interaction

part of the nickel

the limited

especially

under

peaks were detected

nearly

on the XRD

100% for all the catalysts

and hence the reducibility

species

formation

severe

seem to be affected

of only the

by the preparation

conditions. Hence,

the reduction

of nickel, as already lites

of these Ni-A1203

shown

(which are more selective

nickel

carbonate

and smaller

come from nickel

species

nickel-aluminium

compounds.

the Ni-A1203 difference

catalysts

between

(Table NCO-5

compound,

H2 reduction.

The finding

enantioselectivity conditions

catalysts

originate

For the precursors

prepared

with NaOH,

and hence with high reducibility,

ditions

became

support

interaction,

small nickel

The reduction

of the Ni-A1203 and NOH-5

in Table

agreement

with each other.

The proportion estimated

1).

prepared

groups

and found

C18,22,24,25].

lites from the nickel the enantioselectivity was added tation

when

interaction our reaction

reducibility,

by using NaOH under

a

support

crystal-

inter-

the preparation species will

con-

with a stronger

result

in only

and the low selectivity

severe

species

having

a strong

conditions

having

a strong

of the Ni-A1203 on A1203

with Na2C03.

severe

with

(NOH-4

and,

to metal.

interaction

precursors

of small interaction

a small amount conditions

prior

in addition,

As shown

was

with various

the results

The Fe salt was expected

to the Ni salt with the support when reduced

support

catalysts,

under

support

of Ni-A1203

in agreement

In order to prevent the formation

species

conditions

Ni(OH)2

the high activity

to be lo-20%,

species

and precipitated

of nickel

nickel

low reducibility.

disappeared

on the basis of the TG measurements

loadings,

of smaller

mild

In these cases, the values of DC and Ds are in fair

of the nickel

nickel

after

as high an

relatively

without

of remaining

This explains

catalysts

with

of the non-reducible

can exhibit under

having

in these catalysts

crystallites

the species

and hence with a lower

crystallites.

reduced

species

action,

severe.

nickel

in terms of the absence

from the nickel

line broadening

from the precursor

formation

catalysts

when

of

The significant

from X-ray

obtained

of smaller

that the Ni-A1203

as Ni-Si02

possible

(D,) for the catalysts

to the partial

basic

and selectivity

as the precipitant.

areas

CSD

crystal-

but less selective)

of small crystallites

the proportion

[7] is also explained

lites which

surface

nickel

including

the low activity

size obtained

the presence

in a bimodal

larger

(more active

high OY for the catalyst

diminishes

result

interaction,

by using Na2C03

1 could be attributed

which

support

crystallite

from metal

supports

will

come from non-interacting

crystallites

This explains

prepared

1). The relatively in Table

nickel

the nickel

DC strongly

but less active)

with a strong

(DC) and that estimated larger

precursors

by TPR [ZZ] and EM [23] studies;

nickel

of other crystal-

and to increase of an Fe salt to the precipi-

to have a similar to be inactive

in Figure

under

2, the addition

147

I

Fe/(Fe+Ni) FIGURE

2

Dependence

Ni-Fe-A1203;

FIGURE

3

Heating

TABLE

of optical Ni-Fe-Si02.

DTG-in-H2

profiles

Fe contents,

rate:

Temperature/"C

yields

on the Fe content

of Ni-Fe-A1203

Fe/(Fe+Ni):

precursors

(a) 0 wt%;

in the catalysts.

prepared

(b) 7 wt%;

(c) 14 wt%;

(d) 21 wt%.

S"C/min.

of support

on the properties

of supported

Ni catalysts.

OY/%

DJnm

SiO

49.7

8

2 Si02-A1203

3

Si02-A1203

4

A1203

(SAL)a

28.9

9

(SAH)~

23.9

14

18.3

24

aAl

content

13.8%.

bA1203

content

28.6%.

of about

IO wt% of Fe to Ni was found

enantioselectivity crystallites action.

(0)

under severe

Support

2

500

2

Effects

1

1

I

300

100

(wt%)

(0)

conditions.

40

30

20

10

f

1

I

I

of Ni-A1203

originating

The Ni-Fe-A1203

selectivity

to be most effective.

catalysts

from the nickel (9:l:lO)

catalyst

but also as high an activity

by the significant in the species

decrease

having

of added Fe, as shown

in the amount

a mild support in Figure

is attributable species

Accordingly,

the low

to the small nickel

having a strong

support

inter-

had not only as high an enantioas Ni-Si02

catalysts.

of free nickel

interaction

3. On the other

with

This can be explained

species

and the increase

an increase

hand, the addition

in the amount of Fe to the

148

FIGURE

4

listed

in Table

Ni-SiD2

DTG-in-H2

500

of the precursors -1 .

prepared

catalyst

had negative

effects

just as with

the addition

Silica-alumina

with different

of the support

in the enantioselective

the Ni-silica-alumina

catalysts

catalysts.

The acidity

enantioselectivity explained supports

which

between

effect

least partly,

explanation

out previously

catalysts

in Table

intermediate

appears

Ni-y-A1203

it may affect

of crystallite

and the support.

will be required.

[7,8], the difference catalysts

of nickel species

on different

in the precursors,

from the catalyst

accompanying

studies

concerning

in

can be

metal

surface

[14] can also be ascribed,

in the DC of nickel [6]. Further

influence

studies

and Ni-Si02

of

and

the CSD of

the metal

with nickel

catalysts

those of Ni-Si02

between

papers

of aluminium

4, the

behaviour

to have no direct

in the morphology

interactions

to examine Ni catalysts

2 and Figure

between

although

in our previous

[261.

of supported

sizes and the reduction

the interaction

Raney-Ni

to an increase

nickel

As shown

catalyst,

of the removal

of the effects

supports

and the selectivity elsewhere

was used as a support

the properties

of a support

modified

of modified

pointed

contents

of this point further

suggested

have different

the selectivity

modified

were

in terms of the difference

The favourable

already

by affecting

discussion

Thus, as already

of Pd reported

crystallite

of the resulting

Ni in the catalyst For a detailed

A1203

hydrogenation. the mean

on the properties

on both the activity

influences

enantioselectivities,

Ni-A1203

by using different

rate: 5°C min

of the catalyst,

if the acidity

I

300 Temperature/"C

profiles

2. Heating

I

I

I

I

100

on

at

the procedure,

as

the detailed

size on the enantioselectivity

of

are in progress.

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