AU635757B2 - Moulded parts made of macro-porous ion exchanging resins as well as use of the moulded parts - Google Patents

Abstract

Shaped bodies of macroporous, strongly acidic or basic ion exchanger resin in the form of packing such as Raschig rings, Berl saddles, torus saddles, packing rings with a web or cross bar, Pall rings, other hollow bodies, hollow spheres and the like having a hollow space fraction of 5 to 95 % by volume of the macroform without pores, a BET surface area from 0.01 to 1,000 and preferably 20 to 600 m<2>/g and an exchange capacity from 0.05 to 10 and preferably 3 to 6 meq/g, are used as a catalytically active packing for chemical reactions, especially etherification, hydration, dimerisation, oligomerisation, esterification, hydrogenation or alkylation, or combinations thereof. By means of simultaneously applied separation operations such as adsorption, absorption, extraction, stripping, distillation, rectification, fractionation, membrane processes or the like, a combination of a chemical reaction with a simultaneous separation of the components of the reaction mixture in one apparatus is achieved. In one of the examples, methanol and isobutene are reacted to give methyl tert.-butyl ether (MTBE), using Raschig rings of strongly acidic macroporous divinylbenzene/styrene copolymer.

Description

635757 COMMONWEALTH OF AUSTRALIA Patents Act 1952 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number Lodged Complete Specification Lodged Accepted Published Priority 13 September 1989 Related Art Name of Applicant 0 Address of Applicant S VEBA OEL AKTIENGESELLSCHAFT Alexander-von-Humboldt- Strasse, Gelsenkirchen Hassel WEST GERMANY Klaus Gottlieb, Wilfried Graf, Kuno Schadlich,,.Ulrich Hoffmann, Alwin Rehfinger Jorg Flato F.B. RICE CO., Patent Attorneys 28A Montague Street BALMAIN NSW 2041 Actual Inventor(s) Address for Service Complete Specification for the invention entitled: "MOULDED PARTS MADE OF MACRO-POROUS ION EXCHANGING RESINS AS WELL AS USE OF THE MOULDED PARTS" The following statement is a full description of this invention including the best method of performing it known to us/me:- In The invention concerns formed bodies made of macroporous ion exchange resin as well as the utilisation of such formed bodies.

Macro-porous ion exchange resins are well known as packing materials, for example for chromatographic columns. Thus, the separation of sugars by means of liquid chromatography over a column packed with porous sulfonic acid divinyl-styrol-copolymerate is described in the publication EP 0 104 912 A. The packing material is available in particle sizes of 1 to 30 Om.

In the thesis of A. Rehfinger, Technical University of Clausthal, 1988 the etherification of isobutylene and methanol to form tertiary butyl ether (MBTE) on macroporous strongly acid ion exchange resin as catalyst, has been subjected to a detailed investigation regarding Sreaction technique. The catalyst used was available in particle sizes of 0.3 to 1.2 mm.

In the document J 58 133 821-A a platinised hydrophobic catalyst with *o a styrol-divinyl-copolymerate or similar as carrier has been used o~ in the form little spheres, pellets, woven or knitted cloths, Raschig 0 -2rings or similar, in a process for the exchange of the hydrogen isotope deuterium against hydrogen in an equilibrium reaction between gaseous hydrogen and water vapour. The catalyst is incorporated in a stainless steel or plastic mesh which impedes the passage of liquid water.

In the final report by R.P. Arganbright, Dennis Hearn, Edward Jones, Lawrence Smith, DOE/CS/40 454-T3, September 1986 of the Chemical Research and Licensing Company and Neochem Corporation a new process is described for the production of MTBE by means of catalytic )O distillation which permits simultaneous catalysis and distillation in a reactor. Sulfonic acid divinyl benzyl-styrol-copolymerate in particle sizes of 0.1 to 0.5 mm was used as catalyst which is incorporated in pockets formed by by stitching of strips which have the shape of belts of a fibre glass material. After filling of the I, 15 pockets their openings are also stitched closed and the belts together with interspersed layers of a stainless steel wire mesh structure 0* with a mesh size of 12 in. are rolled up to form cylindrical bodies which are to be used in a fixed bed column.

These methods have, however, the disadvantage that the mass transfer deteriorates considerably because of the coating of the actual ion exchanger.

The task of the present invention is now to achieve the combination 25 of a chemical reaction with the simultaneous material separation of the reaction mixture in an apparatus whereby a catalytically active column packing installed in this apparatus accelerates the reaction making possible the intensive mass transfer necessary for the separation.

3 Accordingly, the present invention comprises formed bodies made of rmacroporous strongly acid or basic ion exchange resin in the shape of column packings such as Raschig rings, Berl saddles, Torus saddles, packing rings with bar or cross bar, Pall rings, other hollow bodies, hollow spheres and similar, with a percentage of voidage of 5 to 95% of the macro-form without pores, a BET-surface of 0.01 to 1,000, preferable 20 to 60 m2/g and an exchange capacity of 0.05 to 30, preferably 3 to 6 meq/g.

In a first embodiment, the formed bodies of the present invention may be used to catalytically active column packings for chemical reactions, especially ether formation, hydration, dimerisation, oligomerisation, .i esterification, hydrogenation or alkylation or 15 combinations of these.

In another embodiment, the formed bodies of the present invention may also be used for simultaneously carrying out a separating operation such as adsorption, absorption, extraction, stripping, distillation, rectification, fractionation, membrane processes or similar.

aciThe formed bodies consist of strongly acid, weakly acid or basic macroporous ion exchange resin or else of .gel type resins in the shape of separation body forms, 25 i.e. forms of filler bodies which in chemical technology serve the purpose of accelerating reactions by increasing surfaces between gases or vapours or else of liquids in counter or parallel current, for example Raschig rings, Berl saddles, Torus saddles, ring tower packing with bar or cross bar, Pall rings, other hollow bodies, hollow spheres or similar.

The formed bodies are produced and used, based on the macro form without pores, with a proportion of hollow space of 50 to 95% by volume, a BET-surface of 0.01 to 1,000, preferably 20 to 60 m 2 and an exchange 3a capacity of 0.05 to 10, preferably 3 to 6 meq/g. The Measurement of the BET-surface is carried out according to the single point difference method according to Haul-Duemgen (DIN 66132).

The formed bodies are produced most suitably by the application of polymerisation initiation, for example by the addition of an initiator which supplies radicals, and by copolymerisation from styrol and divinyl benzene in the weight ratio of 200:1 to 1:8, preferably of 20:1 to 5:1, possibly with the addition of 2 to 80, preferably 10 to by weight of pore forming agents to the total mixture.

0* 0* 0 0* 0 4 iiz 4' -4- An important group of formed bodies is produced from strongly acid macroporous ion exchange resin by means of generating or creating acid centres, especially by subsequent acid treatment, for example with sulfonic acid.

It is best for certain reactions to coat formed bodies of the type described above, with metals of the 7th or 8th subgroup of the periodic system, especially palladium, platinum, rutheniumor rhodium in amounts of 0.1 to 100 g/L of ion exchange resin.

A suitable external shaping of the formed bodies is the form of Raschig rings with internal diameters of 0.5 to 100 mm, wall thicknesses of 0.1 to 20 mm preferably 0.5 to 3 mm and a length, which corresponds to 0.1 to 20 times the internal diameter.

15 The invention consists, furthermore, in the utilisation of the above defined formed bodies as catalytically active column packings for chemical reactions or combinations of these, especially ether 0 formation, hydration, dimerisation, oligomerisation, esterification, hydrogenation or alkylation.

Especially preferred is the use of the formed bodies with simultaneously applied separation stages such as adsorption, absorption, extraction, stripping, distillation, rectification, fractionation, membrane processes or similar.

0 see 0 1.

•e

I

Through the production and utilisation of an ion exchange resin as formed body it has become possible to use the ion exchanger simultaneously as column packing for the purpose of creating a phase boundary and as catalyst in a packed tower reactor column. The S production of the new formed bodies, for examples with dimensions which correspond to those of a traditional 7 mm Raschig ring with a wall thickness of 1 mmn, for the first time does make possible the required voidage for counter current operation of gas and liquid phase of a bed of ion exchange material.

to Furthermore, the even material dimensions made possible by the formed bodies according to the invention, compared to former attempts to transform individual little spheres of the ion exchanger into larger units with corresponding voidage by the aggregation of individual $5 little spheres, is advantageous for a purposeful course of the reaction.

Suitable ion exchange resins are especially resins from divinyl-styrolcoplymerates, but also phenol formaldehyde resins, urea resins or condensation products of aromatic diamines with formaldehyde.

o The production of formed bodies can be carried out by means of bulk polymerisation of monomer mixtures in appropriate casting moulds, J. for example by ring cleavage polymerisation in teflon casting moulds.

e 25 Other devices are also suitable, for example extruders or injection moulding machines as well as other devices available to the expert for the shaping of polymerisation compositions which are undegoing curing.

o -6- Gel type resins are especially suitable as well for producing formed bodies and can be processed into the desired column packing forms in the suitable devices. Thus, it is also possible to transform incompletely cured resins which are still plastic into corresponding column packing shapes in order to guarantee, by the use of suitable conditions after shaping, a final curing for the purpose of obtaining the required strengths for use as column packings in process equipment.

By the addition of inert pore forming agents such as alkanes, for 1 0 example n-petadecane, in the weight ratio given it is possible to produce the desired macroporous structure which corresponds to the desired specifications.

*0 Further auxiliary materials such as polymerisation initiators such 15 as, for example, azo-isobutyric acid nitrile (AIBN) or others can also be used.

In the case of the strongly acid macroporous ion exchange resins produced from polystyrol cross bonded with divinyl benzene the SO 3

H

o groups anchored by sulfonation on the polymer matrix, as charge carriers are responsible for the exchange capacity and also for the catalytic activity.

The quoted values of the internal surface which are obtained through 25 the macroporous structure correspond to the traditional commercial macro-porous types.

II

-7- Below the production is described of a special macroporous strongly acid resin from divinyl benzene-styrol-copolymerisate in the shape of Raschig rings Example 1: A monomer mixture of styrol and divinyl benzene is prepared with the weight ratio of 13:1. After addition of n-pentadecane in a quantity of 35 by weight and of an effective quantity of AIBN as polymerisation initiator the mixture is ready for charging into the casting mould.

S An annular gap made of teflon tubes which are reinforced on .the inside and outside serves as casting mould. Two teflon 1 ring segments are used as seals and as spacers. The annular gap had an internal diameter of 4 mm with a wall thickness of 0.5 mm.

The mixture was allowed to react for 5 hours at 80 0 C. After 1o that the crude bodies were pulled out of the mould and were sawed off according to the correct length. A first rinsing with chloroform was carried out for the purpose of removing Sthe n-pentadecane from the finished formed bodies.

S

For the purpose of sulfonation 350 ml of the Raschig rings,produced according to the above description, were allowed complete reaction with 600 ml of chloroform and 80 ml of 2, chlorosulfonic acid in a round bottom flask in an ice bath and with reflux cooling and occasional stirring for 20 hours.

-8- Following this a.further 40 ml of chlorosulfonic acid were added and allowed to react for a further 3 to 5 hours at room temperature.

g The sulfonated rings were at first washed with chloroform and then with methanol and finally with water until a pIH value of at least 3.0 was attained. The rings were stored in distilled water.

S Coatidg of strongly acid formed bodies of macroporous resins with one or more metals of the 7th or 8th subgroup of the periodic system o of elements can, for example, be achieved by at first treating the *o formed bodies with a solution of the desired metals, for example with an aqueous solution of non-complexed ionic salts. Such metal salts S 15 can, for example, be chlorides, bromides, nitrates, sulfates and/or acetates. The quantity of salts is chosen in such a manner that after treatment and especially after reduction the desired quantities of metal are on the formed bodies. After treatment with metal salt solution the formed bodies are washed to neutrality with water and 0o* 'o dried, for example aL elevated temperature and possibly at reduced pressure. The transformation of the incorporated metals into the elementary state is carried out with reducing agents, for example hydrogen, for instance at a pressure of 2 to 50, preferably 20 to bar, and a temperature of 50 to 140, preferably of 80 to 120 OC.

-9- The formed bodies are suitable for use as catalytically active column packings for single phase and multiphase gas and liquid reactions, especially when the phases are moving in counter current as they have a high degree of voidage and therefore cause little loss of pressure.

The formed bodies are especially suitable for use as catalytically active column packings for carrying out so-called catalytic distillations in which the reaction and the subsequent processing of the reaction products by distillation respectively rectification, oD which is usually carried out in a further process stage, proceed simultaneously in one reactor.

The installation of the formed bodies into the reactor is best carried .i out by pouring them loosely onto support sieves. Reactor inlet and 20 outlet can be provided with a sieve cloth so as to retain smaller particles, fragments, abraded dust or similar, respectively to avoid carry-over of such particles. In order to reduce mechanical loading the formed bodies can be arranged on several support sieves whicha re arranged one above the other.

Chemical reactions in which the boiling points of the reactants and of the products are different are especially suitable for this manner of managing the reaction.

0 10 In order that the nature of the asent invention may be more clearly understood, the embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings in which: Figure 1 is a flow diagram of a chemical reaction using the formed bodies of the present invention in which the reaction products formed have lower boiling points than the starting mixture; Figure 2 is a flcw diagram of a chemical reaction using the formed bodies of the present invention in which the products formed have boiling points which are higher and lower than the starting mixture; Figure 3 is a flow diagram of a chemical reaction using the formed bodies of the present invention in which the reaction products all have similar boiling points which are just below the boiling point of the starting too mixture; Figure 4 is a flow diagram of an MTBE synthesis 0 process using the formed products of the present invention and; Figure 5 is a flow diagram of a separation process using the formed bodies of the present invention.

In figure 1, the starting mixture passes by way of pipe 1 into the boiling vessel 5 which is filled with formed bodies 4. The reaction forming reaction products are separated in the rectification column 6 according to their boiling points and are removed by way of pipe 2 and 3.

In figure 2, the starting mixture is fed in by way of pipe I and is reacted in the packing into a lighter and a heavier boiling component. The lighter boiling component is withdrawn at the head of rectification columm 6 by way of pipe 3, and the heavier boiling component is withdrawn from the sump by way of pipe 2.

The example represented in figure 3 concerns the case 0 10a where the stream of a starting mixture lB consists of several components the boiling points of which are not much different. Seen as a whole its boiling temperature is, however, the lowest. The stream of the starting mixture lA represents only *4 4 4* 4.

4. 4 4. 4* 4 4 4 .4 4.

44 4 4* 4.

4 4 44 4 4 44*4 11 a single component and has a boiling point just above the boiling temperature of the reaction product 2, but considerably higher than that of the stream of the starting mixture 1A, respectively of the head product 3.

The heavier boiling stream of the starting mixture 1A is fed into the head, above the catalyst ring packing 4, the lighter boiling stream into the centre below the packing into a rectification column 5. Depending on their boiling points t the components of the material stream IA tend to enrich in the lower half of the column, and the components of the material stream 1B tend to enrich at the head of the column.

On the way there, however, the components of IA react highly *i selectively with one component of lB forming the heavy boiling product stream 2 which can be withdrawn from the sump. The distillate 3, which is reduced in content by one component, can be fed into subsequent processes (figure 3).

The "catalytic distillation has, beside the advantage of saving one process step and thereby reducing the outlay for equipment, alsO advantages with respect of managing the process. This process which

O

is especially suitable for exothermic reactions makes possible the immediate utilisation of the heat of reaction as it becomes available for the simultaneous distillation of the reaction products. The reaction temperature is controlled in such a manner that it corresponds to tile boiling point of the product, whereby a simple temperature control is achieved.

S 12 The reaction product formed is immediately withdrawn from the reaction zone by the simultaneous distillation whereby the formation of decay products or else parallel products is reduced. Because of the immediate removal of the reaction products equilibrium reactions can go almost to completion. In accordance with the equilibrium constants new reaction product is formed immediately.

Reactions, which can be operated according to this principle of catalytic distillation, are exothermal reactions like ether formation, as an example the production of isopropanol from propylene and water, dimerisation, for example of isobutylene to di-isobutylene, esterification, for example of acetic acid with isopropanol to .2 isopropyl acetate, alkylation, for example of phenol and propene to propyl phenol and oligomerisation, for example of butenes to IS valuable components of so-called alkylate benzines.

The formed bodies as bifunctionally catalyticlly active column packings a are suitable for catalytic reactions of hydration and ether formation with simultaneous hydrogenation. An example of this is the .0 etherification of pyrolysis light benzine to tertiary amyl methyl ,OB, ether with simultaneous selective hydration of dienes, for example of cyclopentadiene and its derivatives to the corresponding monoolefines.

*S

S

I

13 The decomposition of MTBE to MTBE and methanol can also be effected by the process principle of catalytic distillation. From this a method is obtained for the recovery of highly pure products, in the present case of highly purified isobutene. A further application is the separation of isoamylene from a C 5 -cut by first forming a tertiary amyl alkyl ether by means of catalytic distillation and decomposing it in a second catalytic distillation into highly pure isoamylene and the alcohol.

I0 With respect to the application as column packing material for catalytic distillations the formed bodies according to the invention exhibit decisive advantages when compared to the commercial small sphere ion exchange material made from divinyl-benzol-copolymerisate.

They serve simultaneously as column packing for the creation of a i5 phase boundary surface and as catalyst. Such a simultaneous operation ,is made possible by the small pressure loss of the formed bodies.

Investigations of reaction technology have shown that the formed bodies according to the invention exhibit the same activity as comparable 2o traditional catalysts. Over and above that a special advantage is seen in the fact that a catalytically active ion exchange resin in the shape of formed bodies is made available which, because of their high degree of voidage make the use of column packings possible and which guarantee the best possible exchange of heat and material between the fluid phases involved.

o• 14 Turning now to figure 4, for the investigation of the reaction kinetics of the MTBE synthesis, the reactants methanol and isobutene together with a dilutant 1-butene are fed by means of dosage pumps 1, 2, 3 into a stirred reaction vessel 4. The stirrer 5 is driven by a motor 6, the outlet is regulated by a flow control valve 7.

The following comparative experimental results elucidate by means of the example of the MTBE synthesis that the formed bodies made from ion exchange resin have a catalytic activity (example 2) comparable to that of a commercial catalyst (in this case Amberlyst 15), which was available in the form of particles with an average :diameter of 0.2 to 2mm (comparison example 3).

Example 2: 15 For the investigation of the reaction kinetics of the *1 MTBE synthesis the reactants methanol and isobutene S. together with the dilutant 1-butene are fed by means of dosage pumps into a stirred reaction vessel of 106 ml capacity. The volume stream was selected so as to obtain 20 a mean residence time of 5.3 min. in the reactor.

Figure 4 shows the arrangement in principle.

The catalyst rings are threaded onto a fixed teflon tube in the reactor.

Sampling is carried out by way of a partial stream of the outlet mixture which is passed continually through a sampling loop.

The results obtained with the parameters used are reproduced in the table below.

15 Concentrations in by weight MeOHl lB lB MTBE DIB U MeOH in 7 42.7 30,8 16.9 5.96 4.53 3.03 55,7 57.8 60.5 62.5 63.1 63.2 1.63 9.43 1.97 20.0 2.51 29.6 1.40 30.4 1.41 31.5 1.43 0.088 0.507 0.556 0.740 1 .37 2.27 5.12 7.86 10.2 15.5 8e p S S

S.

S

S

SO

b a 3 d~ @9 6 0S

S

590 4 Reaction velocities in mmol/s eq DIB MTBE 16.8 19.5 0.66 23.9 8.45 29.7 9.24 29.8 12.2 .1 Abbreviations: 32.3 MeOllI

IB

MT BE

DIB

lB 6O 0 04t S Op a S S a se methanol isobutene methyl-tert.'-butyl ether diisobutene 1-butene 16 Reaction equations: MEOII IB MTBE IB IB DIB Reaction conditions: T 60°C, p 21 bar Catalyst volume: 1.0 g Raschig rings made of strongly acid macroporous divinyl benzene-styrol-copolymerisate, dimensions (swelled up in water) 6 x 6 x 1 mm, swelling up (dry withregard to water) 80 by volume, Percentage of voids o about 45 by volume, Cross bonding 7.5 by weight divinyl benzene in monomeric mixture with styrol, BET-surface (1-point method, N 2 -adsorption) 30 m 2 exchange capacity 4.5 meq/g.

The determined starting reaction velocity for the catalyst rings S. forming the subject of the patent is in practice exactly the same as for Amberlyst 15 used under comparable conditions, as shown by comparison with the example 3 below.

e* S S to Example 3 (comparison example) The experimental results given below were obtained under the same conditions as in example 2 with the sole difference that the catalyst was now present in the shape of little spheres and was not fixed in the reactor but was maintained in 2 suspension by the stirrer. The weighed quantity of catalyst St was also 1.0 g S* *o 17 No. Concentrations in by weight U MeOT in MeOll IB 1B MTBE DIB 39. 2 22.0 9.2 4.25 2.72 55.0 58.0 61.0 60.3 60.2 5.22 19.4 28.7 33.2 34.3 0.544 0.549 1 .02 1 .88 2 .34 0.097 0.295 0.474 0.502 0.898 3.870 13.800 23.800 0

S.

e.i .5 e 0* Se

S.

0 0 0*

SOS.

S S 00 S

S.

I~ 0 0.e C Reaction velocities in mmol/s eq DIB MTBE 18.2 17.5 2.30 31.3 6.18 56.8 9.21 70.6 eCOS 9 'See See.

45 OS C *Go

A.

Ce S tee e Ge C S 5 9 V CS Example 4: In ongoing experiments the catalyst rings according to the invention were used in a pqcked column made of stainless steel (Wst.No. 1,4571) The reactants mnethanol. and isobutene together with the dilutant 1-butene were fed into the head of the column by means of dosing pumps.The mixture is heated approximately to boiling temperature.

18 The upper half of the separating column is filled with the chemically active formed bodies in the shape of catalyst rings while the lower half is filled with inert ceramic rings.

The lighter boiling residual butene can be withdrawn at the head of the column and the heavier boiling component, which comprises the product MTBE and residual methanol, can be withdrawn from the sump.

The column had an internal diameter of 53mm. The total height of the column packing was im. In order to reduce the mechanical load the catalyst rings were supported by three support sieves one above the other.

.o Sampling was carried out by way of a partial stream *of the head, respectively the sump product which were 15 continually passed through sample loops.

In the following tables the results of several experimental runs 1 to 9 in the previously described equipment with the catalyst rings according to the invention, are represented, whereby the material stream 20 for the feed products had the value of 25 ml/min at a plant pressure of 6 bar (absolute) and a temperature below the catalyst packing of Molar composition of the feed in No XMeOH XIB

XIB

1 25.0 63.75 11.25 2 25.0 50.5 24.5 3 25.0 37.5 37.5 4 52.5 23.5 24.0 52.5 32.0 15.5 6 52.5 40.5 7 80.0 10.0 10.0 8 80.0 13.5 r137 9 80.0 17.0 19 Molar composition of the sump product No. X MTBE X MeOI X DI X X Tri X Ti IB exchange 73.08 84.01 67.78 44.75 22.94 9.29 13.52 6.32 3.44 26.92 15.99 14.48 55.25 76.89 90.71 86.48 93.68 96.56 traces traces 12.83 traces 0.085 0 0 0 0 0 traces 4.305 traces 0.083 0 0 0 0 0 0 0.28 traces traces 0 0 0 0 0 0 0.326 traces traces 0 0 0 0 58.79 70.07 79.02 71.65 69.40 66.06 84.98 80.12 73.69 a .e

SE

C. C S C

CC

CC

C S

C.

CC OS C C C CC C

S.

C C .RC C Abbreviations Me Ol

MTBE

ct-DI 13-Dl ct-Tri f3-Tri 1-B

IB

methanol methyl-tent. -butyl ether c-diisobutene: 2, 4,4 trimethyl-2-pentene f-diisobutene: 2,4,4 trimethyl pentene c-triisobutene:2,4,4,6,6 pentamethyl-1-heptene 0-triisobutene: 2,4,4,6,6 pentamethyl-2-heptene 1-butene is'Thutene

RSCS

C

CCC S *0 Ce C

C.

C

CCC

In accordance with the task of the invention it can be seen that the sump product is free from lower boiling butenes.

a CC C Cm a 5 9

SC

20 In addition to the comparative kinetic studies which have been reported above, extended period investigations were carried out regarding the storage properties of the catalyst according to the invention in a tube shaped reactor and using various catalyst loadings.

An 8/18 stainless steel tube of 770 mm length and 20 ml diameter was used as reactor which was filled with the catalyst according to the invention in the form of Raschig rings to two thirds of its capacity.

Commercial C 4 cuts of the refinery were used as C -mixtures which jo contained 10 respectively 49 by weight of isobutene. The results of ether formation of isopropene respectively methanol with isobutene under selected operating parameters are summarised in tables 1 and 2.

o e

S.

S

et

*G

t

S*

S S

S

C

S..

*S

S

C. S C et 21 By adding a water wash and a so-called police filter in series prior to the inlet for the C 4 -cut into the reaction-separation column interfering constituents which reduce the activity of the catalyst rings, for example weak bases such as amines or cations like sodium can be effectively removed. Depending on the quality of the methanol inlet stream the insertion of a police filter prior to the inlet of the stream might be advantageous here also. Mechanical defects on the catalyst rings were observed to a minor degree only. The catalyst rings made of sulfonated macroporous styrol-polymerisate were used as hollow cylinders with dimensions of about 6 mm external and internal diameter and 8 mm height. The colour of the hollow cylinders was white to cream coloured. The exchange capacity was determined according to the usual method (Fisher and Kunin, Analyt. Chem. 27, 1955, 1191- 1194) as being 4.44 mg H+/g of contact (dry). The swelled volume of :i 23 ml dry contact catalyst in the form moistened by water or methanol was 50 ml corresponding to a dry apparent density of 0.275 g/ml respectively 0.127 g/ml moist. The degree of bonding of the catalyst 6 used corresponds to the nominal content of divinyl benzene in the monomeric starting mixture. The BET surface of the contact catalyst ;o was determined according to the 1-point method with N 2 The formed bodies according to the invention in the shape of hollow cylinders made of sulfonated styrol polymerisate were tried out with good success in the following other reactions, apart from the 26 experimental runs of the ether formation from various i-butene cuts with isopropanol respectively with methanol the results of which were reported above. The same apparatus was used as in the running of the above mentioned long period experiments.

a a a 22 1. Hydration of propene with water (table 3) 2. Hydration of i-butene with water (table 4) 3. Ether formation of 2-methyl-2-butene with methanol (table 4. Dimerisation of i-C 4 (table 6) Furthermore, the hollow cylinders according to the invention made from sulfonated macroporous styrol polymerisate were coated with palladium and tested to determine their suitability as catalysts for the hydrating ether formation.

The palladium coating was carried out as described below: 0.63 Pd (NO 3 2 were dissolved in 60 ml of water.

The solution was yellowish-brown in colour. 100 ml of H20 moistened styrol polymerisate formed bodies were added to this. The styrol polymerisate was completely covered by the palladium nitrate solution.

After allowing to stand for 1 day the aqueous solution was clear and colourless which indicated that the palladium had been exchanged.

Commercial methanol and and light benzine from an olefine plant were used as starting materials.

After charging the formed bodies into the tube reactor already described the residual water contained in the Raschig rings was displaced by methanol and the palladium was reduced at a temperature of 70 0 C and a pressure of 11 bar with 6 normal litres of hydrogen 23 in 150 ml of methanol per hour. After 48 hours the methanol was replaced by the reaction feed mixture of benzine/methanol. The other reaction conditions were: Catalyst quantity: 100 ml (swelled in water) Temperature: 70 75 °C Pressure: 10 11 bar Feed: Crack-L-distillate from VC with 10 methanol p Quantity of feed: 150 ml/h 103 g/h Quantity of hydrogen: 7 NL/h Bi/H 2 ratio: 200 g/g 0 S 15 The experiment has shown that the formed bodies according to the invention which have been coated with palladium are very selective in the hydrogenation of the polyunsaturated olefines (dienes) contained in the pyrolysis light benzine, and at the same time catalyse the ether formation of tertiary monoolefines with primary and secondary g? alcohols. Results are given in table 7.

9 0 e 0 *b •Q «D a..

a a a a- U U a a a a a -a 0 S *s a a C. 4 a. a a a a a. a a aS 0 a a a a a a a a a a a a a..

T A BLE Ether Formation of C 4 Cut with IPA 12 3 4 5 6 7 8 9 Experiment No.

Cat. volume swelled (mil) 160 160 160 160 160 160 160 160 160 LHSV (ml feed! ml catalyst) 2,46 2,46 2,46 2,46 2,46 2,46 2,46 2,46 4,92 Mol ratio (isobutene:isopropanoi 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 Feeds C -cut mi/h 33 3' 333 333 333 333 333 333 667 I A mi/h 160 60 60 60 60 120- 60 60 120 Temperatures, Pressure Oulet C) 53,2 53,8 54,2 58,6 58,6 58,7 58,6 58,7 58,7 Prue (ba) 55,2 56,4 57,2 59,0 59,2 59,2 59,2 59,4 59,5 Yield isopropyl tert.butyl ether 56,0 56,5 56,4 55,6- 54,5 51,8 54,4 54,8 46,3 Running time at the end of the experiment 1 12 30 44 65 79 91 105 119 6268J

S

S

S

TA B LE 2 *5S S S S a S S S 5 S. S S S

S

*5 4 g* Ether formation of i-Butene with Methanol Experiment No.

4 I 4- I 4 1 Cat, volume, swelled

LBHSV

Mol ratio (isi Mass streams

G

4 -cut Qg methanol Qg (ml) (ml feed/ml cat.) obutene :methanol) /h) /h) 200 3,98 0,83 370; 6 124,3 59,0 62,6 10 200 3,99 0,83 371,0 124,8 58,0 62,9 10 200 4,03 0,85 375,6 125,1 59,7 62,6 10 200 3,97 0,83 369,9 123,5 60,4 62,7 10 200 6,80 0,84 633,3 209,4 49,1 67,3 10 206 6 84 0,83 636,3 214,6 200 6,85 0,82 635,2 216,5 49,0 65,3 Temperature, Pressure Inlet Outlet Pressure

C

0

C)

OC)

(bar) 48,0 65,2 10 Yield MTBE 80,1 82,1 83,4 83,3 64,6 60,4 62,1 Running time at the end 714 21 28 35 42 49.

of the experiment 6175J 9 .9 9 9 99 9*9 :9 9 0*99 9 9 9 9 9- 99 9 a 9 99 9 9*9 9 9 ago 9- sop9 9 T AB-L E 3 Hydration of Propene. with Water- Experiment No. 1 2 3 4 5 6 Cat. volume,swelled (ml) 1 200 200 200 200 200 20G0 LHSV (ml feed/mi cat.) 1 1 1 0,5 0,5 Nol ratio (H 2 0/C 3 10,3 9,2 9,8 10,2 10,4 10,3 Mass streams Propene 32,6 32,1 32,2 15,9 15,8 15,7 Water (glh) 142,0 128,0 134,0 69,0 70,0 68,5 Outlet (glh) 144,2 131,5 139,9 73,2 74,4 73,1 Temperature, Pressure- 121314191918 Inlet 0 c) 10111- 3 3 3 Outlet C 0 C) 118 128 138 137. 137 137 Pressure (bar) 80 80 80 80 80 IPA content of the reaction product 2,2 3,8 6,0 8,2 8,5 8,9 Exchange propene M% 6,8 10,9 18,;13 26,4 28,0 29,0 Cat. running time at end of experiment (h)l 7 14 -21 28 35 42 6173J egs

S

o S 5

S

*5S S S S S Op 56 TAkB LE

S

S

S S S S S S S S S* S S S

S

Hydrati iiof- i-butane with Wt- Experiment No. 7 8 9 10 11 12 Cat. volume, swelled (m)200 200 200 200 200 200 LSHV (ml feed/ml catalyst) 0,5 0,49 0,51 0,24 0,22 0,23 Hal ratio (H 2 0/i-C 4 10,1 10,2 10,2 12,3 11,2 9,2 Has streams i-butene 20,2 19,7 20,7 8,4 8,3 9,7 Water 66,2 65,2 67,6 33,3 29,8 28,6 Outlet, stabilised (glh) 67,7 66,9 69,3 34,4 31,0 30,0 Temperatures, Pressure '0 02 8, 017, 877, Inlet (C802 828017878789 Outlet (OC) 79,7 80,2 80,4 79,5 81,3 81,3 Pressure (bar) 80 80 80 80 80 80 1' TBA content of the reaction product 3,0 3,3 3,0 4,1 5,2 Exchange i-butene 7,6 8,5 7,6 12,7 14,7 14,3 Catalyst running time end of experiment 49 56 -63 70 77 84 6174J g *so p S A

S

5 eAR U U S a p pep SP P a p.

S. U *ep S p 0 P 0* S P 5* p Re C p 5 p C 55 C p p S C PS P p C *pp *fr.

T A BLE Ether Formation of 2-Methyl-2-Butene with Methanol I" r 1 r T T I Experiment No. 8 .111 14 1* 1* Cat, volume, swelled LHSV (ml. feed/ Mol ratio (g/h) Mass streams 2-methyl-2-butene Methanol Temperatures, Pressure Inlet Outlet Pressure (ml) al catalyst) (g/h) (g/h) 200 4,0 0,84 364,5 198,6 59,0 62,6 10 200 4,0 0,92 374,5 185,8 58,0 61,5 10 200 4,0 0,91 375,3 187,4 58,0 61,9 10 200 4,1 0,92 379,3 187,9 58,0 61,9 10 200 2,0 0,90 185,7 94,7 61,3 59,9 10 200 2,0 0,89 185,2 95,3 61,2 59,8 10 200 2,0 0,87 184;8 -96,6 60,8 59,7 200 0,87 184,2 95,9 61,3 59,8 0

C)

0

C)

(bar) Yield TAME* (Mol-%o) 26,9 24,3 25,0 23,7 37,3 37,3 .37,4 37,5 Cata.running time at 140 147 154 161 168 175 182 189 end of experiment *TM Tertiaer-anyl--Methylether 6176J be

S

C.

S

S C C C S S C SC S C C C *5 S 55* 5 C C C S C C S S. 5 6 S C .C C S C C C S 5# S C C 5CC 535 T AB-L E 6 Dimerisation of Isobutene Experiment No. 1 2 3 4 5 I 6 7 Cat. volume, swelled (ml) 200 200 200 200* 200 206t' 200 LHSVI (ml feed :ml catalyst) V 111111 2 Feed

C

4 mixture (glh) 118,5 117,7 *11.4,3 113,7 116,7 116,7 233,0 i 4Butene* (glh) 57,8 57,4 *55,8 55,9 56,9 54,8 109,5 Temperature, Pressure Inlet temperature (OC) 73,8 74,4 72,2 72,5 82,8 82,6 90,1 Pressure (bar) 20,0 20,0 20,0 20,P 20,0 20,0 20,0 Yield of dimers' (Mo1-7.) 1 92,9 94,4 95,8 93,5 93,5 94,3 96,3 Cat. running time 197 205 213 221 245 253- 261 oxitaifred in the C 4 -Imlxture 6177J eq.

&*3 4.

a

C

pg. a at.. 9 3 a a a a S C C CS C C .5 C *9 0 'TA B LE 7 a a .G4C C e3 a t a a a p a C S a S a .a fW* Ca.

I

under hydrogenating Ether Formation Conditions Component Einsatz Reaktionsprodukt Methanol I10,5 6,8 E 2-Methyl butene, 17,4 12,8 E 2-Methyl pentene. 5,7 4,6 Cyclopentadiene 0,59 0,005 cis-Pentadiene 0,12 0,005 trans-Pentadien 0,21 0,005 Methyl butadiene 0,11 0,005 TAME 6,7 2-Methoxy-2-methyl pentane Other oxygen containing components -2,1 62"70J

Claims (9)

1. Formed bodies made of macroporous strongly acid or basic ion exchange resin in the shape of column packings such as Raschig rings, Berl saddles, Torus saddles, packing rings with bar or cross bar, Pall rings, other hollow bodies, hollow spheres and similar, with a percentage of voidage of 5 to 95 of the macro-form without pores, a BET-surface of 0.01 to 1,000, preferably 20 to 60 m2/g and an exchange capacity of 0.05 to 10, preferably 3 to 6 meq/g.

2. Formed bodies according to claim 1 made of strongly acid macroporous ion exchange resin produced in shapes suitable Sfor the forming of column packings or by means of suitable devices for the production of formed bodies or parts by using S' a polymerisation initiation and copolymerisation of styrol and divinyl benzene in a weight ratio of 200:1 to 8:1, preferably of 20:1 to 5:1, possibly with the addition of pore generators in a quantity of 2 to 80, preferably 10 to 40 by weight of the total mixture. «J4.

3. Formed bodies according to claim 1 made of strongly acid macroporous ion exchange resin, produced by the generation or creation of acid centres, especially by subsequent acid treatment, for example with sulfonic acid. 4 Lb b 32

4. Formed bodies according to claim 1 coated with metals of the 7th or 8th subgroup of the periodic system, especially palladium, platinum, ruthenium, rhodium, in quantities of 0.1 to 100 g/L of ion exchange resin.

5. Formed bodies according to claim 1 in the form of Raschig rings with an internal diameter of 0.5 to 100 mm, preferably 4 to 20 mm, a wall thickness of 0.1 to 20 mm, preferably 0.5 to 3 mm and a length which corresponds to 0.1 to 20 times the internal diameter.

6. Utilisation of the formed bodies according to any one of the claims 1 to 5 as catalytically active column packings for chemical reactions, especially ether formation, hydration, dimerisation, oligomerisation, G. esterification, hydrogenation or alkylation or 15 combinations of these.

7. Use of the formed bodies according to claim 6, S y** characterised by simultaneously carrying out a separating operation such as adsorption, absorption, extraction, stripping, distillation, rectification, fractionation, 20 membrane processes or similar.

8. Use of the formed bodies according to claim 6, characterised by counter current flow of gas and liquid g e phase.

9. Formed bodies made of macroporous strongly acid or 25 basic ion exchange resin substantially as hereinbefore described with reference to the accompanying drawings and examples but excluding comparative examples. Use of formed bodies made of macroporous strongly acid or basic ion exchange resin as catalytically active column packings substantially as hereinbefore described with reference to the accompanying drawing and examples but excluding comparative examples. DATED this 3rd day of February 1993 VEBA OEL AKTIENGESELLSCHAFT Zf, c- Patent Attorneys for the Applicant: F.B. RICE CO.