DE1201819B - Process for the activation of lithium phosphate catalysts for the isomerization of alkylene oxides in the vapor phase to the corresponding alkenols - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

BOIj

German class: 12 g -4 / 64- //// ic;

Number: 1 201 819

File number: O 7418 IV a / 12 g

Filing date: May 18, 1960

Opening day: September 30, 1965

Highly effective catalysts for this type of conversion contain leached basic lithium phosphate (German patent specification 1 099 524).

The inventive method for activating lithium phosphate catalysts for isomerization from alkylene oxides in the vapor phase to the corresponding alkenols is characterized by that the catalyst at 25 to 300 ° C, but at least 25 ° C below the critical Temperature of the solvent, with water and / or alkylene oxide, ethers, ketones, carboxylic acids, alcohols, Aldehydes or esters in a ratio of 1 to 30 parts by volume of liquid per part by volume of catalyst treated.

When using the activation process according to the invention, the catalysts can be used many times can be reused, yet they still have their high initial activity and selectivity and even be improved a little after regeneration.

So far one has for the isomerization of alkylene oxides in the vapor phase to the corresponding Alkenols used catalysts, which have inadequate degrees of conversion and inadequate production capacities revealed. It is known from US Pat. No. 2,426,624 that the one described there Trilithium phosphate catalyst for each pass only has a conversion level of about 17 to 21% propylene oxide to allyl alcohol in production processes for activating lithium phosphate catalysts for the isomerization of alkylene oxides in the vapor phase to the corresponding Alkenols

Applicant:

Olin Mathieson Chemical Corporation, New York, N.Y. (V. St. A.)

Representative:

Dr. W. Kühl, patent attorney,

Hamburg 36, Esplanade 36 a

Named as inventor:

William I. Denton, Cheshire, Conn. (V. St. A.)

Claimed priority:

V. St. ν. America 8 June 1959 (818 516, 818 557)

Activity of 61 (61% of the propylene oxide passed over the catalyst was converted to AlIyI-

speeds of 60 to 179 g of allyl alcohol per 30 alcohol converted) and an initial selectivity liter Catalyst per hour results. did of 85 (85% of the

With the catalysts activated according to the invention, on the other hand, degrees of conversion of alkylene oxide are achieved Propylene oxide passed to alkenol per pass of 60 to about 85% of the satorbett became allyl alcohol implemented) goes after the treatment according to the USA patent in its activity on one

and final yields of 83 to 95% with a production value of 43 and its selectivity to a rate of 250 to about 550 g alkenol value of 80, and after repeated treatment per liter of the activated catalyst per hour. Catalysts whose activity has decreased during operation
can be re-opened by the activation process according to the invention
bring straight.

Try to heat the catalyst in air,
To activate mixtures of air with oxygen or water vapor or mixtures of oxygen with water vapor, as is sampled in U.S. Pat. No. 45, it is sometimes advantageous to use an aqueous 2,426,624 for low-activity catalysts solution which is a polar organic is described, are contained when applied to catalysis solvents.

gates of initially high effectiveness unsuccessful After treating the catalyst with the

remained. The activity of such catalysts is water, the organic solvent or the not increased by this treatment, but in 50 aqueous solution of the same at temperatures before the opposite decreased. A leached basic one, preferably in the range from 100 to 200 ° C., results Lithium phosphate catalyst from an initial one to a substantial improvement in the catalyst.

509 689/404

According to the USA patent, the activity is only 29 and the selectivity is 62.

It has also been found that the inventive Effectiveness according to the activation process also the effectiveness

increased by batches of freshly prepared catalyst, which do not have the desired high effectiveness from the outset.
Although pure water in a liquid state is effective

The best working temperature for the respective activation liquid depends on a certain amount Degrees on the amount used and the degree of loss of activity of the catalyst.

The quantitative ratio of activating liquid to the catalyst to be treated depends largely according to the degree of contamination of the catalytic converter. Generally one uses 1 to 15 parts by volume of liquid, preferably 2 to 10 parts by volume of liquid per part by volume of catalyst. Occasionally, however, higher volume ratios can also be advantageous, e.g. B. when a catalyst is heavily soiled by being used for a period of 100 hours or more; in In this case, it may be appropriate to use 30 parts by volume of the aqueous liquid per part by volume of catalyst to work.

The treatment is generally carried out so that fresh liquid is generally 2 to 10 hours is pumped through the catalyst for a long time. The volume ratio can be less than 5 parts of space Liquid per volume of catalyst can be reduced if the catalyst is no longer in the process has been used for 48 hours or when cycling the fluid. Lower volume ratios are also used when the regeneration is carried out using a conventional extraction process he follows.

The regeneration is most advantageously carried out without the catalyst bed from the isomerizer to remove.

The organic solvent used is preferably one which has no more than 6 carbon atoms contains per molecule.

In the following Examples 1 to 21, catalysts are examined for their effectiveness by propylene oxide through the catalyst bed at a temperature of 275 ° C and atmospheric pressure as well as a throughput rate of 0.5 passes and the product to its content Allyl alcohol, recovered propylene oxide and other carbonyl compounds analyzed. The activating Treatment with the organic solvent is carried out with catalyst batches of 120 g each performed after this under the conditions given above, unless otherwise specified is, 24 to 48 hours have been used for the isomerization process and catalytic Have lost their effectiveness.

50

example

catalyst

Freshly made, leached alkaline
Lithium phosphate

As Example 1,

after 30 hours longer
use

Like example 2,

after 2 hours of treatment at 10 ccm / min.
liquid acetone
170 ⁰ C and 20.4 atm

yield
of allyl alcohol

ever

Passage

58.1

48.1

65.2

End of the booty

82

87

86

60

65

at
game catalyst the end
to Ally
ever
By
corridor today
!alcohol
End
the end
prey 4th As Example 3,
after 50 hours longer
use 37.1 82 5 As Example 4,
after 60 hours of operation
treatment with air
290 ° C and 3 hours long
ger treatment with air
at 315 ° C 34.7 59 6th Freshly made, from
alkaline leached
Lithium phosphate 57.9 80 7th As Example 6,
after 69 hours longer
use 23.0 79 8th Like example 7,
after 5.5 hours longer
Treatment with
10 cc / min. liquid
Propylene oxide at 127 ^° C
and 20.4 atm 61.0 88 9 As Example 8,
after 44 hours longer
use 44.0 87 10 As Example 9,
after 2 hours of operation
action at 10 ccm / min.
liquid dioxane at 170 ° C
and 20.4 atm 57.4 86 11 Like example 10,
after 40 hours longer
use 50.0 88 12th As Example 11,
after 4 hours of operation
action at 10 ccm / min.
liquid ethyl acetate
150 ° C and 20.4 atm 55.6 89 13th Freshly made, from
alkaline leached
Lithium phosphate 60.3 87 14th Like example 13,
48 hours longer
use 44.8 89 15th As Example 14,
after 4 hours of operation
action at 6 ccm / min.
liquid ethyl alcohol, the
5 weight percent water
contains, at 150 ° C and
"20.4 atm 54 6 85 16 As Example 15,
after 43 hours longer
use 44.4 83

at
game catalyst Working out
Allylal
ever
By
corridor itean
alcohol
End
the end
prey 17th Like example 16,
after 3.33 hours longer
Treatment with 6 ecm /
Min. Liquid acetone,
which is 30 percent by weight
Contains water at 125 ° C
and 20.4 atm 59.1 89 18th As Example 17,
after 42 hours longer
use 46.9 87 19th As Example 18,
after 3.5 hours longer
Treatment with 3.5 ecm /
Min. Liquid butyl acetate
at 150 ° C and 20.4 atm. 64.1 86 20th As Example 19,
after 44 hours longer
use 39.1 84 21 Like example 20,
after 3 hours of operation
action at 6 ccm / min.
liquid acetone
150 ° C and 20.4 atmospheres .... 62.6 86

The following results of Examples 22 to 29 are obtained by activating for 2 hours 120 ecm catalyst at a flow rate of 2 ccm / min. at different temperatures and the specified pressures. The values for the activity and the selectivity before and after the activating treatment are indicated separately.

example

temperature
⁰ C

pressure
atü

Activity before I after ι

Selectivity before after

Solvent: liquid acetone

170 20.4 46 62 82 170 20.4 56 65 80 100 20.4 55 64 84 50 20.4 53 57 85 25th 0 26th 57 64

Solvent: 20.4 Liquid propylene oxide 61 79 27 125 20.4 23 52 87 28 75 3.4 42 59 77 29 25th 30th

85 83 85 84 82

88 82

Example 30

In this example, a leached basic lithium phosphate catalyst is used, which is used in the Isomerization of propylene oxide to allyl alcohol initially has an activity of 62.3 (62.3 "/ 0IgCr conversion of propylene oxide to allyl alcohol per pass through the catalyst bed) and a selectivity of 85 (85% final yield of allyl alcohol).

The catalyst is then used in five consecutive trials lasting 24 to 48 hours used for isomerization and after each experiment liquid by treatment with 10 parts by volume Acetone regenerates at 125 to 200 ° C to essentially restore its initial effectiveness.

Then the catalyst remains in the isomerization process for 350 hours without regeneration used, its effectiveness on an activity value of 5 and a selectivity value of 45 ίο decreases.

Treatment with liquid acetone as described above increases the effectiveness to only one Activity value of 20 and a selectivity value of 72. On a second regenerative treatment with acetone these values increase only slightly, namely the activity to 27 and the selectivity on 75.

The catalyst is then treated for 2 hours with liquid water at 170 ° C. and 20.4 atm and a flow rate treated by 10 ecm of water per minute through the catalyst bed.

The activity of the catalyst increases to 60 and the selectivity to 85.

Example 31

A leached basic lithium phosphate catalyst that has an initial activity of 60 and has an initial selectivity of 83, becomes 100 hours for isomerization of impure Propylene oxide used to allyl alcohol, the propylene oxide containing a catalyst poison. Through this the effectiveness of the catalyst is greatly reduced, namely to an activity of 17 and one Selectivity of 59.

By treatment with liquid propylene oxide at a flow rate of 4 ccm / min. for a period of 2 hours at 125 ° C. and 20.4 atmospheres, the activity only rises to 36.6 and the selectivity on 75.

Then the catalyst is 2 hours with a mixture of equal parts by weight of water and Propylene oxide at 150 ° C. and 20.4 atmospheres with a flow rate of 6 ccm / min. treated. The catalyst now has an activity of 65.2 and a selectivity of 86.

Example 32

A catalyst which, according to Example 1, deactivates to an activity of 45 and a selectivity of 82 has been, is treated at 100 ° C and 13.6 atmospheres with an aqueous liquid that consists of 60 percent by weight ethyl alcohol and 40 percent by weight water. The liquid is left for 2.5 hours. through the catalyst bed at a rate of 5 cc / min. directed. The catalyst has on it an activity of 63.5 and a selectivity of 84.

Example 33

A catalyst which, according to Example 2, deactivates to an activity of 48 and a selectivity of 84 has been, is at 125 ° C and 20.4 atü with a solution of 50 percent by weight acetone in Treated water. The liquid is 2 hours at a flow rate of 4 ccm / min. passed through the catalyst. This is what the

55

Catalyst an activity of 65.8 and a selectivity of 85.

Example 34

A leached basic lithium phosphate catalyst, which initially has an activity of 71.5 and a selectivity of 89, becomes 19 hours long used in the isomerization process. The activity then fell to 65.4, while the selectivity has remained unchanged.

The catalyst is now ^{treated at 150 °} C. and 20.4 atmospheres with a solution of 50 percent by weight acetone in water. The aqueous liquid is 105 minutes at a flow rate of 8 ccm / min. passed through the catalyst, whereupon the catalyst has assumed an activity of 75.4 and a selectivity of 88.

The aqueous activating liquid can contain two or more such solvents. So can the aqueous liquid z. B. ethyl alcohol, methyl alcohol or acetone in combination with propylene oxide or propionaldehyde or contain the latter two compounds together.

Is water used as the activating liquid or does the activating liquid have a high Water content, a small amount of the catalyst dissolves in it at the high activation temperatures.

The best results are generally obtained when the aqueous liquid is electrolyte-free, so z. B. contains distilled or ion-exchanged water. By this precaution will reduce the deterioration of the catalyst due to the presence of additional Anions or cations prevented. The organic solvents are practically electrolyte-free Easily obtainable in the state or, if necessary, they can be purified by distillation.

Claims (4)

Patent claims: 1. A method for activating lithium phosphate catalysts for the isomerization of alkylene oxides in the vapor phase to the corresponding alkenols, characterized in that the catalyst at 25 to 300 ⁰ C but at least 25 ° C below the critical temperature of the solvent, with water and / or alkylene oxides, ethers, ketones, carboxylic acids, alcohols, aldehydes or esters in a ratio of 1 to 30 parts by volume of liquid per part by volume of catalyst. 2. The method according to claim 1, characterized in that the catalyst is ^{treated at a temperature between about 100 and 200 0} C with an activating liquid which contains at least 30 percent by weight of water, which is practically free of added electrolytes, and the rest of the liquid organic solvent. 3. The method according to claim 1 or 2, characterized in that there is used as the activating liquid one used which consists of two of the organic solvents mentioned. 4. The method according to claim 1 or 2, characterized in that one is used as the activating liquid one used consisting of practically equal parts by weight of water and one of the organic solvents mentioned. Considered publications:
German interpretative document No. 1 099 524. 509 689/404 9.65 © Bundesdruckerei Berlin