US005985786A

United States Patent [19]

[11]

Patent Number:

Diercks et al.

[45]

Date of Patent:

[54]

PACKED SILVER-CATALYST BED DOPED

5,854,163

5,985,786
Nov. 16, 1999

12/1998 Diercks et al. ......................... .. 502/56

WITH PHOSPHORUS
FOREIGN PATENT DOCUMENTS

[75]

Inventors: Rainer Diercks, Neuhofen; Bernhard

Knuth, LudWigshafen; Albrecht

Aicher, Frankenthal, all of Germany

[73] Assignee: BASF Aktiengesellschaft,

LudWigshafen, Germany

104666
0 467 169

4/1984
1/1992

European Pat. Off. .

European Pat. Off. .

WO 96/28249

9/1996

WIPO .

[21] Appl. No.:

09/117,538

Primary ExaminerMark L. Bell

Assistant ExaminerPatricia L. Hailey

[22]

PCT Filed:

Feb. 10, 1997

Attorney, Agent, or FirmOblon, Spivak, McClelland,

[86]

PCT No.:

PCT/EP97/00601

371 Date:

Aug. 5, 1998

102(e) Date: Aug. 5, 1998

[87]

Maier & Neustadt, PC.

[57]

ABSTRACT

A phosphorus-doped silver catalyst ?xed bed is obtainable

by

PCT Pub. No.: WO97/30014

I. arranging silver crystals obtained by electrolytic depo

PCT Pub. Date: Aug. 21, 1997

form a starting silver catalyst ?xed bed,

II. producing an activated silver catalyst ?xed bed from

sition of silver from an aqueous silver salt solution to

[30]

Foreign Application Priority Data

Feb. 13, 1996

[51]

[DE]

Germany ......................... .. 196 05 212

the starting silver catalyst ?xed bed by passing through

the latter, at from 150 to 800 C., a gas mixture

Int. Cl.6 ........................... .. B01] 27/14; B01] 20/34;

comprising methanol and oxygen (gas mixture M), and

B01] 23/02; B01] 23/48

III. bringing the activated silver catalyst ?xed bed into

contact With from 1 to 20,000 ppm by Weight of
phosphorus, based on the silver, in the form of a ?nely

[52]

U.S. Cl. ............................ .. 502/208; 502/34; 502/38;

[58]

Field of Search ................................... .. 502/208, 344,

divided phosphorus compound having a melting point

502/347, 353, 34, 56, 38

or decomposition temperature of more than 500 C.

502/56; 502/344; 502/347; 502/353

[56]

(phosphorus compound P).

References Cited
U.S. PATENT DOCUMENTS
4,235,823

11/1980 Dudeck et al. ....................... .. 568/402

9 Claims, No Drawings

5,985,786
1

PACKED SILVER-CATALYST BED DOPED

WITH PHOSPHORUS

and, When the catalyst has reached the required temperature,

adding the gaseous reactants to the gas stream. Once the

reaction has started and the catalyst has reached its full
activity the heating of the catalyst ?xed bed is no longer

The present invention relates to a phosphorus

doped silver catalyst ?xed bed obtainable by

I. arranging silver crystals obtained by electrolytic depo

necessary since the oxidation of the methanol to formalde

hyde is exothermic and the reaction Zone, ie. the catalyst

sition of silver from an aqueous silver salt solution to

?xed bed, heats up to from 500 to 700 C. and thus has the

form a starting silver catalyst ?xed bed,

II. producing an activated silver catalyst ?xed bed from

minimum temperature required for the activation of the

reaction. Since the catalyst ?xed bed does not yet have its

the starting silver catalyst ?xed bed by passing through

10

the latter, at from 150 to 800 C., a gas mixture

comprising methanol and oxygen (gas mixture M), and

full activity immediately after the reaction starts, only small

amounts of the reactants may be passed through the catalyst

divided phosphorus compound having a melting point

?xed bed at the beginning, since otherWise the reaction

proceeds With little selectivity or there is even the danger of
the catalyst ?xed bed assuming a modi?cation in Which it is
inactive. Only after about 30 hours has the catalyst ?xed bed
reached its full activity and the maximum amount of reac

or decomposition temperature of more than 500 C.

tants per unit time can be passed over it.

(phosphorus compound P).

Since during the activation phase, Which is necessary to

produce a catalyst ?xed bed in a modi?ation of high activity
from that described in EP-A-0 467 169, the space-time yield
is relatively loW, there is a need for catalyst ?xed beds Which
require a shorter activation phase to reach their ?nal high
activity modi?cation. In addition, the activation energy
necessary for the reaction over the freshly produced catalyst
?xed bed (ie. the minimum temperature Which the catalyst

III. bringing the activated silver catalyst ?xed bed into

contact With from 1 to 20,000 ppm by Weight of
phosphorus, based on the silver, in the form of a ?nely

The invention further relates to a process for producing

this and also a process for preparing formaldehyde using a

15

20

phosphorus-doped silver catalyst ?xed bed according to the

present invention.
Silver catalysts Which are suitable for the oxidation of

methanol to give formaldehyde are generally knoWn (cf.

Ullmanns EnZyklopadie der technischen Chemie, 3rd

25

?xed bed must have for the reaction to start) should be as

loW as possible.
It is an object of the present invention to provide a catalyst

edition, Urban und SchWarZenberg, Munich-Berlin, 1956,

Volume 7, pp. 660 to 663). According to this process, silver
is oxidiZed anodically in an electrolysis cell to form silver
ions and these are again cathodically reduced to give silver.
The coarsely crystalline silver formed at the cathode is
suitable as catalyst for the synthesis of formaldehyde from
methanol.

?xed bed Which is simple to produce, makes possible the

30

of methanol in high yield and With a high conversion and

does not have the de?ciencies described. In particular, the
activation step Which is generally carried out in the produc
tion plant for preparing formaldehyde should be as short as

Advantageous effects Which occur When using phospho

rus compounds as promoters for the oxidation of methanol
to formaldehyde in the presence of a silver catalyst are also
knoWn from CN-A-85 100 530, EP-A-0 467 169 and JP-A

preparation of formaldehyde by oxidative dehydrogenation

35

possible. Furthermore, the economical production of form

aldehyde should be possible even during this time, so that

38227/83.

the production stoppage necessitated by the replacement of

EP-A-0 467 169 describes the production of a catalyst

?xed bed built up of layers of silver crystals containing a
pulverulent phosphorus-containing salt as promoter. In this
process, the phosphorus-containing salt is applied to the

the catalyst ?xed bed is as short as possible.

40

We have found that this object is achieved by the

phosphorus-doped silver catalyst ?xed bed described in the
introduction.

The preparation of the silver crystals described in step I is

silver catalyst before the silver catalyst is brought into

generally knoWn (cf. Ullmanns EnZyklopadie der technis

contact With a hot gas mixture comprising oxygen and

methanol.
ence are in a modi?cation of loW activity immediately after

chen Chemie, 3rd edition, Urban und SchWarZenberg,

Munich-Berlin, 1956, Vol.7, pp. 660 to 663). Particularly
good results are achieved using the starting catalyst ?xed

application of the phosphorus-containing salt and transform

beds described in DE-A-23 22 757.

only relatively sloWly into a modi?cation of high activity by

Suitable silver crystals are obtained, in particular, When

the electrolysis is carried out according to the process
described in the German patent 11 66 171.
The electrolyte used is preferably an aqueous silver nitrate
solution. This silver nitrate solution generally has a pH of
from 1 to 4 and contains from 1 to 5% by Weight of silver.

HoWever, the catalyst ?xed beds described in that refer

45

means of Which formaldehyde can be prepared in high yield

and at a high conversion. This is associated With the fol

50

loWing problems:
A catalyst ?xed bed described in EP-A-0 467 169, Which
is used for the industrial production of formaldehyde in a

generally customary, continuously operated plant, loses

activity With time so that the yield drops. Therefore, to be
able to operate the plant economically the used catalyst ?xed

The pH is advantageously set using nitric acid.

55

bed has to be replaced by a fresh one after a certain operating

time, for Which purpose the synthesis process has to be

interrupted. In order to subsequently restart the synthesis
process, it is necessary to preheat the catalyst ?xed bed to at

60

least 360 C. so as to make available the activation energy

required for the reaction. HoWever, oWing to the fact that the
heat is rapidly given off because of the high surface area of
the catalyst it is technically not simple to achieve such high
temperatures. In practice, the catalyst ?xed bed is heated, for

example, by passing a hot inert gas stream (for example

nitrogen or carbon dioxide) through the catalyst ?xed bed

65

Electrodes employed are those customarily used in the

electrolysis of silver. Suitable anodes are sacks Which have
been charged With the silver to be oxidiZed, generally as
granules or as poWders. Suitable cathodes are, in particular,
sheets of silver.
The electrolysis is advantageously carried out at current
densities of from 80 to 500 A/m2 of cathode area and
electrolyte temperatures of from 10 to 30 C.
To achieve these current densities, voltages of from 1 to
15 volt are required in most electrolysis cells.
It is advisable to continually remove silver crystals

formed from the cathode. In general, silver crystals having

a particle siZe of from 0.2 to 5 mm are obtained.

5,985,786
4

Suitable phosphorus compounds (P) are phosphorus

Aone-off electrolysis is usually suf?cient to obtain usable

silver crystals.

containing salts. Examples of these are the phosphorus

containing salts mentioned in DE-A-4 022 603, eg. inor
ganic phosphates of alkali metals, alkaline earth metals and

Such ?xed beds, Which are also referred to as short

beds, are generally known and described, for example in

Ullmanns Encyklopadie der technischen Chemie, 4th

heavy metals such as Ag, Zn and Fe or of boron and

ammonium.

Edition, Verlag Chemie, Weinheim-NeW York, Volume 13,

pp. 539 to 541.

Preference is given to phosphates or pyrophosphates of

alkali metals or alkaline earth metals, eg. Na4P2O7, Li3PO4,

In general, the silver crystals are arranged to form a

starting silver catalyst ?xed bed comprising from 1 to 9

layers of silver crystals and having a total bed thickness of
from 1 to 10 cm. Such silver catalyst ?xed beds are knoWn,

Mg3(PO4)2> Ca3(PO4)2~
10

for example, from DE-C-23 22 757, Which are hereby fully

silver catalyst ?xed bed or to impregnate it With a solution

incorporated by reference.

of the phosphorus compound (P) and alloW the solvent to

In step II, the starting silver catalyst ?xed bed is activated

by passing through it, preferably continuously, at from 100

to 800 C., preferably from 200 to 700 C., a gas mixture

In general, the procedure is to sprinkle a ?nely divided

poWder of the phosphorus compound (P) onto the activated

15

evaporate.
The particle siZe of the phosphorus compound (P) used as

(M) comprising methanol and oxygen. The gas mixture

generally contains from 0.25 to 0.60 mol, preferably from

poWder is not critical, it is generally from about 1 mm to 1

pm.

0.35 to 0.50 mol, of oxygen per mol of methanol and from

0.2 to 3.0 mol, preferably from 0.67 to 1.75 mol, of Water per
mol of methanol and from 0.9 to 2.3 mol, preferably from
1.3 to 1.8 mol, of nitrogen per mol of methanol. To achieve

The solutions of the phosphorus compounds (P) are

generally aqueous solutions containing from 0.01 to 50% by

the temperature de?ned according to the present invention it

is advantageous to preheat the gas mixture to these tem
peratures at the commencement of the passing-through of
the gas mixture. In general, the preheating of the gas mixture
(M) becomes super?uous after a certain time, since the ?xed
bed is heated to the required temperature by the heat of
reaction Which is liberated.
The activation of the starting catalyst ?xed bed is advan
tageously carried out in a ?xed-bed reactor as is customarily

20

Weight of the phosphorus compound

To impregnate the

activated silver catalyst ?xed bed, it is soaked With one of

25

these solutions or, particularly advantageously, the solutions

are sprayed onto the activated silver catalyst ?xed bed, and
the solvent is subsequently evaporated.
The amount of phosphorus compound (P) sprayed on or
sprinkled on is preferably selected such that the amount of
phosphorus is from 0.01 to 100 mg, preferably from 0.05 to
10 mg, per cm2 of cross-sectional area of the phosphorus

doped silver catalyst ?xed bed.

30

used for the preparation of formaldehyde by oxidative

dehydrogenation of methanol and the gas mixture (M) is

It is advantageous not to interrupt the passing-through of

the gas stream (M) While applying the phosphorus com
pound (P) to the activated silver catalyst ?xed bed.

passed continuously through this reactor. Preferably, the

This procedure has the advantage that, if the production of

reactor is upright and the gas mixture (M) is passed through

the phosphorus-doped silver catalyst ?xed bed is carried out

the reactor from the top doWnWards. Such reactors and

35

DE-A-24 44 586 and EP-A-0 150 436, Which are here

incorporated in full by reference.

invention can immediately folloW the production of the

Advantageously, the cross-sectional area of the reactor

and that of the starting silver catalyst ?xed bed are selected

in a ?xed-bed reactor Which is also suitable for the oxidative

dehydrogenation of methanol to give formaldehyde, the

preparation of formaldehyde from the gas mixture (M) using
the phosphorus-doped silver catalyst ?xed bed of the present

processes are described, for example, in EP-A-467 169,

40

latter. The gas mixture (M) used for activating the starting

so as to be the same and the ?xed bed is arranged in the

reactor so that the layers of the silver crystals are perpen
dicular to the How direction of the gas mixture

silver catalyst ?xed bed usually has the same composition as

that used for preparing formaldehyde from the gas mixture

To produce the activated silver catalyst ?xed bed, it is

generally suf?cient to pass from 0.0001 to 0.5 kg, preferably

this Way, it is possible to particularly ef?ciently combine the

(M) using the phosphorus-doped silver catalyst ?xed bed. In

45

from 0.01 to 0.5 kg, of methanol in the form of the gas

mixture (M) per cm2 of cross-sectional area of the starting
silver catalyst ?xed bed at from 100 to 500 C., preferably

from 200 to 700 C., through the starting silver catalyst ?xed
bed. The indicated amounts of the gas mixture (M) are

advantageously passed through at a velocity Which is gen

erally selected such that the gas mixture (M) is passed
through in from 0.01 to 500 hours, preferably from 0.1 to
100 hours, particularly preferably from 1 to 500 hours.
Even during the activation phase, the methanol present in
the gas mixture (M) is converted virtually quantitatively into

50

production of the phosphorus-doped silver catalyst ?xed

bed, during Which formaldehyde can also be produced, With
the production of formaldehye using the catalyst ?xed bed of
the present invention.
It is also possible to produce a phosphorus-doped silver
catalyst ?xed bed having maximum activity in an iterative
process by, in step III, ?rst applying only part of the
phosphorus, advantageously from 0.01 to 2 mg, preferably
from 0.05 to 1 mg, per cm2 of the cross-sectional area of the

activated silver catalyst ?xed bed, to the latter in the form of

55

the phosphorus compound (P) and increasing the amount of

phosphorus compound (P) stepWise, for example in steps of

formaldehyde. This means that step II can also be utiliZed for

from 1 to 100%, based on the amount initially applied, and

the production of formaldehyde, even if the space-time yield

simultaneously monitoring the yield of formaldehyde. The

amount of phosphorus compound (P) applied is increased

is not yet quite as high as in the case of the phosphorus

doped silver catalyst ?xed bed of the present invention.

In step III, the activated silver catalyst ?xed bed is
brought into contact With from 1 to 20,000 ppm by Weight,
preferably from 5 to 5000 ppm by Weight, of phosphorus,

60

application of the phosphorus compound

The phosphorus-doped silver catalyst ?xed beds, like
previously knoWn silver catalysts, continually lose activity
during use for preparing formaldehyde, Which is made

based on the silver, in the form of a ?nely divided phos

phorus compound having a melting point or decomposition

temperature of more than 500 C. (phosphorus compound

P).

stepWise until no increase in yield can be achieved by further

65

apparent by falling conversion and yields of formaldehyde.

This activity loss of the catalysts of the present invention
can be partly avoided if in addition, either continuously or

5,985,786
5

discontinuously (in each case 1 portion after introducing a

been heated to 340 C. During the activation period of 23

hours, the amount Was increased to 32 kg/h of methanol,

de?ned amount of gas mixture (M)), from 0.01 to 100 ppm

by Weight of phosphorus, based on the phosphorus-doped

21.4 kg/h of Water and 54 kg/h of air (?nal throughput). At
the end of the activation period, the temperature in the ?xed
silver catalyst ?xed bed, is applied to the latter in the form
of the phosphorus compound (P) per kg of methanol in the 5 bed was 7000 C. This How Was kept constant during the
entire duration of the experiment. Subsequently, 0.42 mg of
form of the gas mixture (M) Which is passed through the
phosphorus per cm2 of the cross-sectional area of the
phosphorus-doped silver catalyst ?xed bed per 1 cm2 of the
cross-sectional area of the latter, Without interrupting the
introduction of the gas mixture

In the case of continu

ous application, the activity loss can be sloWed doWn, in the

case of the stepWise discontinuous application it can be

10

mixture Was continued.

partly reversed.
This further application of the phosphorus compound (P)

The reactor continued to be operated continuously and

after a certain operating time of the reactor further amounts

can be carried out in the same Way as described in step II for

the production of the phosphorus-doped silver catalyst ?xed

of phosphorus Were applied to the phosphorus-doped silver

15

bed.

catalyst ?xed bed. The respective amounts (the cumulative

amounts are indicated in the table), the yields of formalde
hyde achieved and the time at Which further phosphorus Was
applied, calculated from the time at Which the phosphorus

If the further application of the phosphorus compound (P)

is carried out discontinuously, the intervals betWeen the

further applications of the phosphorus compound (P) to the

phosphorus-doped silver catalyst ?xed bed are usually

activated silver catalyst ?xed bed Was sprayed onto the

surface of the latter in the form of a 3% strength by Weight
aqueous solution of Na4P2O7, While the feeding in of the gas

doped silver catalyst ?xed bed Was produced by applying

20

selected such that during this time not more than 500 kg,
preferably from 1 to 5 kg, of methanol in the form of the gas

phosphorus for the ?rst time to the activated silver catalyst

?xed bed, are shoWn in the table.

mixture (M) are passed through the phosphorus-doped silver

Example 2 (For Comparison)

catalyst ?xed bed per 1 cm2 of the cross-sectional area of the

latter, since otherWise the yield Would drop too much in

25

The starting silver catalyst ?xed bed Was produced as

betWeen.

described in Example 1. Phosphorus in the form of pulveru

The preparation process for formaldehyde by oxidative

dehydrogenation of methanol using the catalyst ?xed bed of

lent Na4P2O7 Was sprinkled onto its surface in an amount of

1.3 mg of phosphorus (calculated as elemental phosphorus)

the present invention is otherWise carried out in a manner

knoWn per se, by passing the gas mixture (M) at from about
500 to 750 C., in particular from 600 to 710 C., through
the phosphorus-doped silver catalyst ?xed bed. The process
is generally carried out continuously at a pressure of from
0.5 to 2 bar, preferably from 0.8 to 1.8 bar. It is advantageous

30

to alloW the reaction gases leaving the catalyst Zone to cool

for a short time, eg. to from 50 to 350 C. The cooled gas
mixture is then advantageously fed to an absorption toWer in

35

mixture indicated in Example 1 (same composition as in

Example 1). The ?nal throughput through the ?xed bed

could be achieved only after activation for 28 hours. The
yield as a function of the operating time, from the time at
Which activation Was complete (achievement of the ?nal

throughput), is shoWn in the table.

Example 3 (For Comparison)

Which the formaldehyde is scrubbed from the gas mixture by

means of Water. Speci?c, particularly advantageous variants

of the generally knoWn process for preparing formaldehyde,

per cm2 of cross-sectional area of the ?xed bed. The catalyst

?xed bed Was heated to 360 C. and activated using the gas

40

Which can also be employed in the process of the present

invention, are recommended in DE-A-24 44 586, DE-A-24
51 990, EP-A-0 083 427 and EP-A-0 150 436, Whose subject

The procedure described in Example 2 Was repeated, but

the temperature of the gas mixture introduced for activating
the catalyst Was only 340 C. The ?xed bed Was not able to
be activated in this Way.

matter is hereby incorporated by reference.

The use of the catalyst ?xed bed of the present invention 45

enables formaldehyde to be prepared particularly economi

cally by oxidative dehydrogenation of methanol.
In particular, the methanol- and oxygen-containing gas
mixture Which is passed through the ?xed bed at the com
mencement of the synthesis process to activate it only has to
be preheated to a comparatively loW temperature.

Operating

Amount of phosphorus

Yield

Example

days

[mg/cm2]

[%]

0
1
2
13
14

0.42
0.67
1.13
1.13
1.78

89.8
90.2
90.6
88.7
90.0

2(c)

1.30

90.3

1.30

90.1

50

Furthermore, the time required for the activaton is relatively

short, so that overall the space-time yield of the process for

preparing formaldehyde is higher.

We claim:

1. A phosphorus-doped silver catalyst ?xed bed obtained

EXAMPLE 1

by

A three-layer starting silver catalyst ?xed bed having a

diameter of 15 cm and a total bed thickness of 2 cm Was

I. arranging silver crystals obtained by electrolytic depo

installed in an upright experimental reactor having an inter

nal diameter of 15 cm. The loWer layer comprised 1000 g of 60
silver crystals having a particle siZe of from 1 to 2.5 mm, the

form a starting silver catalyst ?xed bed,

II. producing an activated silver catalyst ?xed bed from

sition of silver from an aqueous silver salt solution to

middle layer comprised 65 g of silver crystals having a

the starting silver catalyst ?xed bed by passing through

particle siZe of from 0.75 to 1 mm and the upper layer

the latter, at from 150 to 800 C., a gas mixture

comprising methanol and oxygen (gas mixture M), and

comprised 185 g of silver crystals having a particle siZe of

from 0.2 to 0.75 mm.

A gas mixture comprising methanol, Water and air Was

passed through a starting silver catalyst ?xed bed Which had

65

III. bringing the activated silver catalyst ?xed bed into

contact With from 1 to 20,000 ppm by Weight of
phosphorus, based on the silver, in the form of a ?nely

5,985,786
8

7
divided phosphorus compound having a melting point

gas mixture (M) at from 150 to 800 C. through a

phosphorus-doped silver catalyst ?xed bed as claimed in
claim 1.
8. Aprocess as claimed in claim 7, Wherein from 0.01 to

or decomposition temperature of more than 500 C.

(phosphorus compound P).

2. A phosphorus-doped silver catalyst ?xed bed as

claimed in claim 1, Wherein the starting silver catalyst ?xed

100 ppm by Weight of phosphorus compound (P), based on

the phosphorus-doped silver catalyst ?xed bed, is applied to

bed comprises one or more layers of silver crystals Whose

longest mean diameter is from 0.2 to 10 mm, and the total

the latter per kg of methanol Which is passed in the form of

bed thickness is from 1 to 10 cm.

the gas mixture (M) through the phosphorus-doped silver

3. A phosphorus-doped silver catalyst ?xed bed as

claimed in claim 1, obtained by, in step III, sprinkling the

phosphorus compound (P) in the form of a poWder onto the
activated silver catalyst ?xed bed.

catalyst ?xed bed per cm2 of the cross-sectional area of the

10

mixture
9. A process for producing a phosphorus-doped silver

4. A phosphorus-doped silver catalyst ?xed bed as

catalyst ?xed bed, Which comprises

I. arranging silver crystals obtained by electrolytic depo

claimed in claim 1, obtained by, in step III, impregnating the

activated silver catalyst ?xed bed With a solution of a

sition of silver from an aqueous silver salt solution to

phosphorus compound and evaporating the solution.

form a starting silver catalyst ?xed bed,

II. producing an activated silver catalyst ?xed bed from

5. A phosphorus-doped silver catalyst ?xed bed as

claimed in claim 1, obtained by, for the activation of the

starting silver catalyst ?xed bed, arranging the latter in a

?xed-bed reactor and continuously passing the gas mixture

the starting silver catalyst ?xed bed by passing through

20

the latter, at from 150 to 800 C., a gas mixture

comprising methanol and oxygen (gas mixture M), and

(M) through the reactor.

6. A phosphorus-doped silver catalyst ?xed bed as
claimed in claim 1, obtained by, for the production of the
activated silver catalyst ?xed bed, passing from 0.01 to 50
kg of methanol in the form of the gas mixture (M) per cm2
of cross-sectional area of the starting silver catalyst ?xed
bed through the latter.

latter, Without interrupting the passing-through of the gas

III. bringing the activated silver catalyst ?xed bed into

contact With from 1 to 20,000 ppm by Weight of
phosphorus, based on the silver, in the form of a ?nely
25

divided phosphorus compound having a melting point

or decomposition temperature of more than 500 C.

(phosphorus compound P).

7. A process for preparing formaldehyde by oxidative

dehydrogenation of methanol, Which comprises passing the