BE537405A - - Google Patents

Description

       

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   The present invention relates to the production of long chain olefin polymers, and more particularly to long chain olefins having relatively straight chain configurations which are particularly freely useful for the alkylation of aromatic hydrocarbons and for the production of detergents. of the alkyl aryl sulfonate type.



    A very effective type of detergent has been developed in the art which detergent is characterized as being an aryl alkyl sulfonate containing only one, and not more than one, alkyl group of about 10 to 18 carbon atoms per. group, and preferably having a straight or slightly derivatized chain configuration, such detergents being further characterized in that they contain less than 3, and preferably no more than a single other alkyl substituent containing less than 3 carbon atoms. carbon per group, an aromatic ring, preferably a benzenoid, and a sulphonate salt radical whose cation has a metallic or non-metallic composition derived from the corresponding inorganic base or from organic bases containing nitrogen.



   A method of producing the type of detergent mentioned above comprises the alkylation of an aromatic hydrocarbon, which if it is benzenoide, may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, methyl ethylbenzene and diethylbanzene with an olefinic, preferably straight chain, hydrocarbon containing about 10 to 18 carbon atoms per molleoule, sulfonation of the resulting alkyl aryl hydrocarbon and neutralization of the sulfonic acid formed therefrom with an organic base containing nitrogen or an organic alkali, as desired.



   The present invention relates firstly to the preparation of a suitable olefinic material which can be used as an alkylating agent for the preparation of detergents of the type mentioned above, said olefinic alkylating agent being formed by polymerizing propylene. .



   One of the objects of the present invention is to provide an improved process for the polymerization of propylene to form monoolefins having from about 10 to 18 carbon atoms per molecule which can be used in the preparation of detergents of the alkyl aryl sulfonate type. .



   Another object of the invention is to increase the yield of desirable olefin polymers having a boiling point of between about 335 F and 435 F produced by the polymerization of propylene.
Another object of the invention is the production of olefinic polymers having a boiling point between about 335 and 435 F starting from propylene and polymers of propylene having less than about 12 carbon atoms per molecule.



   A specific embodiment of the present invention relates to a process which comprises the polymerization of substantially dry propylene in the presence of a solid form polymerization catalyst, the substantially continuous separation of the resulting product from a fraction. containing olefins having about 10 to 18 carbon atoms per molecule, and recirculating polymers containing about less than 12 carbon atoms per molecule in the polymerization zone along with additional raw material containing propylene.



   Another embodiment of the present invention relates to a process for the production of polymers having a boiling point of between about 335 and 435 F, in which a mixture consisting of

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 by a propane-propylene fraction and by a polymer fraction of propylene having a boiling point of less than about 335 F, in contact with a phosphoric acid catalyst in solid form at a temperature of between about 250 and 450 F, and at a pressure of from about 100 to 2000 pounds per square inch, the resulting product being fractionally distilled to separate the desired polymer fraction from lower or higher boiling point polymers. high,

   and by returning to the circuit at least a part of said polymers with a lower boiling point in the zone of initial polymerization.



     Another embodiment of the present invention relates to a process for the production of polymers having a boiling point of from about 355 to 410 F, in which a mixture consisting of a propane-propylene fraction and a fraction of polymer of propylene having a boiling point below about 355 F in contact with a phosphoric acid catalyst in solid form at a temperature of about 275 to 375 F and a pressure of about 600 and 1200 pounds per square inch, fractional distillation of the resulting product to separate the desired polymer fraction from lower or higher boiling point polymers,

   and the reintroduction into the circuit of at least a part of said polymers with a lower boiling point towards the initial polymerization zone.



   It has now been found that the production of high boiling point polymers (and more particularly tetramers and higher polymers) starting from propylene and its low boiling point polymers is improved by achieving the treatment for polymerization on substantially dry raw material and in the presence of a phosphoric acid catalyst in solid form, prepared as disclosed in US Pat. No. 1,993,513 and other patents. .

   This finding contradicts previous findings made in the production of motor fuel having a boiling point close to that of gasoline by the polymerization of propylene and propylene-butylene mixtures starting from mixtures of gasoline. gaseous hydrocarbons also containing propane, butanes, and other normally gaseous hydrocarbons. In olefin polymerization operations to produce polymerized gasoline, it has been the usual practice to add water or steam to the inlet of each polymerization reactor containing a phospho acid catalyst. - solid ric, in order to maintain the state of hydration and the activity of the catalyst and to reduce the tendency for deposits of coke or other substances similar to coke, on the catalyst.

   It has now been found in the polymerization of a propane-propylene fraction in the presence of a recirculated liquid polymer such as nonylene, that a decrease in the water content of the raw material increases the conversion per pass for a separation. given operating conditions, and also improves the yield of C12 and higher olefins based on the amount of propylene converted.



  The operation envisaged with dry raw materials is only carried out when substantially large quantities of liquid polymers are reintroduced into the process in the reaction section, so that the concentration of liquid polymers is relatively high in the layer. catalyst. This type of polymerization process produces a high yield of propylene tetramers and higher polymers from propylene and its polymers, the latter containing up to about 12 carbon atoms per molecule.



   It is well known that the solid phosphoric acid catalyst can be used for a considerable period of time without regeneration.

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 for the polymerization of propylene to produce boiling point polymers similar to those of gasoline. Maintaining the activity of the catalyst for an extended period of time is achieved by introducing small amounts of water and thereby maintaining the catalyst in the selected state of hydration which is necessary to retain its. activity at a catalyst temperature which generally is about 450 to 550 F. Catalyst lives in the range of about 100 to 125 gallons of polymer per pound of catalyst are quite normal in gasoline production operations.

   However, when the phosphoric acid catalyst was employed to produce olefinic polymers containing long chain olefinic hydrocarbons having about 10 to 18 carbon atoms per molecule by re-circulating polymers having a lower number. of carbon atoms it was found that the activity of the solid phosphoric acid catalyst fell very quickly and catalyst lifetimes of only 5 to 10 gallons per pound were obtained. that instead of having to maintain a specific water content in order to maintain the catalyst in the state of hydration as was necessary in the gasoline production operation,

   just the opposite was needed in the production of long chain olefinic hydrocarbons from propylene and low boiling point polymers back into the circuit. In order to obtain a catalyst life long enough to make the operation commercially possible when entering polymers into the circuit, it has been found essential to maintain the water content of the newly introduced propylene in the circuit. - below about 0.03 mole percent. When a water content appreciably in excess of this amount is employed, the catalyst instead of retaining its activity as one would expect from the findings in the polymerization of propylene for gasoline, in fact loses its activity quickly.



   The present process is also carried out in a continuous manner by directing a propane-propylene fraction and a mixture of polymers of propylene to a reactor of suitable construction containing a solid phosphoric acid catalyst, and more particularly a precalcified mixture. born from an acid of phosphorus and diatomaceous earth or other silicious adsorbent such as montmorillonite, etc., maintained at a temperature of about 250 to 450 F and a pressure of about 100 to 2000 pounds per square inch. The process is preferably carried out with a catalyst temperature of about 275 to 375 F and a pressure of about 600 to 1200 pounds per square inch.

   By this treatment, a substantial proportion of the propylene present in the introduced propane-propylene mixture is converted to polymers, including the trimers, pentamers, and higher boiling point propylene polymers. In order to produce relatively high yields of the higher boiling point polymers, it has been found advantageous to separate the lower boiling point polymers, for example by means of fractional distillation, and to return these. lower boiling point polymers containing a relatively high proportion of nonylenes in the polymerization reactor into which the new propane-propylene fraction is introduced.



   The recirculation material to the polymerization reactor may also include monoolefins, preferably straight chain or slightly branched chain structure, from any other source, such as from another polymerization process or cracking. hydrocarbons or dehydrogenation process, which gives a mixture of saturated and monoolefinic hydrocarbons containing about 6 to 12 carbon atoms per molecule.

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   In addition, in order to obtain a relatively high yield of polymers with a boiling point of about 335 to 435 F, it has been found necessary to dry the propane-propylene raw material so that it does not contain more. about 0.03 mole percent and preferably no more than about 0.1 mole percent water. When the mixture consisting of a propane-propylene fraction and recirculated polymers is substantially dry, 60 to 80% or more of the resulting polymer is obtained having a boiling point of approximately between the desired limits of 335 to 435 Fo
The amount of water which is allowed in the mixture of propane-propylene and material reintroduced into the circuit also depends on the temperature and pressure employed for the polymerization.

   At the higher temperature between the limits of about 250 and 450 F, more water may be present than when operating at the lower temperatures. The amount of water in the total feed may also be greater at low pressures than at high pressures.



   In order to achieve these relatively high yields of higher boiling point polymer fractions, the liquefied propane-propylene fraction fed to the process is mixed with from about 0.2 to about 5 times its volume of polymers. propylene with a boiling point of less than 335 Fo The mixture of hydrocarbons thus introduced to come into contact with the solid phosphoric acid catalyst contains approximately between 0.2 volumes of propylene polymers for a volume of new fraction C3 and 5 volumes of low-boiling polymers for one volume of new fraction C3 Thus, the volumetric ratio of total feed relative to fraction C3 is approximately from 1.2 to 6 while the ratio preferred of the total volumetric feed is about 2.0 to 3.5,

   that is, a single volume of liquid C3 fraction and 1.0 to 2.5 volumes of low boiling point liquid polymers. In order to produce a relatively high yield of long chain olefinic hydrocarbons containing about 10 to 18 carbon atoms per molecule, the new propane-propylene fraction is also introduced at a rate corresponding to an hourly space velocity. of liquid fraction C3 from 0.1 to approximately 5. By the expression “hourly liquid space velocity” is meant the volumes of liquid admitted per hour per volume of catalyst.

   These new propane-propylene feed rate limits are influenced by the final propylene conversion required, since in some cases high conversions corresponding to low feed rates may be desirable, and on the other hand, in other cases, low conversions may be satisfactory obtainable by operations at high feed rates.



   The propane-propylene fraction introduced into the process can be dried by any suitable means such as distillation, or by passing through a tower containing activated alumina which absorbs water from the treated hydrocarbons, or else the propane fraction. propylene can be cooled to a relatively low temperature in order to remove virtually all of the water contained therein.

   Other means, such as rinsing with a high boiling point glycol or other suitable dehydrating agent may also be employed.
The preferred polymer fraction formed by the present process and having a boiling point of between about 325 and 435 F at pres-

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 The concentration of 760 mmo of mercury consists essentially of monoolefinic hydrocarbons having from about 10 to 14 carbon atoms per molecule and having a appreciably greater proportion of monoolefinic hydrocarbons with 12 carbon atoms per molecule.

   These monoolefinic hydrocarbons can be employed as described below to produce alkyl aromatic hydrocarbons convertible (by sulfonation and neutralization with a base) to surface active compounds useful as detergents.



   The process according to the present invention is further illustrated by the accompanying drawing which shows a suitable apparatus in which the process can be carried out. Thus, a propane-propylene fraction containing about 30 to 60% propylene, a relatively large amount of propane and small amounts of paraffinic and olefinic hydrocarbons containing 2 to 4 carbon atoms per molecule, is introduced by line 1 and valve 2 to pump or compressor 3 which discharges through line 4 and valve 5 into heating coil 6 which receives heat from heater 7.

   From coil 6, the heated hydrocarbons are directed through line 8 and valve 9 to reactor 10 containing one or more layers or sections of solid phosphoric acid catalyst which is a precalcined mixture of phosphoric acids and earth. diatoms.



  From reactor 10 the resulting mixture of propane, unconverted propylene and polymers of propylene is discharged through line 11 and valve 12 into stabilizer 13 which receives heat from the boiling coil 14. gaseous hydrocarbon forms separated from the polymers in the stabilizer. 13 are directed through line 15 and valve 16 to storage or other use not shown in the attached schematic drawing, while stabilized liquid polymers are discharged from stabilizer 13 through line 17 and valve 18 into the fractionator 19 to which heat is supplied by means of the boiling coil 20.



   From the top of the fractionator 19, a mixture of low boiling point polymers, such as those containing 6 to 12 carbon atoms, are distilled and directed through line 21 and valve 22 to. the condenser 23 and the resulting mixture of condensate and non-condensed vapors then pass through the downward pipe 24 and valve 25 to the manifold 26 having a pipe 27 serving for the evacuation of the gas and containing the valve 28. The low boiling point liquefied polymers comprising essentially C6 to C12 olefins which are also collected in the manifold 26, are continuously withdrawn through line 29 and valve 30 by pump 31 which discharges into line 12. containing valve 33.

   At least part of the hydrocarbons which pass through line 32 is directed therefrom through bypass line 34 and valve 35 into line 4 already mentioned through which the new propane-propylene fraction is introduced into the polymerization process. If desired, some of the raw material can be drained from line 32 through valve 33 to storage or other use not shown in the accompanying drawing.



  Also, some of the low boiling point polymers passing through line 32 may be returned to the vicinity of the top of fractionator 19 by means not shown in the drawing, to help control temperatures therein. .



   The desired polymer fraction from which the low boiling polymers are thus separated in the fractionator 19 accumulates near the bottom of said fractionator and is removed therefrom.

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 through line 36 and valve 37 to cooling and storage not shown in the drawing The higher boiling point polymer fraction thus discharged through line 36 is useful for alkylating an aromatic hydrocarbon to form an alkylated aromatic hydrocarbon convertible into an alkaryleo sulfonate detergent If desired,

   this higher boiling point polymer fraction may be subjected to fractional distillation to separate a desired boiling point fraction from a higher boiling point residue.



   Example 1
Several tests were made in which a substantially dry hydrocarbon fraction, containing 0.2 mole percent ethylene, 3.0 percent ethane, 33.3 percent propylene, 63.1 percent propane , 0.1 percent butylene, and 0.3 percent butane, were mixed with polymers formed from said gas mixture and having a boiling point of between about 100 and 356 F. The reaction was carried out. the mixture of c3 hydrocarbons and low boiling point propylene polymers at a temperature (maximum reactor temperature) of about 300 to 400 F in the presence of a calcined mixture of pyrophosphoric acid and diatomaceous earth under shape of cylindrical pellets of 5 x 5 mm.

   The polymerization tests mentioned in Table 1 were carried out at a gauge pressure of 750 to 760 pounds per square inch.



   Other operating conditions, such as the amount of water present in mole percent in the propane-propylene raw material and the hourly rate at which this raw material was introduced into the process, are shown in the table with the yields. as a fraction of polymers with a boiling point of between 356 and 410 F. and generally indicated as "the tetramer fraction".

   The water present in the combined feed to the polymerization reactor was determined by the method of Karl Fischer Angew Chem 48 394 (1935), whereby the excess water content of about 0.0008 mole percent , can be determined:
Table 1 Polymerization of a propane-propylene fraction in the presence of a phosphoric acid catalyst in the solid state.

   

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<tb> Test <SEP> N <SEP> 1 <SEP> 2 <SEP> 3
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 ------------------ 'V'iI7TI¯¯¯¯¯¯ ----------------.----- --------
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<tb> Duration <SEP> of <SEP> test <SEP> in <SEP> hours <SEP> 24 <SEP> 9 <SEP> 29
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<tb> Operating <SEP> conditions
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<tb> Temperature <SEP> in <SEP> F <SEP> to <SEP> the <SEP> output <SEP> of the
<tb>
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<tb> preheater <SEP> of the <SEP> reactor <SEP> @ <SEP> 266 <SEP> 355 <SEP> 390
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<tb> Maximum <SEP> temperature <SEP> in <SEP> F <SEP> of the
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 reactor 00000000000000000.0.00.0 300 399 399 Reactor pressure in pounds per square inch .000.0000000000 .... 0. 750 751 760 Ratio (volumetric) of the total supply 00000..00..0 .... 00 ...

   2.13 1.99 1.94
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<tb> Spatial <SEP> speed <SEP> hourly <SEP> of liquid <SEP>
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 of the new power supply ôeooo * o 0.36 0.58 0.50
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<tb> Spatial <SEP> speed <SEP> hourly <SEP> of liquid <SEP>
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<tb>
<tb> New <SEP> power supply <SEP> BPD <SEP> 1
<tb>
<tb>
<tb> per <SEP> 1000 <SEP> pounds <SEP> of <SEP> catalyst <SEP> @ <SEP> 26.6 <SEP> 43. <SEP> 1 <SEP> 36.7
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<tb>
<tb> Propylene <SEP> BPD1 <SEP> per <SEP> 1000 <SEP> pounds <SEP> of
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 catalyst e a o o e o 0 0 0 0 0 0 o a o o .. e o 0 o e.

   8.2 13.8 1 V o 6 Water in mole percent in the total supply 0000.000..000.0.00 0.00 0.03 0.03
 EMI7.9
 
<tb> Yields <SEP> in <SEP> polymers <SEP> of <SEP> the <SEP> fraction
<tb> 356-410 F
<tb> Books / pound <SEP> of <SEP> propylene <SEP> allowed <SEP> @ <SEP> 0.66 <SEP> 0.52 <SEP> 0.45
<tb> Pounds / pound <SEP> of <SEP> propylene <SEP> converted <SEP> 0.83 <SEP> 0.56 <SEP> 0.52
<tb> Volume <SEP> for <SEP> one hundred <SEP> of <SEP> propylene <SEP> allowed <SEP> 44.7 <SEP> 3506 <SEP> 30. <SEP> 4
<tb> Pounds / Hour / Pound <SEP> of <SEP> catalyst ...

   <SEP> 0.036 <SEP> 0.040 <SEP> 0.031
<tb> Products <SEP> polymers, <SEP> total <SEP> net
<tb>
 
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 ZoaPa-356 Fooaeooooo00oooooeaaoooo 7.7 15.5 17.4 3.16 -410 Foeooeaoo.ooooooe.oo.ooooo 83.5 56.4 52.0 Above 410 oooomoeooaooeoo0o 808 28.1 30.6
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<tb> Total <SEP> @ <SEP> 100.0 <SEP> 100.0 <SEP> 10000
<tb>
 Barrels of liquid per day (24 hours).



   The results in Table 1 show that from the dry starting material (0.00% water) yields of olefin polymers were obtained at
 EMI7.12
 boiling point between 356 and 4100F. 9 lower than those obtained when the combined feed comprising a new fraction of propane-propylenes and polymers re-introduced into the circuit (IBP at 356 F) contained 0.03 mole percent d 'water.



  Example II
Another polymerization test was carried out on a propane-propylene fraction containing 42 mole percent propylene and using a solid phosphoric acid catalyst whose analysis gives 62 percent P2O5 obtained by calcining at about. 370 0 (698 F) a mixture of phosphoric acid (mainly pyrophosphoric acid) and diato-

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   meso In Table 2 which gives the operating conditions and the results, the expression "less than 0,

  0008 mole percent water in the total feed "is approximately the minimum quantity determined by the method of water analysis also employed for the new propane-propylene fraction introduced. The new propane-propylene fraction had markedly dryness. greater than that represented by this value and the total feed was even drier because the recirculated polymers were dehydrated in the depropanizer equipment.



   Table II Polymerization of a propane-propylene fraction in the presence of a solid phosphoric acid catalyst
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<tb> Duration <SEP> of <SEP> test <SEP> in <SEP> hours <SEP> 12
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<tb> <SEP> operating conditions <SEP>: <SEP>
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<tb> Temperature <SEP> in <SEP> F <SEP> to <SEP> input <SEP> of <SEP> reactor <SEP> 281
<tb>
<tb> Maximum <SEP> temperature <SEP> of the <SEP> reactor <SEP> in <SEP> F <SEP> 354
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<tb> Pressure <SEP> of the <SEP> reactor <SEP> in <SEP> pounds <SEP> by <SEP> inch
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 square to the pressure gauge 000000000000000.0.0 .. 755 Ratio (volumetric) of the total supply 00000000008000000000.00000.0 .... 0 3006
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<tb> Spatial <SEP> speed <SEP> hourly <SEP> of the <SEP> liquid <SEP> of
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 the new power supply 0.00000000 .....

   0.66
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<tb> Spatial <SEP> speed <SEP> hourly <SEP> of the <SEP> liquid <SEP> of
<tb>
 
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 total feed esaoooeoooeooeoees 2.02 New feed BDP per 1000 pounds of catalyst 000.00000.0.000000 .... 00 .. 4808 Propylene BDP per 1000 pounds of catalyst o000ooooosooeeooeoeoaoonesaovevoese 1907 Mole percent water in the combined feed, less than .0000.000000.000.0 ... 000008 Age of catalyst, gallons of bottoms per pound oo.o ... ocooeQo.o.ee.006.00..0 4.24 Conversion of propylene o.oo ... ,, oeo , o, o.ooooo 74
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<tb> Experimental <SEP> recovery, <SEP> in <SEP> weight <SEP> for <SEP> hundred <SEP> 97.3
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<tb> Yields <SEP> (for <SEP> a <SEP> recovery <SEP> of <SEP> 100%) <SEP>:

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<tb> fraction <SEP> 356-410 F-
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<tb> Books / book <SEP> of <SEP> propylene <SEP> admitted <SEP> .. <SEP> 0.53
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<tb> Pounds / pound <SEP> of <SEP> propylene <SEP> converted <SEP> 0.72
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<tb> Volume <SEP> for <SEP> one hundred <SEP> of <SEP> propylene <SEP> allowed <SEP> 36.1
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 catalyst 0..0..000..0..0 ... 00 .... 0.07
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<tb> Fraction <SEP> 338-438 F <SEP> of <SEP> "bottoms",
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<tb> books / book <SEP> of <SEP> propylene <SEP> conver-
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 ti ..............................

   0.80
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<tb> Weight <SEP> in <SEP> for <SEP> one hundred <SEP> of <SEP> propylene <SEP> allowed <SEP> -
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<tb> Propylene <SEP> in <SEP> the <SEP> gas <SEP> exhausted <SEP> @ <SEP> 26
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 Total polymer product 00.0000000 ...... 0 74 Net liquid passing through the fractionator 000000000000 ...... 0..00 ... 10.9
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<tb> Weight <SEP> for <SEP> hundred <SEP> of <SEP> propylene <SEP> converted <SEP> Liquid <SEP> net <SEP> of <SEP> passage <SEP> of <SEP> the device <SEP> of
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 I BOP at 356 F 000000000000..00.00..0 14.0 Above 356 F .00.00.000000 ... 0. 007 Tctal 00000000..0000000.00 l4eT

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<tb> Product <SEP> polymerized <SEP> total <SEP> -
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 IoBoPo at 356 Foo..ooooo.o.o ....... oo ... oo.o.o.ooo 22.0 356-41o Foasoooaoeoooosaseoeseeeooaoaoeoaeoooaoae 71.7 Above 410 Foeoweoo * o * .. oooooe ... ooee.oeoe * 6.3
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<tb>
<tb> New <SEP> supply <SEP> in <SEP> mole <SEP> for <SEP> hundred <SEP> of <SEP> propylene <SEP> @ <SEP> 42.0
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<tb> Gas <SEP> of <SEP> stabilization <SEP> in <SEP> mole <SEP> for <SEP> hundred <SEP> of <SEP> propylene <SEP> @ <SEP> 15.8
<tb>
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 in circuit), spec. at 60 F .......................... 0.7378
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<tb> Distillation <SEP> Engler <SEP> - <SEP>
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 Initial boiling point in F .......... 0 ...... 0 .. 144 End point in F 0..0..0..0 ........ ......... 0 ....... 353 Podbieiniak distillation-volume of liquid percent above 356 Pao..o ..,. Oe.o ........ o ...... o ..... oo, e.oo. 5.0 Average molecular weight 0 ............................... 0. 124
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<tb> Weight <SEP> by <SEP> centolefins, <SEP> before <SEP> and <SEP> after <SEP> test <SEP> 91-92
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<tb> "Bottoms" <SEP> of <SEP> the <SEP> of <SEP> fractionation <SEP> (tetramers <SEP> and <SEP> poly-
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<tb> mothers <SEP> plus <SEP> high) <SEP>:

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 Specific gravity at 60 F, o, ow ....... o .... * .......... oo..o. 0.7775 Engler Distillation - Initial boiling point in F ..................... 356 End point in oF ........... ......................... 469 Podbielni distillation, volume of liquid in percent ...



  IOBOP. to 356 F. 080080.0 ............ & .......... 0 ....... 9.5 356 to 410 F .00 ....... ................................. 83.5 410 to 428 F .00 .......... ..0 ........................... 1.8 428 to 446 F .0000000..0..00 ....... .................. 0 .. 2.8 446 to 464 F .0 ....... 0 ..... 0 ........ ................... 1.4 Above 464 F 0 ....... 000 ............... 0 ....... 0. 1.0 Percent volume (356 to 410 F) in the fraction boiling above 356 P ........., w 92.3 I.BoPo at, 3., ô Feeoesoeeeeeeesaeeeeeseoeeseeeoooe 3.3 33Bo at 438 F 0 ....... 0 ......................... 92.9 Fraction 356-410 F:

   Specific gravity at 60 F oseooeeeoseeeoeeeeeeeo. 0.7766 Bromide index .... 00 ................ 0 ... 0 ...... 106
The results given in Table 2 show that the total polymer product contained 22 percent of the boiling point polymers below 356 F, 71.7 percent of the boiling point fraction between 356 and 410 F and 6 percent of the higher boiling point hydrocarbons. The "bottoms" of the fractionator which included the polymers remaining after removal of the recirculated material contained 92.9 vol. liquid percent of hydrocarbons with a boiling point between 338 and 438 F and 83,

  5 percent hydrocarbon
 EMI9.11
 essentially monoolefin3ques with boiling points between 356 and 410 f About 6 percent of the "bottoms" of the fractionator had a boiling point of between 410 and 464 F at a pressure of one atmosphere absolute.

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 Example III
The test mentioned in Example 2 at a pressure of about 750 pounds per square inch was continued for 927 hours on the propane-propylene fraction containing 40-42 mole percent propylene and then for a period of 927 hours. Another 244 hours on a Ce fraction containing 31-33 percent propylene and during this time a total of 14.8 gallons of polymer was produced per pound of catalyst.

   These C3 fractions were so dry that the combined feed contained less than 0.0008 mole percent water.



  The total production of the 338-438 F. fraction of these polymers was 13.7 gallons per pound of catalyst; after that the test was stopped, although the catalyst was still active and in good physical condition and could have been used for a longer period. The results obtained in these tests are shown in Table 3 below:

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Table 3.



  Conversion of propylene and I.B.P. polymers - 356 f re-circuited to higher boiling olefins in the presence of a phosphoric acid catalyst, in the solid state.
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<tb>
<tb>
<tb> mole <SEP> for <SEP> hundred <SEP> C3H6 <SEP> 41.8 <SEP> 42.8 <SEP> 41.9 <SEP> 40.3 <SEP> 32.4 <SEP> 31.5 <SEP> 33.4
<tb>
<tb>
<tb>
<tb> Combined <SEP> power supply,
<tb>
<tb>
<tb> mole <SEP> for <SEP> hundred <SEP> C3H6 <SEP> 20.9 <SEP> 21.0 <SEP> 21.4 <SEP> 20. <SEP> 2 <SEP> 16.2 <SEP> 16.1 <SEP> 17.

   <SEP> 3
<tb>
<tb>
<tb>
<tb>
<tb> Total <SEP> duration <SEP> of <SEP> the op-
<tb>
<tb>
<tb> ration <SEP> from <SEP> the <SEP> com
<tb>
<tb>
<tb> start <SEP> of <SEP> test
<tb>
<tb>
<tb> in <SEP> hours <SEP> @ <SEP> 499 <SEP> 801 <SEP> 882 <SEP> 927 <SEP> 1.085 <SEP> 1.142 <SEP> 1.171
<tb>
<tb>
<tb>
<tb> Temp <SEP> f <SEP> of the preheating <SEP>
<tb>
<tb>
<tb>
<tb> feur <SEP> of the <SEP> reactor ..... <SEP> 280 <SEP> 245 <SEP> 255 <SEP> 262 <SEP> 310 <SEP> 310 <SEP> 310
<tb>
<tb>
<tb> Temp.max.in <SEP> f <SEP> of the <SEP> cata-
<tb>
<tb>
<tb> lyzer.

   <SEP> 350 <SEP> 350 <SEP> 350 <SEP> 353 <SEP> 371 <SEP> 370 <SEP> 369
<tb>
<tb>
<tb>
<tb> Volumetric <SEP> report
<tb>
<tb>
<tb>
<tb> from <SEP> the power supply <SEP> tota-
<tb>
 
 EMI11.4
 the ..o..e .... o .., o, oe..3 .o 3.1 2.9 3.0 2.8 2.9 2.9
 EMI11.5
 
<tb> New <SEP> power supply,
<tb>
<tb>
<tb>
<tb> L.H.S.V. <SEP> 0.70 <SEP> 0.66 <SEP> 0.69 <SEP> 0.69 <SEP> 0.92 <SEP> 0. <SEP> 92 <SEP> 0.92
<tb>
<tb>
<tb>
<tb>
<tb> Combined <SEP> power supply,
<tb>
<tb>
<tb>
<tb>
<tb> L.H.SoV. <SEP> 2.10 <SEP> 2. <SEP> 03 <SEP> 2. <SEP> 01 <SEP> 2. <SEP> 05 <SEP> 2. <SEP> 62 <SEP> 2.

   <SEP> 68 <SEP> 2.64
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Age <SEP> of <SEP> catalyst, <SEP> in
<tb>
<tb>
<tb>
<tb>
<tb> gallons <SEP> of <SEP> the <SEP> fraction
<tb>
<tb>
<tb>
<tb>
<tb> 338-438 F <SEP> by <SEP> book <SEP> of
<tb>
 
 EMI11.6
 catalyst ** o * o, oooot 3-59 7.8 9.3 9.8 12.2 13.2 13.7
 EMI11.7
 
<tb> Conversion <SEP> of the <SEP> propylè-
<tb>
<tb>
<tb> ne, <SEP> for <SEP> hundred <SEP> @ <SEP> 68 <SEP> 73 <SEP> 74 <SEP> 72 <SEP> 75 <SEP> 73 <SEP> 77
<tb>
<tb>
<tb>
<tb> <SEP> yields in <SEP> polymers,
<tb>
<tb>
<tb>
<tb>
<tb> weight <SEP> for <SEP> hundred <SEP> of <SEP> C3H6
<tb>
<tb>
<tb>
<tb>
<tb> converted
<tb>
<tb>
<tb>
<tb> I.B.P.- <SEP> 356 F <SEP> @ <SEP> 12. <SEP> 7 <SEP> 7.1 <SEP> 20.3 <SEP> 17.9 <SEP> 16.2 <SEP> 15.5 <SEP> 18.9
<tb>
<tb>
<tb>
<tb> 356-410 F <SEP> @ <SEP> 79.4 <SEP> 80.7 <SEP> 68.

   <SEP> 2 <SEP> 66.5 <SEP> 65.9 <SEP> 66.1 <SEP> 64.1
<tb>
<tb>
<tb>
<tb> Above <SEP> of <SEP> 410 f <SEP> 7. <SEP> 9 <SEP> 12.2 <SEP> 11.5 <SEP> 15. <SEP> 6 <SEP> 17.9 <SEP> 18. <SEP> 4 <SEP> 17.0
<tb>
<tb>
<tb>
<tb> Fraction <SEP> 356-410 F, weight
<tb>
 
 EMI11.8
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 EMI11.9
 
<tb> Index <SEP> bromide <SEP> @ <SEP> 105 <SEP> 104 <SEP> 103 <SEP> 102 <SEP> 98 <SEP> 98 <SEP> 99
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Fraction <SEP> 338-438 F <SEP> for
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 100 <SEP> of <SEP> polymers <SEP> total <SEP> 98.0 <SEP> 90.4 <SEP> 87.1 <SEP> 88.9 <SEP> 77. <SEP> 7 <SEP> 82. <SEP> 1 <SEP> 83.

   <SEP> 9
<tb>
 
The results given in Table 3 show that the polymers produced in the various phases of this test contained about 80 to 64 percent by weight of the fraction with a boiling point between 356 and 410 F., and consisting essentially of monoolefinic hydrocarbons. .

   he

 <Desc / Clms Page number 12>

 It should also be noted that the fraction of polymers with a boiling point of between 338 and 438 F represented 78 to 98 percent by volume of the total polymers. During the 1,171 hours during which this catalyst was used, one obtained per pound of catalyst a total of 13.76 pounds of fraction 338 to 438 Fo In these various phases of the test, the propylene conversion was maintained between 68 and 77 percent per pass by gradually increasing the temperature of the reactor preheater thereby if that the maximum temperature of the catalyst, while the ratio of the combined feed was maintained between 2.8 and 3.2
At the end of period 13,

   the catalyst was still strongly active and could have been used for a longer period if it had been desired Example 4
The results given in Example 3 show that the solid phosphoric acid catalyst remained active for a long period of time when acting on a dry mixture of a propane-propylene fraction and on polymers of propylene containing. up to about 12 carbon atoms per molecule. This long catalyst life is surprising, since previous work on the polymerization of propylene in the absence of a polymer recirculation indicated that it was necessary
 EMI12.1
 adding water vapor to the introduced propane-propylene fraction in order to prevent dehydration of the catalyst and rapid loss of catalyst activity.



   Table 4 below shows a comparison of the results obtained by the polymerization of propylene starting from dry and wet propane-propylenes fractions in the presence of the solid phosphoric acid catalyst by non-selective polymerization, without re-heating. polymer circuit
Table 4.



  Non-selective polymerization of dry and wet propane-propylene fractions.
 EMI12.2
 
<tb>



  Gas <SEP> Gas
<tb> dry <SEP> wet
<tb>
<tb> <SEP> content in <SEP> propylene <SEP> of a <SEP> fraction <SEP> propanepropylene <SEP> in <SEP> mole <SEP> for <SEP> hundred <SEP> @ <SEP> 34.7 <SEP> 26.0
<tb> <SEP> content in <SEP> water <SEP> of a <SEP> fraction <SEP> propane-pro
<tb>
 
 EMI12.3
 pylene in mole percent 0000000.0..0..0 ... 0.00 2.5
 EMI12.4
 
<tb> Temperature <SEP> of <SEP> treatment <SEP> in <SEP> degrees <SEP> F. <SEP> 435 <SEP> 435
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Pressure <SEP> of <SEP> treatment <SEP> in <SEP> pounds <SEP> by <SEP> inch
<tb>
 
 EMI12.5
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   132 175
 EMI12.6
 
<tb> Total number <SEP> <SEP> of hours <SEP> of the <SEP> treatment <SEP> 42 <SEP> 360
<tb> Decrease <SEP> of <SEP> the <SEP> activity of the <SEP> catalyst,
<tb>
 
 EMI12.7
 percent aooaaooeaoooaeaaeoeooroaaorsr 70 None
 EMI12.8
 
<tb> Gain <SEP> in <SEP> weight <SEP> of the <SEP> catalyst, <SEP> for <SEP> hundred ..... <SEP> 4.5 <SEP> 1.8
<tb>
<tb> Production <SEP> of <SEP> polymers <SEP> by <SEP> book <SEP> of <SEP> cataly-
<tb>
 
 EMI12.9
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 <Desc / Clms Page number 13>

 
The above data show the rapid decrease in the activity of the polymerization catalyst when treating a propane-propylene cuttlefish fraction in the absence of recirculated polymers.

   The test carried out on the propane-propylene fraction containing 2.5 mole percent of water vapor was stopped after 15 days and at the end of this period there was no drop in the activity of the catalyst. A much longer catalyst life than the mentioned 4.5 gallons of polymer per pound of catalyst could have been obtained if the test had been continued. Thus, in the polymerization of propylene by a non-selective polymerization, which is a one-pass operation, it is essential to introduce sufficient water, dry or wet steam with the new fraction. propane-propylene so that the sum of the water already present in the gas stream plus that which is added is sufficient to prevent water loss from the catalyst.



   The changes in single-pass polymerization activities of catalysts acting on dry and wet propane-propylene moieties (2.5 mole percent water) are shown later in Table 5.
Table 5.



  Changes in the catalytic activities of the solid phosphoric acid catalyst acting on dry and wet propane-propylene fractions.
 EMI13.1
 
<tb>



  Polymerization <SEP> of <SEP> propylene <SEP> for <SEP> hundred
<tb>
<tb>
<tb> Dry <SEP> fraction <SEP> Wet <SEP> fraction
<tb>
<tb> propane- <SEP> propane-
<tb>
<tb> propylene <SEP> propylene
<tb>
<tb>
<tb>
<tb> Duration <SEP> of <SEP> test <SEP> in <SEP> hours
<tb>
 
 EMI13.2
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Claims (1)

CLAIMS AND SUMMARY ... 1 A process for the polymerization of propylene containing not more than about 0.03 mole percent of water in the presence of a solid polymerization catalyst containing a phosphoric acid catalytic compound, in which the resulting polymer is separated of a fraction comprising essentially olefins having more than 10 carbon atoms per molecule, and polymers containing less than about 12 carbon atoms per molecule are returned to the circuit in the polymerization zone at the same time as the new raw material containing propylene. 2 A process for the production of polymers having a boiling point between about 335 and 435 F in which a mixture of a propane-propylene fraction and a fraction of propylene polymers having a boiling point below about 335 F said mixture containing not more than 0.03 mole percent of water, in contact with a phosphoric acid catalyst, in the solid state, at a temperature of between about 250 and 450 F and at a pressure of about 100 to 2,000 pounds per square inch, the resulting product being fractionated to separate the desired polymer fraction from the lower and higher boiling polymers, and at least a portion of said lower boiling point polymers being recirculated to the polymerization zone. 3 A process for the production of polymers having a boiling point of between about 350 and 410 F., wherein a mixture of a propane-propylene moiety and a propylene polymer moiety having a boiling point are reacted. boiling less than about 355 F ', said mixture containing not more than about 0.03 mole percent water, in contact with a phosphoric acid catalyst, in a solid state, at a temperature. - temperature between approximately 275 and 375 F., and at a pressure between approximately 600 and 10,200 pounds per square inch, the resulting product being subjected to fractional distillation to separate the fraction of desired polymers from the lower and higher boiling point polymers and re-introducing into the circuit at least a portion of the higher boiling point polymers. bottom, in the polymerization zone. 4 A process for the production of polymers having a boiling point between about 355 and 410 F., wherein a liquid volume mixture of a propane-propylene fraction containing not more than about is reacted. 0.03 mole percent water and about 0.2 to 5 liquid volumes of a fraction of polymers of propylene boiling below 355 F. in contact with a solid precalinated mixture of a phosphorus acid and a siliceous adsorbent at a temperature of between about 250 and about 450 Fo and at a pressure of between about 600 and about 1,200 pounds per square inch, the resulting product being subjected to fractional distillation to separate the desired polymer fraction from the lower and higher boiling fractions, and at least a part of the lower boiling polymers being recirculated to the polymerization zone. 50 The method of claim 4, wherein the silica adsorbent consists of diatomaceous earth. 60 A process according to claims 4 or 5, wherein the reaction takes place between a propane-propylene fraction containing no more <Desc / Clms Page number 15> of 0.03 mole percent water and about 1.0 to 2.5 liquid volumes fraction of the propylene polymer at a boiling point below 335 F. 7 A continuous process for the polymerization of propylene containing not more than about 0.03 mole percent of water in the presence of a solid phosphoric acid catalyst, in which the resulting product is continuously separated. a fraction comprising essentially olefins with more than 10 carbon atoms and polymers containing less than 12 carbon atoms per molecule are continuously recirculated in the polymerization zone together with a new quantity of starting material containing propylene. 8 A continuous process for the production of polymers having a boiling point between about 335 and 435 F, in which a mixture of propane-propylene fraction and a propylene polymer fraction of boiling point below about 335 F., said mixture containing not more than about 0.03 mole percent water, in contact with a solid phosphoric acid catalyst and at a temperature of between about 250 and 450 F. and at a pressure of between about 100 and 2,000 pounds per square inch, the resulting product being subjected to continuous fractional distillation to separate the desired polymer fraction from the lower and higher boiling point polymers, and at least a part of said lower boiling point polymers being continuously recirculated in the polymerization zone. 9. A continuous process for the production of polymers having a boiling point of between about 355 and 410 F., in which a mixture of one liquid volume of a propane-propylene fraction containing no more than 0 is reacted. .03 mole percent water and about 0.2 to 5 fluid volumes of a fraction of polymers of propylene boiling below about 355 F. in contact with a solid precalcined mixture of a phosphoric acid and diatomaceous earth at a temperature between 250 and 450 Fo and at a pressure between approximately 600 and 1,200 pounds per square inch, the resulting product being continuously subjected to fractional distillation to separate the desired polymer fraction from the lower and higher boiling point polymers, and by continuously returning at least part of said poly (s) to the circuit. - mothers with lower boiling points in the polymerization zone. The process according to 9, wherein the propane-propylene fraction contains about 1.0 to 2.5 liquid volumes of a fraction of polymers of propylene boiling below about 335 F. 11 A process for the production of polymers having a boiling point of about 335 to 435 F., in which a mixture consisting of a propane-propylene fraction and a fraction of boiling point propylene polymers is reacted less than about 335 F., said mixture containing not more than about 0.01 mole percent water, in contact with a solid phosphoric acid catalyst at a temperature of between about 250 and 450 F . and a pressure of between about 100 and 20,000 pounds per square inch, the resulting product being subjected to fractional distillation to separate the desired polymer fraction from the lower and higher boiling point polymers, and returning at least a portion of said lower boiling point polymers to the polymerization zone. 12 The process of 11, wherein the polymer fraction of propylene has a boiling point of less than about 355 F. and the temperature <Desc / Clms Page number 16> working temperature is between about 2750 and about 375 F 13 A process for the production of monoolefins having a boiling point of between about 335 and 435 F in which a mixture of hydrocarbons containing not more than about 0.03 mole percent water and comprising water is reacted. propylene and a monoolefin containing 6 to 12 carbon atoms per molecule as its essential unsaturated constituents in contact with a phosphoric acid catalyst, in the solid state, at a temperature of between 250 and 450 F approximately and at a pressure between approximately 100 and 20,000 pounds per square inch, the resulting product being subjected to fractional distillation to separate the desired olefin fraction from the lower and higher boiling olefins, and returning at least part of said lower boiling olefins to the circuit in the polymerization zone. 14 A continuous process for the production of monoolefins having a boiling point of between about 335 and 435 F in which a liquid volume of a propane-propylene fraction containing not more than about 0.03 mole percent of is reacted. water and from about 0.2 to about 5 liquid volumes of a monoolefinic fraction containing hydrocarbons having 6 to 12 carbon atoms per molecule as its essential unsaturated constituents in contact with a solid precalcined mixture of a phosphoric acid and a silicate adsorbent at a polymerization temperature of between about 250 and 450 F and a pressure of between about 100 and 2000 pounds per square inch, the resulting product containing olefins being distilled by separating the desired fraction containing the olefins from a lower boiling fraction and a higher boiling fraction, and returning to the circuit at least part of the lower boiling fraction in the polymerization zone. A process which comprises polymerizing propylene containing not more than about 0.03 mole percent water in the presence of a solid state polymerization catalyst containing phosphoric acid, a fraction being separated from the polymer resulting in which essentially contains olefins having no more than 10 carbon atoms per molecule, and by returning to the circuit polymers containing less than about 10 carbon atoms per molecule in the polymerization zone at the same time as starting material supplement containing propylene. 16. A process for the polymerization of propylene substantially as described and / or with reference to the accompanying drawings.