��: hydrogenation lactic acid

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mybb@mybb.ru (maxifa) — Sun, 18 Sep 2011 14:58:59 +0400

�� 9
�� , �� CG6M-F.
2 0 CG6M-F ��
� �� 4. �� 110 + 200 �� 728 � 2 �� (� �� -��, Inc.) �� 5,0% ��
25 ��
�� 13%. �� , �� 3 � �� 1.
�� 10
3 0 �� , ��
�� SG6-D.
Catalyst SG6-D �� 4. �� 100 ��
3 5 777 � 2 �� (� �� -��, Inc.)
�� 4,4% �� , �� 10%. �� , �� 5 � �� 1.
5
�� 11
�� , �� CG5P-N01-I.
Catalyst CG5P-N01-I ��
10 �� 4. ��
CG5P-200 �� 648 � 2 �� (� �� -��, Inc.) �� 5,0% �� , ��
15 �� 38%. ��
��, �� 6 � �� 1.
�� 12
�� , ��
20 �� CG5P-.
Catalyst CG5P-�� 4. �� CG5P 20 * 50 �� 648 � 2 �� (� �� -��, Inc.)
25 �� 5,4% �� , ��
�� 10%. �� , �� 7 � �� 1.
3 0 �� 13
�� , �� SA135-C.
Catalyst SA135-C ��
�� 4. ��
3 5 �� 13 5, -10 0 ��
440 �2 �� (� �� Aldrich Chemical
Company). �� 5% ��
�� , ��
�� 14%.
5 �� , �� 4 � �� 1.
�� 14
�� , ��
�� TiP25-C19-J.
Catalyst TiP25 10-C19-J ��
�� 4. �� 200
�� 4 9 �2 ��
(� �� Degussa Corporation). ��
�� 5% �� , ��
15, �� .
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�� 15
�� , ��
20 �� ALG-E.
Catalyst ALG-E �� 4. �� +200 �� 45 �2 �� (�� ,
25 Inc.) �� 4,7% ��
�� 13,5%. �� , �� 9 � �� 1.
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(�) �� .
-2 -
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-3 -
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-4 -
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-11 -
�� .1, �� fermentate �� .
-12 -
. �� .1, ��
�� .1, �� 80% � �� , �� 80%.
-14 -
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20 �� 16,5 ��
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(�) �� .
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. �� 14 � �� fermentate ��
�� 14 �� 15 �� .
-17 -
�� 16, ��
H2S04.
-18 -
�� .17 �� H2S04 �� .
-19 -
�� .15 �� 5% �� 50% �� .
-20 -
�� 14 � �� 3,4 �� 8,3 ��.
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�� 14 � �� 50 � C �� 200 � �.
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, �� 10 ��
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(�) �� 400 � � �
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(�) �� 16 ��, �
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�� 28 �� .
��
�� PC17US99/27421
�. ��
�� (7): B01J 21/08. 23/40; C07C 27/00
�� CL: 502/261. 326; 568/864 � �� (��), �� , ��
R ��
�� (�� )
��: 502/261, 326, 568/864
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XX

XX
X, P
�� 2607807 (FORD) 19 �� 1952 ��, �� .
�� 4343955 (OSHIMA � ��.) 10 �� 1982 ��, �� .
�� 5478952 (��) 26 �� 1995 ��, �� .
�� 5600028 (GUBITOSA � ��.) 04 �� 1997 ��, �� .
�� 5731479 (��) 24 �� 1998 ��, �� .
�� 5958825 (��-�� .) 28 �� 1999 ��, ��. �� .
1-35 28-35
1-35
28-35
1-35 1-35

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�� PCT/ISA/210 (�� sheetXJuly 1992) *

WO0030744A1 (�� 10)

mybb@mybb.ru (maxifa) — Sun, 18 Sep 2011 14:52:08 +0400

EXAMPLE 9
This example shows the preparation of preferred catalyst CG6M-F.
2 0 CG6M-F was made according to the method shown
in Example 4. The support was a 110 + 200 mesh particle size carbon support with a BET surface area of 728 m2 per gram (available from Cameron-Yakima, Inc.). The ruthenium metal loading was 5.0 wt% which was applied to
25 the support as an aqueous solution of ruthenium chloride
hydrate with a dispersion of 13%. This catalyst is shown as run 3 in Table 1.

EXAMPLE 10
3 0 This example shows the preparation of
preferred catalyst SG6-D.
Catalyst SG6-D was made according to the method in Example 4. The support was a 100 mesh microporous carbon support with a BET surface area of
3 5 777 m2 per gram (available from Cameron-Yakima, Inc.) .
The ruthenium metal loading was 4.4 wt% which was applied as an aqueous solution of ruthenium chloride hydrate with a dispersion of 10%. This catalyst is shown as run 5 in Table 1.
5
EXAMPLE 11
This example shows the preparation of preferred catalyst CG5P-N01-I.
Catalyst CG5P-N01-I was made according to the
10 method in Example 4. The support was a microporous
CG5P-200 mesh carbon support with a BET surface area of 648 m2 per gram (available from Cameron-Yakima, Inc.). The ruthenium metal loading was 5.0 wt% which was applied as an aqueous solution of ruthenium nitrosyl
15 nitrate hydrate with a dispersion of 38%. This catalyst
is shown as run 6 in Table 1.

EXAMPLE 12
This example shows the preparation of
20 preferred catalyst CG5P-A.
Catalyst CG5P-A was made according to the method in Example 4. The support was a microporous CG5P 20*50 mesh carbon support with a BET surface area of 648 m2 per gram (available from Cameron-Yakima, Inc.). The
25 ruthenium metal loading was 5.4 wt% which was applied as
an aqueous solution of ruthenium chloride hydrate with a dispersion of 10%. This catalyst is shown as run 7 in Table 1.

3 0 EXAMPLE 13
This example shows the preparation of preferred catalyst SA135-C.
Catalyst SA135-C was made according to the
method in Example 4. The support was a silica-alumina
3 5 grade 13 5, -10 0 mesh support with a BET surface area of
440 m2 per gram (available from Aldrich Chemical
Company). The ruthenium metal loading was 5 wt% which
was applied to the support as an aqueous solution of
ruthenium chloride hydrate with a dispersion of 14%.
5 This catalyst is shown as run 4 in Table 1.

EXAMPLE 14
This example shows the preparation of
preferred catalyst TiP25-C19-J.
10 Catalyst TiP25-C19-J was made according to the
method in Example 4. The support was a titania 200
mesh support with a BET surface area of 4 9 m2 per gram
(available from Degussa Corporation). The ruthenium
metal loading was 5 wt% which was applied to the support
15 as an aqueous solution of ruthenium chloride hydrate.
This catalyst is shown as run 8 in Table 1.

EXAMPLE 15
This example shows the preparation of
20 preferred catalyst ALg-E.
Catalyst ALg-E was made according to the method in Example 4. The support was a gamma aluminum oxide +200 mesh support with a BET surface area of 45 m2 per gram (available from Johnson Matthey Chemicals,
25 Inc.) . The ruthenium metal loading was 4.7 wt% which
was applied to the support as an aqueous solution of ruthenium chloride hydrate with a dispersion of 13.5%. This catalyst is shown as run 9 in Table 1.
While the present invention is described
30 herein with reference to illustrated embodiments, it
should be understood that the invention is not limited hereto. Those having ordinary skill in the art and access to the teachings herein will recognize additional modifications and embodiments within the scope thereof.
35 Therefore, the present invention is limited only by the

Claims attached herein.

WE CLAIM:

-1-
A process for the production of propylene glycol, which comprises:
(a) reacting a reaction mixture of lactic acid in water and hydrogen with a ruthenium catalyst on an inert support with a BET surface area between about 1 to 1,000 m2 per gram at a hydrogen pressure between about 3.4 to 16.5 MPa and a temperature between about 50� to 2 00�C; and
(b) recovering the propylene glycol from the reaction mixture.

-2-
The process of Claim 1 wherein the concentration of lactic acid is between about 5% and 50% by weight of the reaction mixture.

-3-
The process of Claim 1 wherein the hydrogen pressure is between about 3.4 to 8.3 MPa.

-4-
The process of Claim 1 or 2 wherein the temperature is between about 70� to 150�C.

-5-
The process of Claim 1 as a batch process wherein the reaction mixture is in a closed reaction vessel provided with a stirrer which agitates the reaction mixture.
The process of Claim 1 as a continuous process wherein the reaction mixture is trickled through a bed of the catalyst.

-7-
The process of Claim 1 wherein the ruthenium is supported on an inert support.

-8-
The process of Claim 7 wherein the inert support is selected from the group consisting of alumina, titania, silica, aluminosilicate, and microporous carbon.

-9-
The process of Claim 1 as a continuous process wherein the reaction mixture has a space velocity of between about 0.5 and 5 grams of lactic acid per gram of catalyst per hour.

-10-
The process of Claim 1 as a batch process in a closed reaction vessel provided with stirrer which agitates the reaction mixture for between about 2 to 12 hours prior to recovering the propylene glycol.

-11-
The process of Claim 1 wherein the lactic acid is present in an aqueous fermentate produced by a microorganism.

-12-
The process of Claim 1 wherein the reaction mixture contains sulfur.
The process of Claim 1 wherein the propylene glycol is recovered in a yield of at least 80% and a selectivity to propylene glycol of at least 80%.

-14-
A process for preparation of propylene glycol
comprises:
(a) providing a ruthenium metal catalyst
prepared by reacting hydrogen-containing gas with a
5 ruthenium salt deposited and dried on an inert
microporous support having a BET surface area between about 1 and 1,0 00 m2 per gram;
(b) drying the catalyst in an oxygen
containing atmosphere so as to provide oxide of the
10 ruthenium on surfaces of the ruthenium;
(c) introducing the dried catalyst into a reaction vessel;
(d) reacting the catalyst with the oxide on the surface with hydrogen in the vessel;
15 (e) reacting in the vessel at elevated
pressures and at elevated temperatures, a reaction mixture of lactic acid in water in the presence of the catalyst, wherein the temperature is between about 70� to 170�C and the hydrogen pressure is between about 3.4
20 to 16.5 MPa to produce the propylene glycol in the
reaction mixture; and
(f) recovering the propylene glycol from the reaction mixture.

-15-
The process of Claim 14 wherein the lactic acid is provided as a fermentate produced by a microorganism.
The process of Claim 14 or 15 wherein the lactic acid is provided in an impure form as its salt or a partially acidulated salt and the reaction mixture further comprises an acid.

-17-
The process of Claim 16 wherein the acid is
H2S04.

-18-
The process of Claim 17 wherein the H2S04 is added to provide a molar ratio of lactate salt to acid equivalent of one to one.

-19-
The process of Claim 15 wherein the lactic acid is provided at a concentration between about 5% and 50% by weight of the reaction mixture.

-20-
The process of Claim 14 wherein the hydrogen pressure is between about 3.4 to 8.3 MPa.

-21-
The process of Claim 14 wherein the temperature is between about 50�C to 200�C.

-22-
The process Claim 14 wherein the support is selected from the group consisting of alumina, titania, silica, aluminosilicate, and microporous carbon.
The process of Claim 14 as a batch process wherein the reaction mixture is in a closed vessel provided with a stirrer which agitates the reaction mixture.

-24-
The process of Claim 14 as a continuous process wherein the reaction mixture is trickled through a bed of the catalyst.

-25-
The process of Claim 14 as a continuous process wherein the reaction mixture has a space velocity of between about 0.5 and 5 grams of the lactic acid per gram of the catalyst per hour.

-26-
The process of Claim 14 wherein the reaction mixture further contains sulfur.

-27-
The process of either Claim 1 or 14 wherein the propylene glycol is recovered in a yield of at least 80% and a selectivity to propylene glycol of at least 80%.
A composition which comprises an essentially-
pure elemental ruthenium on an inert microporous
support, wherein the ruthenium is deposited on the
support by drying a water solution of ruthenium salt on
5 the support, reducing the salt to elemental ruthenium on
the support with hydrogen, and passivating the composition in an oxygen containing atmosphere so as to provide an oxide of the ruthenium on surfaces of the ruthenium.

-29-
The composition of Claim 28 wherein the inert microporous support is selected from the group consisting of alumina, titania, silica, alumina silicate, and microporous carbon.

-30-
The composition of Claim 28 wherein the inert microporous support has a BET surface area between about 1 to 1,00 0 m2 per gram.

-31-
The composition of Claim 28 wherein drying the ruthenium salt on the catalyst is at about 25�C for about 5 hours and then under a vacuum of about 3 0 inches of mercury at about 100�C for 12 hours.
The composition of Claim 28 wherein reducing the ruthenium salt to elemental ruthenium comprises the steps of
(a) heating the catalyst from 25�C to 400�C at
a rate of about 0.5�C per minute under a flow of a gas
consisting of 10 volume percent of hydrogen in helium at
a rate of about 3 0 ml per minute;
(b) maintaining the catalyst at 400�C and
changing the gas to pure hydrogen;
(c) reducing the catalyst in the pure hydrogen for about 16 hours; and
(d) cooling the catalyst under a helium flow to room temperature.

-33-
The composition of Claim 2 8 wherein passivating the catalyst comprises of placing the reduced catalyst in a stream of about between 1 to 10 volume percent of oxygen in an inert gas at room temperature for about 1 hour.

-34-
The composition of Claim 2 8 wherein the inert gas is between about 1 to 3 volume percent.

-35-
The composition of Claim 28 wherein the ruthenium is reduced in a reaction vessel with hydrogen prior to contact with a reaction mixture.

INTERNATIONAL SEARCH REPORT

International application No. PC17US99/27421

A. CLASSIFICATION OF SUBJECT MATTER
IPC(7) :B01J 21/08. 23/40; C07C 27/00
US CL :502/261. 326; 568/864 According to International Patent Classification (IPC) or to both national classification and IPC
R FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
U.S. : 502/261, 326; 568/864

Documentation searched other than minimum documentation to the extent that such documents are included in me fields searched

Electronic data base consulted during the international search (name of data base and. where practicable, search terms used)

DOCUMENTS CONSIDERED TO BE RELEVANT

Category*

Citation of document, with indication, where appropriate, of the relevant passages

Relevant to claim No.

X X

X X
X, P

US 2,607,807 A (FORD) 19 August 1952, see entire document.

US 4,343,955 A (OSHIMA et al) 10 August 1982, see entire document.

US 5,478,952 A (SCHWARTZ) 26 December 1995, see entire document.

US 5,600,028 A (GUBITOSA et al) 04 February 1997, see entire document.

US 5,731,479 A (ANTONS) 24 March 1998, see entire document.

US 5,958,825 A (WULFF-DORING et al) 28 September 1999, see entire document.

1-35 28-35

1-35

28-35

1-35 1-35

Special categories of cited document!:
"A" document defining the general state of the art which is not considered
to be of particular relevance
*E" earlier document published on or after the international filing date
"L" document which may throw doubts on priority claim(s) or which is
cited to establish the publication date of another citation or other special reason (as specified)
"O* document referring to an oral disclosure, use, exhibition or other
means later document published after the international filing date or priority date and not in conflict with the application but cited to understand the principle or theory underlying the invention
document of particular relevance; the claimed invention cannot be considered novel or cannot be considered to involve an inventive step when the document is taken alone

Form PCT/ISA/210 (second sheetXJuly 1992)*

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mybb@mybb.ru (maxifa) — Sun, 18 Sep 2011 14:30:59 +0400

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�����: hydrogenation lactic acid

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