CA1037458A - Method for producing catalyst based on cation-exchange resins - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method for producing a catalyst base on cation-exchange resins which comprises mixing a cation-exchange resin with a thermoplastic material and at least one additive selected from organic additives and water and extrusion-moulding of the resulting catalyst mixture at the melding point of the thermoplastic material. The presence of the additives is to simplify the process technology and improve the catalyst quality. The catalysts produces possess high activity, heat resistance, and mechanical strength.

Description

` ~374~3 The present inyention relates to a method for production o~ catalysts bas~d on cation-exchange resins.
Such catalysts are widely used in processes of hydration of tertiary olefines, production of olefines from tertiary alcohols, alkylation of phenols with tertiary olefines, synthesis and hydrolysis of esters, synthesis of ethers from tertiary olefines and lower alcohols, dimeriza-tion of olefines, @
and the like.
A method for produc.ing catalysts based on ion-exchange resins is known which comprises mixing an ion-exchange resin with a thermoplastic material, followed by heating and moulding of the resulting mixture. The heat.ing is conductecl up to the : sinterincJ temperAt ure Oe the catalyst m:lxtu.re (se~ U.S. Patent No. 3,2~8,339). 'I'his method has a cl:Lsaclvantage o.E .low procluct-.ivity, since the catalyst mass is sintered in the form oE each separate element oE the catalyst, and only one ca-talytic element . is obtained during one technological cycle by slowly hea-ting . the catalyst mass. This operation usually lasts for 120 -to 130 minutes, and therefore commercial implementation of the process is economically undesirable. Long duration of heating at elevated g . .:
temperatures may result in a thermo-oxidative destruction ofboth ~ thermoplastic material and ion-exchange resin, whereby physico-; mechanical and catalytical properties of the catalyst thus L
: obtained are substantially impaired. Furthermore, uniform heating t ~ of the whole catalyst mass of a catalytic element to the sintering ., . ~
.~ temperature is extremely dif~icult to ensure and at local over-heat:i.ng sites melting of the thermoplastic material may occur, thus causing the formation of impermeable films, which in turn results in the production of an inactive catalyst, Catalyst packings thus obtainecl are suitable ~or applications in packed columns at temperatures of up to 30C, In addition, to ensure uniform mixing of a thermoplastic ma-terial and ion-exchange resin, ' ~,~

~'~` '~1 ' `, ~37~
a finely dispersed thermoplastic material is required, which is rather difficult to prepare. Thus the conventional process for producing a catalyst does allow the use of a granulated thermoplastic material.
The present invention provides a me-thod for producing a catalyst based on cation-exchange resins ~hich improves -the catalyst quality and increases its activity, heat-resis-tance, ancl mechanical strength. The present invention also simplifies ` the process technology.
According to the present invention there is provided a method for producing a catalyst based on cation-exchange resins which comprises mixing a cation exchanc3e resin with a thermoplastic material. in the presence oE at least one ad~iti.ve seleet~d frorn ~n orgclnie addit:ivc~ and water and e~xtrus:Lon~mouldinc3 of the resulting catalyst mixture at the melting point of the thermoplastic material.
i Under the influence of some factors prevailing in an extruder during the mixture processing, namely: high pressures, , effective intermixing of the molten thermoplastic material and cation-exchange resin, elevated temperature within a closed ,~ spaee, and short process duration (5 to 10 minutes), the possibil-:. .
ity of impermeable film formation is considerably reduced, and ~-- favourable conditions are provided for the production of a uniform, high-strength catalyst wi-th a high con-tent of the ion- ~
exchange resin. Therewith, the thermoplastic material may be i employed both in the Eorm oE a finely dispersed powder and c3ranules of various slzes.
In order to impart an enhanced porosity to the eatalyst mouldinq of the eatalyst mixture is desirably effected with simultaneous stretching thereof. This may be efEected using standard equipment Eor processing thermoplastic materials.
The proeess technology is substantially simplified and , .

the catalyst quality is improved hy ~Ising organic substances compatible with the thermoplastic material in an amount of up to 20 weight parts by weight of the catalyst. As such substances mention may be made of mineral oils compressor, transformer and vaseline oils, esters useful as plasticizers such as dioc-tyl phthalate, dibutyl phthalate and dibutyl sebacate and non-ionic-emuls:ifyiny substances sueh as hydroxye-thylated higher aliphatic aleohols and hydroxyethylatecl alkylpheno]s. These substances introduced during mixing of the starting components of the : lO eatalyst has -two effects. In particular, it makes it possible to lower, by 10-15C, the temperature necessary to convert the : thermoplastie material into a molten state, whereby the cleeomposi-tion of the thermoplastic material and cat:ion-exehan-le res.i.n is substant.ially eliminated and to red~lee the v;.sco.q.i.ty ol. the molten eatalyst m.i.xture. This :increases t.he extruder output and improves the eatalyst activity by ineorporating the cation-exehanye resin into the startiny mixture. The catalyst produced by this method has sueh a lower swelling capacity in water and .~ polar solvents, that the chanye in eatalyst volume duriny the process is redueed. The mechanical strenyth of the catalyst ~ is significantly reduced. To increase porosity, to form a : highly developed inner surface which enhances activity of the catalyst containiny said organic additives, it is treated with oryanic solvents sueh as hydroearbons, alcohols and ethers. When the eatalys-t is to be employed in processes contempla-tiny the use of oryanic solvents, sueh treatment takes p:Lace in the process ~;
: itself, and no spc-~ci.al treatment o the catalyst is requi.red. i`
To increase porosity and -to reduce swelling capacity of g the catalyst in water and polar solvents, -the eatalyst preparation may be efEeeted in the presenee o~ water during the mixiny of the starting eomponents of the eatalyst. Alternativel.y, use may be made of water eontained in -the eation exehanye resin, or - ~ .

~ 3 -~ ~37~
~oth procedures may be used in combination, Water content in all the above-mentioned cases ranges from 5 to 50 wei~ht parts byweight of the catalyst. Water, duriny extrusion-moulding of the catalyst mixture, is evaporated due to high temperatures, thus providing, wi-thin the catalyst, an ex-tensive porous network, thus imparting porosity to -the catalyst.
Organlc substances compatible with the thermoplastic material and water may be introduced simul-taneously. This ensures the benefit of -the effec-ts of both additives a-t the same time. In this case, it is advisable to perform -the catalyst treatment with a solvent.
To additionally increase the static exchancJe capacity and activ;ty of -the catalyst thus prepared, it is cle~s:irahle to ~ maintain the catalyst in a chlorinated ali.phat:Lc soLverlt llntll ; it is swollen, and thereaEtar to tr~at tlle cataLyst w:ith a ~,trong sulphonatinc3 agent at a temperature ranging from 30 to 100C.
Such efficient sulphonating treatment of -the catalyst in the swollen state which, in itself, facilitates pene-tration oE the sulphonating agent into the entire ca-talyst volume in a more b .
complete and deeper way, causes the in-teraction of the sulphonating agent with the thermoplastic ma-terial contained in the catalys-t. ~, p'.
As a consequence, ion-exchange and cataly-tic properties are imparted to the catalyst, i.e., its total sta-tic capacity and activity are enhanced. As such highly active sulphonating agents, it :is desirable to use, for example, concen-trated sulphuric acid or chlorosulphonic acid. The treating -temperature depends on the sulphonating agent used as well as on the solvent and thermoplastic material incorporated in the catalyst. When concen-. ~
trated sulphuric acid is used, such trea-tment is effected at a temperature within the ranc3e of from 60 to 100C. ~hen chloro-sulphonlc acid is used, the treatment is effec-ted at a temperature ; of 3n to 60C, and the catalyst is then treated with a saponifying ~; :

-' :
, agent such as ~r example of water ~r an alkaline solution.
, After treatment of the cataly~t with an alkaline solution, it " is desirable to additionally treat the catalyst with a mineral acid solution. To prevent the sulphonating agent activity from reducing, it is desirable to dry the catalyst prior to the treatment -thereof with a chlorinated alipha-tic solvent.
The rnethod of the prcsent invention, as compared to conventional methods, makes it possible to use s-tandard equipment ,' ensuring high efficiency of -the process and allows the use of ' , 10 a thermoplastic material having various degree of fineness in , powder or yranular form. The method oE the present invention also ~, makes it poss,ible to produce a cataly~st oE diE~erenl: shapes and dimensions.
The pro~orties O.e thc catl l~yE~t prC)CIUC'C'~ y th~ method of the present invention are superior to those of the catalysts produced by the conventional processes. The catalyst produced accordirlg to the present invention is more active, heat-resistant;
can wlthstand tempera-tures as high as 110C and possesses high mechanical strength.
These properties of the catalyst allow some processes to be effected, with high yields and efficiency, such as a '~ process for producing olefines by dehydration of tertiary alcohols;
' ' a process for producing p-tert.-butylpyrocatechol by alkylation of h~ pyrocatechol with isobutylene or tert.-butyl alcohols, or 1~ with a mixture thereof. This latter process may be effected, using the catalyst of the present invention, both continuously and bat:chwise.
' Furthermore~ additional treatment of the final catalyst provides for an incxease, by 30-50% .in static exchange capclcity and activity of the catalyst.
The method Oe the present invention is technologically simple and may be effected in the following manner.
!

_ 5 _ ."

,., ~,, .

:~ ~37~5~
A finely divided cation excha~ge resin ls mixed with - a finely divided thermoplastic m~terial, The additives, i,e, the organic substances and/or water, are supplied to the stage of -mixing the starting components of the catalyst.
The resulting mix-ture is fed into an extruder, and in particular, into its Eirst heating zone, wherein the mix-ture is preheated with mixing. Then said mixture i9 passed in-to -the ~ second melting ~ne, wherein the thermoplas-tic material mel-ts with ; thorough mixing of the catalyst mixture. The catalyst mixture ~ 10 is then fed into a hea-ted forming die designed so that the : catalytic mixture may be moulded in the form oE articles of various shapes and cross-sections, for instance in ~he form oE
pipes of diEferent d:iameters and wall th:ickness or in the Eorm of strands (worms) o vari.ous diameters. The catal~st mixtnre extruded from the Eormi.ng die is cooled by a stream of air or water, and is delivered to a stretching device where the required stretching ratio o the material may be obtained by adjusting said device accordingly. The ma-terial is then passed to a cutting device where it is Cllt into annular pieces or granules of appropriate length.
Stretching is however, not required during the production of the catalyst. The catalyst mixture is, simultaneously granulated ~i ~;: p;
and cooled at the outlet of the Eorming die.
To increase s-tatic exchange capaci-ty and ac-tivity of the catalyst, the inal catalyst is placed into a vessel and a chlorinated aliphatic solvent ls poured therein. The catalyst is held in the vessel until it becomes swollen. Then the contents ; t of the vessel is heated to a selected temperature, and a highly active sulpllonatincl agent is added thereto in smal:L portions under 3~ continuous stirring and cooling~ As -the solvent, use is made of, for example, dichloroethane, chloroform and carbon tetrachloride.

The present invention will be further illustrated by , - 6 -way of the following Examples.
Example 1 60 par-ts by weight of a finely divided (0.03-0.1 ~m size) and dried cation-exchange resin ~sulphonated copolymer of styrene and divinyl ben~ene) are mixed with 40 parts by weight of a powder-like (0~1-0.5 mm size) polypropylene. The mixture is charged, a~ter mixing, in-to a double-screw extruder provided with a pipe-extxusion die, cooling means, drawing means, and cutting means.
Extrusion conditions 1. Temperature of the 1 st zone 180C
I'emperature of the 2 nd zone 200C
Die temperature l90C

2. 5crew rotatlon sE~eed fi0 r.p.m.

3. CooLing water tetnpcrature20C
I'he resulting catalyst is in the form of cylindrical rings with the outer diameter oE 8 mm, inner diameter 6 mm, and k 10 mm height.
The catalyst thus produced has the following properties:
Tensile strength 82 kg/cm Longitudinal compression strength 225 kg/cm2 Transverse compression strength 16 kg/cm ~':
- Static exchange capacity, as by 0.1 N NaOH solution 24 mg.equiv./g of dry catalyst Production of ~-tert.-butyl~rocatechol 20 g. of the catalyst thus prepared are charged into a column--type reac-tor provided with a thermostat jacke-t and -the ~
top of the reactor is continuously supplied with ~aseous isobutylene X
30 at a rate o~ 5 l/hr and a solution of 60 g of pyrocatechol in 50 g of tert.-butyl alcohol at a rate of 50 ml/hr. The temperature inside the reactor is maintained at 125-12-7C. The reaction .';' ' .' ~.~3~
mixture is continuously discharged from the bottom part of the . ~
reactor. P-tert.-butylp~rocatechol is isolated from ~aid mixture by rec-tification The yield of para-tert.-butylpyroc~t-~ echol is 93~.
: Example 2 70 parts by weiyht of a finely divided (0.03 to 0.1 mm)and dried cation exchange res:in (sulphonated copolymer o~
styrene with divinyl) are mlxed with 30 parts by weight of granulated (3x3 mm size) polypropylene and 20 parts by weight of dibutyl phthalate. The mixture is charged, af-ter mixing, into a double-screw extruder similar to that oE Example 1, except that no stretching means are providecl. L
Extrus-ti.on condition~
:L. Tempc~raturc oE the :1 st z.one :1.70C
Temperature Oe thc 2 nd ~one 190C
Die temperature 180C
2. Screw rota-tion speed 60 r.p.m.
3. Cooling water temperature 20~C
The resulting catalyst has the shape as described in Example 1.
After treating the catalyst with ethylene glycol i`
` monoethylate, it h~s the following characteristics:
Tensile strength 70 kg/cm - Longitudinal compression strength 180 kg/cm2 - Transverse compression strength 12 kg/cm . . . ~
Static exchange capacity, as by 0.1 N NaOII sol~ltion 3.0 mcl.equiv./cJ
of dry catalyst Example 3 70 parts by weight of a finely clivided (0.03 to 0.1 mm size) and dried cation exchange resin (sulphonated copolymer of styrene with divinylbenzene) are mixed with 30 parts by weight ,'` ' ~.

: , , ., .

~37~
of powder-like ~0.] to 0,5 m~ size) polyethylene! ~nd 20 parts by weight of compressor oil, The mixture is charged into a double-screw extruder provided with the same equipment as that of Example 2.
Extrusion conditions - 1 Tempera-ture of the 1 st zone 140C
Temperature of -the 2 nd zone 160C
D:ie temperature 150C
2. Screw ro-tation speed 30 r.p.m.
3. Cooling water temperature 20C
The resu]ting catalyst has the shape as in Example 1.
After treatiny wi.th ethylene glycol monoethylate, the catalyst has the followiny characterist:ics:
Tensile strenyth 75 kcl/cm2 Longitudinal compres.sion stren(Jth L80 kcJ/cm Transversal compression strenyth 12 ky/cm2 Static exchange capacity, as by ~`
0.1 N NaOH solution 3.0 g.equiv./g of dry catalyst ; 20 Isobutylene_recovery from hydrocarbon -Eractions j~, 30 g of the resultiny catalyst are charged into a - reactor comprising a steel pipe of 12 mm diameter and 1 m length.
~ A mixture consisting of 43% isobutylene and 57% isobutane and a .. . . .
50% aqueous solution of ethylcellosolve in a volumetric ratio between the hydrocarbons and solution equal to 1:5 is continuously passed through -the reactor at a rate of 150 ml/hr. The pressure .~;
: maintained in the reactor is 20 atm, temperature is 90C.
Under these conclit:ions, khe rate o;E conversion oE isobutylene into tert.-butyl alcohol is 92%. Ter-t.-bu-tyl alcohol of a 85%
. 30 concentration is recovered rom the reaction products. The tert.~butyl alcohol is Eurther dehydrated to give isobuty]ene.

i , The dehydration is eEfected in a column-type reactor consis-ting ., ~j.~, .

. ~ , ,. ... ~ . .. . .
~ ;'~. ' , . .:
, , . : ~ :.. . :

~3~
of two zones namely a top reaction zone which is eharged wit-h 30 g. of the catalyst obtained, and a bottom reetifieation zone of 0.5 m height which is packed with nichrome wires, The reactor is provided with a boiler and dephlegmator. The reactor is of 30 mm diameter.
Tertiary butyl alcohol is supplied to the mid-portion oE the reactor below the eatalyst bed at a rate of 50 ml/hr. The reactor is maintained under atmospheric pressure; the reaetion zone temperature is 85-87C. The catalyst is contac-ted by tert.-butyl alcohol in the form of vapours delivered from the bottom ;' ~' rectifieation zone and in the form oE a liquid flowing down from the dephlec~mator~ The resulting gaseous isobutyl.ene along with vapours of unreacted tert.-butyl alcohol, r~ es I.lp the reactor and passes into th~ deph:LecJmator where the ~lcohol :Ls condenc;ecl and recyeled back onto the eatalyst. Isobutylene is evacuated from the reactor, condensed, and purified by rectlfication.
, Concen-tration of isobutylene is 99.95~. Another product of '; the dehydration, namely water in the form of a soluti,on in ' tert.-butyl aleohol is fed into the bottom rectification zone, ,.. , ~,.
, 20 separated from the alcohol, and discharged from the system. The ~' reactor still is maintained at 100C. The to-tal rate of ,, conversion oEtert-butyl alcohol into isobutylene underthese ~: conditions is 100%; the catalyst is used for 4,000 hours without any noticeable decrease of its ac-tivity. ~, Example 4 ' 70 parts by weight oE a finely divided (0.03 to 0.1 mm size) and dried cation-exehancJe resin (sulpllonated copolymer oE
' styrene with divinylbenzene) are mixed with 30 parts by weight ~' of powder-like (0.1 to 0.5 mm size) polyvinyl chloride, and 5 parts by weic311t o~ dioc-tyl phthalate. The mixture is charged into a double-serew extruder provided with the same equipment as in Example 2. ~, ., ~

'~.'' ', , ", : ' ~

9~337~
Extrustion conditions 1, Temperature of -the 1 st zone 1~0~C
Temperature of the 2 nd zone 160PC
Die -temperatIlre 150C
2. Screw rotation speed 60 r.p.m.
3. Cooling water -temperature 20C
The catalyst thus obtained has the shape as in Example 1.
After treatiny with acetone, the catalyst has the following characteris-tics:
Tensile strength 90 kg/cm2 , Longitudinal compression strength 210 kg/cm2 Transversal compression strength 17 Icg/cm Static exchange capacity, as by 0.1 N NaOII so]utiorI 3.0 mcI.ec~Iiv~/cl ,~
of clry soLution ~" Example 5 70 parts by weight of a finely divided (0.03 to 0.1 mm size) and dried cation exchange resin (a condensation produc-t of p-phenolsulphonic acid formaldehyde) are mixed with 30 par-ts j' by weight of polystyrene and 10 parts by weight of hydroxyethylat~
ed higher alcohols. The mixture is charged into a double-screw extruder provided with the same equipment as in Example 2, E
.',' ~,~.
except that it has a granulating die instead of pipe-forming die.
Extrusion conditions ~`
,~ 1. Temperature of the 1 s-t zone 160C
Temperature of the 2 nd zone 180C
~: .
~ D:ie temperature 170C
,' 2. Screw rotation speed 40 r.p.m.
3. Cooling water temperature20C
The catalyst thus produced has the form Oe cylinders of 4 mm diameter and 5 mm height.
AEter treating with ethylene glycol monoe-thylate, the catalyst has the following characteris-tics:

., .. :

~L~337~ 2 Tensile strength 80 kg/cm Compression strength 19~ kg/cm~ ¦;
- Static exchange capacity, as by 0.1 N NaOH 2.8 mg.equiv./g of dry catalyst Example 6 , 60 parts by weight of a finely divided and dried cation-exchange resin (sulphonatecl copolymer of styrene with div:inyl-benzene haviny a macroporous structure) are mixed with 40 parts by weight of powder-like (0.1 to 0.5 mm size) polypropylene and 20 parts by weight of water. The mixture is charged into a double-screw extruder provided with the same equipment as in ; ~xample 5.
Fxtrusion concli-tions 1. Temperature of the 1 st zone 180~C
Temperature of the 2 nd zone 200C
, Die temperature 190C
. 2. Screw rotation speed 60 r.p.m.
~ 3. Cooling water temperature 20C
- 20 The catalyst thus produced has the same form as in .... ..
~' Example 5.

,-~ The resuliny catalyst has the following characteristics:

Tensile strength 90 kg/cm2 Compression strength 230 kg/cm Static exchange capacity, as by 0.1 N NaOH solution 2.5 mg.equiv./g of drycatalyst Example 7 ~;

~- 80 parts of a Einely divided (0.03 -to 0.1 mm size) ."~ .
cation-exchange resin (sulphonated copolymer of styrene with ~; divinylbenzelle) with a water content of 50~, are mixed with 30 parts by weight of powder-like (0.1 to 0.5 mm size) polyethylene.
~' .

, .

The mixture is charged into a double~screw extruder pro~ided with the same equipment as in Example 1, except that a granulating die is employed instead of the pipe-forming die, Extrusion conditions 1~ Temperature of the 1 st zone 140C
Temperature of -the 2 nd zone 160C
Die ternperature 150C
2. Screw rotation speed 60 r.p.m.
3. Cooling water temperature 20C
The resulting catalyst has the same shape as in Example 5.
The catalyst thus produced possesses the followlng characteristics 'I'enslle strenyth 95 kg/cm2 Compression strength 240 kg/cm2 Static exchange capacity, as by 0.1 N NaOH solution 2.4 mg.equiv./g ' of dry catalyst ; Example 8 ~- 20 70 parts by weight of a finely divided (0.03 to 0.1 t~
mm size~ and dried cation-exchange resin (sulphonated copolymer ~, ~,, ~ of styrene with divinylbenzne) are mixed with 30 parts by weight ; of powder-like (0.1 to 0.5 mm size~ polypropylene,and 15 parts ~ by weight of water. The mixture is charged in-to a double-screw .. ~1 extruder provided with the same equipment as in Example 5.
; Extrusion conditions 1. Temperature Oe the 1 st zone 180C
Tempera-ture of -the 2 nd zone 200C
Die temperature 190C
2, Screw rotation speed 60 r.p.m.
3. Cooling water tempera~ure 20C
The resulting catalyst has the same shape as in Example 5.
': ;.
, .

,' ' ' : !

~13~
The catalyst thus produced possesses the ~ollowinc characteristics: ¦
~- Tensile strength 80 kg/cm2 . Compression strength 210 kg/cm Static exchange capacity, as by 0.1 N NaOH solution 2.5 mg.equiv./g of dry eatalyst Recove~ry o:E tertiary isoamylenes from C
_~_____ _______-_ 5 hydrocarbon fraetions . 10 60 g. of the catalyst produced are charged i.nto a reactor cornprising two series-connected s-teel pipes of 12 mm diameter and 1 m length each placed :into a thermostat jaeket. :~
~ C5-Eraetion eonsisting o:E 60Q, 2-methy.l.hutene-2, 18~, 2-methyl-butene-1, 5~ 2-methy.l.but~!ne-3, ancl.L7'k n~ and isop~nkanes is eontinuously fed into th~ r~aetor at a rate of 300 ml/hr in ;, the form of a mixture with methanol at a molar ratio of methanol .
-to the total amount of 2-me-thylbutene-2 and 2-methylbutene-1 .: equal to 65:1. The pressure is maintained a-t 10 atm and the :....................................................................... ....
temperature is 70C. The total rate of conversion of 2-methyl-butene-2 and 2-methylbutene-1 is 79%
An azeotrope eonsisting of 50~ methanol and 50% methyl- ~
tert.-amyl ether and boiling at 62.3C is isolated fram the ~:
. reaction products by rectification. From this azeotrope .~ methyl~tert.-amyl ether of a 99.4% concentration is recovered .. by washing out methanol with water and subjected -to cleeomposit.ion . to give a mixture consisting of 85~ 2-methylbutene-2 and 15%
2-methylbutene-1 wi.th methanol.
The deeomposition is eEEec-ted in a Elow-type reaetor i.
. eomprising a glass pipe of 25 mm diameter provided with a thermo-stat jacket. The catalyst obtai.nc~d is charged into the reactor !~
in the amount of 30 q. Methyl-tert-amyl ether is s~pplied to the reactor at the rate of 50 ml/hr, The reaetor is maintained under , _ .. .

~L~3~
atmospheric pressure and at 80C temperature. Under such condi-tions, the rate of conversion o methyl-tert.-amyl ether is 90%.
The isoamylenes thus produced (85~ of 2-methylbutene-2 and ; 15~ of 2 methylbutene 1), after isolation by rec-tification have the total concentration of 99.9 Example 9 80 parts by weight of a Einely divided (0.03 to 0.1 mm size) and dried catlon-exchange resin (sulphonated copolymer of styrene with divinylbenzne) are mixed with 20 parts by weight of powder-like (0.1 to 0.5 mm size) polypropylene, 20 par-ts by ; weight of compressor oil, and 5 parts by weight oE water.
The mixture is charged into a double-screw extruder r provided with the same equipment as in Example 5.
r~xtrusioll cond:itions L
1. ~'emperature Oe the 1 St ZOlle 180C
Temperature oE the 2 nd zone 200C
Die temperature 190C
2 Screw rotation speed 60 r.p.m.
3. Cooling water temperature 20C
The resulting catalyst has the same shape as in Example 5. After treatimg with toluene, -the catalyst has the following ,, .
characteristics:
Tensile strength 20 kg/cm2 ~.`
Compression strength 80 kg/cm2 Static exchange capacity, as by 0.1 N NaOH solution 3.6 mg.equiv./g o~ dry catalyst Example 10 75 parts by weight o a finely divided (0.03 to 0.1 mm size) and dried cation - exchange resin (sulphonated copolymer of styrene wi-th divinylbenzene) are mixed with 25 parts by weight of powder-like (0.1 to 0.5 mm size) polypropylene, 10 parts by . ,, h~

:
weight of dioctyl phthalate ! and 20 parts by weiyht of water, The mixture is charged into a double~screw ex-truder provided with the same equipment as in Example 5.
Extruslon conditions - 1. Temperature oE the 1 st zone 180C
Temperature of the 2 nd zone 200C
Die temperature 190C
: 2. Screw rotation speed60 r.p.m.
3. Cooling water temperature 20C
The resulting catalyst has the same shape as in Example 5.
~fter treatincJ with hexane, the cat~lyst has the ~ollowing characteristics:
Tens:ile strencJth50 kg/cm2 Compression strength140 kg/cm 3 Static exchange capacity, as by t.
0.1 N NaOH solution 3.3 mg.e~uiv./g of dry ca-talyst ; Example 11 70 parts by weight of a finely divided (0.03 to 0.1 mm !~
size) and dried cation-exchange resin (sulphona-ted copolymer of ~:
styrene with divinylbenzene) with 30 parts by weight of powder-like (0.1 -to 0.5 mm size) polypropylene, 5 parts by weight dibutyl phthalate, and 30 parts by weight of wa-ter. The mixture is charged into a double-screw extruder provided wi-th the same equipment as in Example 5.
Extrustion conditions 1. Temperature of the 1 st zone 180C
Temperature of the 2 nd zone 200C ;
Die temperature 19.0C
2. Screw rotation speed80 r.p.m.
.
3. Cooling water temperature 20C
.

,~ ,,f ~ ~

The resulting catalyst has the same shape as inExample 5, ..
After treating with hexane, the catalyst has the following characteristics:
Tensile strength 80 kg/cm2 Compression strength 180 kg/cm Static exchange capacity, as by ~;
0.1 N NaO~I solution 3.0 mg.equiv./g of dry catalyst Exam~les illustratinq enhanced static exchan~e capacity of the catalyst Example 12 .. i , .
20 g of the catalyst prepared as in Example 1 are ; dried in a dryiny cabinet at a temperature o 105-l.lO'~C for 3 hours ancl therl charc~ed into a 500 ml El~sk, ~ncl 70 ml oE
carbon tetrachloride is pourecl therein. 'rhe catalyst is allowecl to remain at room temperature for one hour. Thereafter, the flask contents is heated to a temperature of 56-58C and 50 ml of chlorosulphonic acid are added in small portions thereto with continuous stirring. During hea-ting to the predetermined temperature and stirring, the catalyst is treated with chloro-sulphonic acid for 3 hours. Then the liquid is drained and the catalyst is treated with water until HCl is absent.
- Isomerization of 2-methylbutene-1 to 2-methylbutene-1 . ~. .
32 g of the resulting catalyst are charged in-to the top of a reactor comprising a steel pipe of 28 mrn diameter and ; 1.5 mm height provided with a boiler and clephlegmator. The remaining volume of the reactor i.s Eilled with rectiElcation packing made of nichrome wire. A starting isoamylene feed consisting of 15~ 2-methylbutene-1 and 85~ 2-methylbutene-2 is continuously supplied to the rectiEication 20ne of the reactor ; at a rate of 100 q/hr, wherefrom vapours of isoamylenes - ~ containinq 70~ 2-methylbutene-1 and 30~ 2-methylbutene-2 are delivered to the catalyst.

~t .. '' .. ': , . ,........ ' ~. ,."' ':

~3~
The reactor is maintained at 70C and under 3 atm pressure. Vnder these conditions, isomerization of 2-methylbu-tene-1 3 into 2-methylbutene-2 takes place. Vapours of 2-methylbutene-2 and unreacted 2-methylbutene-1 are passed into the dephlegmator, condensed therein and in the form of reflux are sprayed on-to the catalyst. 2-methylbutene-2 as a higher-boiling product is concentrated in the lower rectification zone of the reactor and is d:ischarged from the still as the final product of a 99% concen~
tration. The output of 2-methylbutene-2 per kg of the catalyst is ~00 g/hr.
Example 13 20 g of the catalyst prepared as in Example ~ are dried and treated with a solvent under the condltlons of Example 12, exeeE)t that the solvent is cl:ichloroethane in the amount o~ 70 ml, and the temperature oE the eatal~st treatmerlt with ehlorosulphonic 3 acid is maintained within the range of from 35 to 37C for 5 hours.
Example 14 20 g of the catalyst prepared as in Example 3 are treated with dichloroethane under the conditions of Example 12 without pre-drying, while the catalyst treatment with chlorosulphonic - acid is performed as in Example 13, except that the saponification : agent is a 2% NaOH solution. The treatment with this solution is effected until no chlorine ions are detected, whereafter the .;.
catalyst is additionally treated with 300 ml. of a 8 % HCl solu-tion.
Example 15 20 g of the catalyst prepared as in E~ample 6 are clried and treated with diehloroethane uncler the condLt:ions of Example 12, except that the catalyst is treated with concentrated (98~) sulphuric acid for 5 hours at the temperature of 100C, :: ~
wherea~ter the liquid i5 draine~ and the catalyst is washed with water.

Static exchange capacity and activity of the catalyst .. . . . ., ~, , ... . ~

~3~
prior to and after said treatment are shown in the following - Table.
Table : r--------------------Example Static exchange capacity of -the Activity, %
No catalyst, as by 0.1 N NaOH solu-tion; mg.equiv./g. of subs-tance __________________ _______________ _________ __________ prior to after prior to after treatmenttreatment treatment treatment __________ __________________ _______________ __________ ,___________ 12 2.~ 3.7 6~ 84 13 3.0 4.0 65 87 L0 14 3.0 3.74 65 84 15 __________________ _______________ ___________ 1__________ ; The catalys-t static exchange capacity is determinecl by a conventional method such as by treat.:ing thc catalyst with 0.:l N
NaOII solution, fo:l.lo~ed by Ei:Ltration oE ~he unreacted ~laOII
with 0.1 N HCl solution in the presence of an indica-tor such as p t methyl orange. ~-The catalyst activity is determined by the rate of . ~.
isobutylene evolution during dehydration of tert.-butyl alcohol under s-tatic condi-tions according to the following procedure. ,.
50 ml of tert.-butyl alcohol in the form of a 88%
aqueous solution thereof are charged into a flask provided with a reflux condenser, and heated to reflux, whereafter 10 g of a ; ~ .
pre-dried, at 105-110C, catalyst are added thereto. After 2 ` hours from the charging momen-t, the volume oE evolved isobutylene i.5 measured. `
The catalyst activity is calcu:l.ated as a rat:io oE
practically evolved isobutylene to the theoretically possible _ ; amount thereof.
',,' : ' .:; ' ..
.:: -- 19 , ` ' '` ~ ,"', : ,

Claims (18)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for producing a catalyst based on cation-exchange resins which comprises mixing a cation exchange resin with a thermoplastic material in a weight ratio of from 1.5: 1 to 4:1 in the presence of at least one additive selected from up to 20 parts by weight an organic additive compatible with the thermoplastic material and 5 to 50 parts by weight of water based on the weight of the catalyst and extrusion-moulding of the resulting catalyst mixture at the melting point of the thermoplastic material.

2. A method as claimed in claim 1, wherein the catalyst mixture is stretched simultaneously with said moulding.

3. A method as claimed in claim 1, wherein organic additives are soluble in organic solvents.

4. A method as claimed in claim 3, wherein the catalyst is treated with an organic solvent.

5. A method as claimed in claim 1, wherein water is admixed with the resin and thermoplastic material in an amount of from 5 to 30 weight parts by weight of the catalyst.

6. A method as claimed in claim 3, wherein water is admixed in an amount of from 5 to 30 weight parts by weight of the catalyst.

7. A method as claimed in claim 1, wherein the cation-exchange resin provides a water content of from 5 to 50 weight parts by weight of the catalyst.

8. A method as claimed in claim 2, wherein the cation exchange resin provides a water content of from 5 to 50 weight parts by weight of the catalyst.

9. A method as claimed in claim 3, wherein the cation exchange resin provides a water content of from 5 to 50 weight parts by weight of the catalyst.

10. A method as claimed in claim 1, wherein the cation exchange resin contains water and water is supplied to the admixing, the total amount of water being 5 to 50 weight parts by weight of the catalyst.

11. A method as claimed in claim 3, wherein the cation exchange resin contains water and water is supplied to the admixing, the total amount of water being 5 to 50 weight parts by weight of the catalyst.

12. A method as claimed in claim 1, wherein the resulting catalyst is swollen in a chlorinated aliphatic solvent and the swollen catalyst treated with a highly active sulphonating agent at a temperature within the range of from 30 to 100°C.

13. A method as claimed in claim 12, wherein as the sulphonating agent is concentrated sulphuric acid and the catalyst treatment is effected at a temperature within the range of from 60 to 100°C.

14. A method as claimed in claim 12, wherein the sulphonating agent is chlorosulphonic acid and the catalyst treatment is effected at a temperature within the range of from 30 to 60°C, whereafter the catalyst is treated with a saponifying agent.

15. A method as claimed in claim 14, wherein the saponifying agent is water.

16. A method as claimed in claim 14, wherein the saponifying agent is made of an alkali solution and such treatment of the catalyst is further treated with a mineral acid solution.

17. A method as claimed in claim 12, wherein prior to the treatment of the catalyst with the chlorinated aliphatic solvent, said catalyst is pre-dried.

18. A method for producing a highly porous granulated catalyst based on cation-exchange resins which comprises mixing a cation-exchange resin selected from the group consisting of a sulphonated copolymer of styrene with divinylbenzene, a sulphonated copolymer of styrene with butadiene and of the condensation product of phenosulphonic acid with formaldehyde, with a thermoplastic material selected from the group consisting of polyethylene, polypropylene, polyvinylchloride and polystyrene in a weight ratio of cation-exchange resin to said thermoplastic material of from 1.5:1 to 4:1, said mixing being performed in the presence of at least one of water in an amount of from 5 to 50 weight parts by weight of the catalyst and an organic additive in an amount of up to 20 weight parts by weight of the catalyst and selected from the group consisting of a minoral oil, ester plasticizers and non-ionic emulsifiers which are compatible with the thermoplastic material and soluble in organic solvents, followed by extrusion-moulding of the resulting mixture at the melting point of the thermoplastic material in the form of rings, granules, strips and cylinders and treating the catalyst with an organic solvent selected from aliphatic and aromatic hydrocarbons, alcohols and ethers.