BE1009871A3 - Selective hydrogenation of highly unsaturated compounds in hydrocarbon charges. - Google Patents

Abstract

Process for the isomerization of olefins in aliphatic hydrocarbon feeds, carried out at 40 to 300 F under partial pressure in weak hydrogen in the range of approximately 689.48 Pa (0.1 psi) to less than 482,636 Absolute Pa (70 psia) to 0 to manometric Pa (350 psig) in a distillation column reactor containing a hydrogenation catalyst which serves as a component of a distillation structure, for example supported PdO; placed in a tubular reinforcing mesh. There is essentially no hydrogenation of the olefins.

Description

       

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  Selective hydrogenation of highly unsaturated compounds in hydrocarbon feedstocks.



   The present request is a partial continuation of the documents USSN 07/933 753, established on August 24, 1992 and USSN 08/079 975 established on June 21, 1993, which is a continuation of the document USSN 07/833 360 established on February 10, 1992, present abandoned.



   Background of the invention.



  Field of the invention.



   The present invention relates to the selective hydrogenation of diolefins and acetylenic compounds in a feed rich in olefins. More particularly, the invention relates to a process using a hydrogenation catalyst in a structure which serves as a catalyst and a distillation structure for the simultaneous reaction and separation of the reactants and reaction products.



  Prior art.



   Mixed refinery feedstocks often contain a broad spectrum of olefinic compounds. This is particularly true for products from catalytic cracking or thermal cracking processes.



  These unsaturated compounds include ethylene, acetylene, propylene, propadiene, methylacetylene, butenes, butadiene, amylenes, hexenes, etc.



  Many of these compounds are useful, particularly as feedstocks for chemicals. Ethylene is, in particular, recovered. In addition, propylene and butenes are useful. However, olefins having more than one double bond and acetylenic compounds (having a triple bond) have less use and are harmful for many chemical processes in which single double bond compounds are used, for example the

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 polymerization. Among the type of hydrocarbons considered, the elimination of highly unsaturated compounds is advantageous as a preliminary treatment of the feed, since it has frequently been found that these compounds are harmful in the majority of the treatment, storage and use processes. of these charges.



   C4 cuts are sources of alkanes and alkenes for paraffinic alkylation to produce Cg components of gasoline blends and as feedstocks for the production of ethers.



   The Cs refinery cut is useful as a fuel mixture stock and as a source of isoamylene to form an ether by reaction with lower alcohols. T-amylmethylether (TAME) quickly became useful for refiners following the recently ratified Clean Air Act, which established certain new limits in the composition of gasoline. Some of these requirements are: (1) include a certain amount of "oxygenates" such as methyl-t-butyl ether (MTBE), TAME or ethanol; (2) reduce the amount of olefins in gasoline, and (3) reduce the vapor pressure (volatility).
The Cg in the charge of a TAME unit are contained in a single section of "light naphtha" which contains all the compounds between C5 and Ca and higher compounds.

   This mixture can easily contain 150 to 200 components and therefore the identification and separation of the products is difficult. Several of the minor components (diolefins) in the feed react slowly with oxygen during storage to produce "gum" and other undesirable materials. However, these components also react very quickly in the TAME process to form a yellow matter, smelly and tarry odor. It therefore seems desirable to eliminate these components that the cut of "light naphtha" is used only for blends of petrol in

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 itself or as a charge for the TAME process.



   The use of a solid particulate catalyst as part of a distillation structure in a reactor combined with a distillation column, for different reactions is described in U. S. Patents n: (etherification) 4,232,177; 4,307,254; 4,336,407; 4,504,687; 4,918,243; and 4,978,807; (dimerization) 4,242,530; (hydration) 4,982,022; (dissociation) 4,447,668; and (aromatic alkylation) 4,950,834 and 5,019,669. In addition, U.S. Pat. Nos. 4,302,356 and 4,443,559 describe catalytic structures which are useful as distillation structures.



   Hydrogenation is the reaction of hydrogen with a carbon-to-carbon multiple bond to "saturate" the compound. This reaction has been known for a long time and is usually carried out at pressures above atmospheric pressure and at moderate temperatures by means of a large excess of hydrogen over a metal catalyst. Among the metals known to catalyze the hydrogenation reaction are platinum, rhenium, cobalt, molybdenum, nickel, tungsten and palladium. Generally, commercial forms of catalyst use supported oxides of these metals.



  The oxide is reduced to the active form before use with a reducing agent or during use by the hydrogen of the feed. These metals also catalyze other reactions, more particularly dehydrogenation at elevated temperatures. In addition, they can promote the reaction of olefinic compounds with themselves or other olefins to produce dimers or oligomers when the residence time is increased.



   The selective hydrogenation of hydrocarbon compounds has been known for some time. Peterson et al., In "The Selective Hydrogenation of Pyrolysis Gasoline", presented to the Petroleum Division of the American Chemical Society in September 1962, discuss the selective hydrogenation of C4 diolefins and

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 higher. Boitiaux et al., In "Newest Hydrogenation Catalyst", Hydrocarbon Processing, March 1985, present a non-limiting general review of various uses of hydrogenation catalysts, including the selective hydrogenation of a charge rich in propylene and others cuts.

   Conventional liquid phase hydrogenations as implemented today require high partial pressures of hydrogen, usually greater than 1,378,960 Pa (200 psi) and more frequently, in the range of more than 2,747,920 Pa (400 psi) or more. In liquid phase hydrogenation, the partial pressure of hydrogen is essentially the pressure of the system.



   U.S. Patent No. 2,717,202 assigned to Bailey discusses a counter-current process for the hydrogenation of bacon, performed in a plurality of independent vertical chambers using a catalyst pumped under pressure conditions not described. U.S. Patent No. 4,221,653 to Chervenak et al. Describes concurrent hydrogenation for the use of an extremely high pressure bubbling bed. English patent application no. 835 689 describes a concurrent hydrogenation at high pressure, on a flow bed of C2 and C3 fractions to remove the acetylenes.



   US Patent No. 5,087,780 to Arganbright describes a process for the hydroisomerization of butenes using a palladium oxide catalyst supported on alumina, placed in a catalysis and distillation structure in a reactor catalytic distillation. The hydrogenation of the dienes is also observed under a high partial hydrogen pressure, greater than 482,636 Pa absolute (70 psia), but not around 68,948 Pa absolute (10 psia).



   An advantage of the present process is that the diolefins (dienes) and the acetylenic compounds contained in the hydrocarbon feedstock brought into contact with the catalyst are converted into olefins or alkanes with very

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 little if no oligomer formation or little if no saturation of the mono-olefins.



   Overview of the invention.



   The present invention relates to the introduction of a hydrocarbon feed containing highly unsaturated compounds which comprises diolefins and acetylenes as well as a charge of hydrogen at a partial pressure of working hydrogen of at least about 689.48 Absolute Pa (0.1 psia) to less than 482,636 Pa (70 psia), preferably less than 344,740 Pa absolute (50 psia) in a distillation column reactor containing a hydrogenation catalyst which is a component of a distillation structure and the selective hydrogenation of part of the highly unsaturated compounds.

   In the range of partial hydrogen pressures as defined, no more hydrogen is used than is necessary to maintain the catalyst (more likely to reduce the metal oxide of the catalyst and maintain it in the state of 'hydride) and hydrogenate highly unsaturated compounds, since excess hydrogen is usually broken down. This preferably corresponds to a partial hydrogen pressure in the range of about 689.48 Pa to 68,948 Pa absolute (0.1 to 10 psia) and even, advantageously, not more than 48,263.6 Pa absolute (7 psia). Optimal results have been obtained in the range between 3447.4 and 34474 Pa manometric (0.5 and 5 psig) of partial pressure of hydrogen.



   The hydrocarbon feed typically comprises C2 to C9 or C4 to CH aliphatic compounds, which may be narrow sections or include a range of carbon contents. The invention consists in the discovery that a hydrogenation carried out in a catalytic distillation column requires only a fraction of the partial pressure of hydrogen necessary for the liquid phase processes which are the form of

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 previous commercial work for this type of charge, but give the same or better results. Thus, the investment capital and the implementation expenses for the present hydrogenation are significantly lower than the previous commercial implementations.



   Without limiting the scope of the invention, it is proposed that the mechanism which produces the ineffectiveness of the present process is the condensation of part of the vapors in the reaction system, which condenses enough hydrogen in the condensed liquid to obtain contact. intimate necessary between hydrogen and highly unsaturated compounds in the presence of the catalyst which results in their hydrogenation.



   The highly unsaturated compounds can be present in very small amounts, i.e., a few parts per million up to major amounts, i.e. more than 90% by weight. The present invention can be used to remove impurities or to convert quantities of the products of the highly unsaturated compounds to mono-olefins or alkanes, as desired.



   The hydrogen flow rate must be adjusted to the partial pressure described, so that it is sufficient to withstand the hydrogenation reaction and replace the loss of hydrogen from the catalyst, but kept below the pressure leading to the hydrogenation of the mono -olefins, what is meant by "the partial pressure of implementation hydrogen" which is the expression used here.



   As can easily be appreciated, the amount of highly unsaturated compound in the hydrocarbon feedstock is a factor to be considered in choosing the optimal partial hydrogen pressure, since at least a stoichiometric amount of hydrogen must be present in the system. to allow the reaction. When the highly unsaturated compounds are impurities, present in parts per million, the lower range of partial hydrogen pressure is an excess, but it is necessary

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 because of the scarcity of the selective reagent. Likewise, the nature of this reaction between a gas and a liquid and the apparent need to condense the hydrogen in the liquid make an excess of hydrogen at partial pressures, a preferred mode of implementation.



   An additional feature of the process is that some of the mono-olefins contained in the feed or produced by the selective hydrogenation of the diolefins can be isomerized to more desirable products.



  Isomerization can be obtained with the same family of catalysts as those used for the hydrogenations. Generally, the relative reaction rates for different compounds are in order from faster to slower: (1) hydrogenation of diolefins; (2) isomerization of mono-olefins, and (3) hydrogenation of mono-olefins.



   It has been shown, generally, that in a feed containing diolefins, the diolefins will be hydrogenated before isomerization occurs. It has also been shown that very low total pressures can be used for optimal results in some of the present hydrogenations, preferably in the range of 344,740 to 1,034,220 Pa manometric (50 to 150 psig) with the same excellent results. Higher and lower pressures over the wide range can be used with satisfactory results.



   Brief description of the drawings.



   Fig. 1 is a simplified flowchart of an embodiment of the present invention; Fig. 2 is a simplified flowchart of a second embodiment of the present invention; Fig. 3 is a simplified flow diagram of a third embodiment of the present invention, and FIG. 4 is a simplified flowchart of a

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 fourth embodiment of the present invention.



  Detailed description and preferred embodiments.



   Although the hydrogenation reactions have been described as reversible at elevated temperatures, above about 482.2 C (900 F) (see for example the Peterson article cited above) under the temperature conditions used in the present invention, the hydrogenation is not reversible. In the conventional implementation of a process where the catalyst serves as a distillation component, the equilibrium is constantly disturbed, which results in the reaction towards completion, i.e., the reaction has an increased advancing force because the reaction products are eliminated and cannot contribute to a reverse reaction (LeChatelier principle).

   In the present process where there is no reversible reaction, no benefit can be derived from the removal of the reaction products to increase the force of the reaction. Similarly, the low yield of previous hydrogenations in the vapor phase does not suggest the use of the distillation reaction. Thus, it is unexpected that catalytic distillation is advantageous for non-reversible hydrogenation.



   It is believed that in the present reaction catalytic distillation is an advantage, firstly because the reaction is carried out at the same time as the distillation, the initial reaction products and other feed components are removed from the zone reaction as quickly as possible, reducing the likelihood of side reactions. Second, because all of the components are boiling, the reaction temperature is controlled by the boiling point of the mixture at system pressure. The heat of reaction simply creates a higher boil, but does not increase the temperature at a given pressure. As a result, a great power to control the speed of the reaction and the

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 product distribution can be achieved by regulating the system pressure.

   Likewise, the adjustment of the flow rate (residence time = inverse of the hourly space velocity of the liquid) gives additional control over the distribution of the products and controls to a certain extent side reactions such as oligomerization. Another advantage that this reaction can derive from catalytic distillation is that the washing effect which is produced by the internal reflux on the catalyst thus reduces polymer formation and cooking. Internal reflux in the range of 0.2 to 20 L / D (weight of liquid just below the catalyst bed relative to the weight of distillate) gives excellent results and for C3 to C charges, usually in the range of 0.5 to 4 L / D.



   Surprisingly enough, the low partial pressure of hydrogen used in the distillation system does not result in a lack of hydrogenation which would have been expected based on the high partial pressure of hydrogen observed in liquid phase systems which are usually used. As previously observed, the phenomenon of condensation which is a constant factor in a distillation is assumed to result in an availability of identical or better hydrogen than at high pressure in the liquid phase, i.e., hydrogen is introduced into the liquid , so that hydrogenation occurs.



   In one embodiment, the present invention includes the selective hydrogenation of acetylenic compounds and diolefins contained in a feed rich in propylene, to purify the feed and obtain higher amounts of propylene. The feedstock rich in propylene is introduced into a distillation column reactor in a reaction-distillation zone containing a palladium oxide catalyst supported in the form of a catalytic distillation structure. Hydrogen is supplied as necessary in order to carry out the reaction and, it is assumed, to reduce the oxide and

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 maintain it in the hydride state.

   It was previously thought that the hydride state was the active state, however, the very small amounts of hydrogen present, which give excellent results may indicate the opposite. In all cases, the state of the catalyst relates to the theory of mechanisms, which is not the subject of the present invention. The distillation column reactor is operated at a pressure such that the reaction mixture is boiling in the catalyst bed. If desired, a tail charge containing higher boiling material can be extracted to achieve complete separation.



   In an embodiment with C ,, by means of the partial pressure of hydrogen as mentioned, the present invention comprises a process for the selective hydrogenation of diolefins and acetylenic compounds contained in a feed rich in propylene, comprising the steps of: (a) introduction: (1) of a first charge comprising propylene, diolefins and acetylenic compounds, and (2) of a second charge containing hydrogen, in a distillation column reactor, in an introduction area; (b) simultaneously, in the distillation column reactor:

   (i) bringing the first and second charges into contact in a reaction-distillation zone with a hydrogenation catalyst capable of acting as a distillation structure so as to react essentially all the diolefins and all the acetylenic compounds with hydrogen to forming propylene and other hydrogenated products in a reaction mixture, and (ii) separating the propylene contained in the first charge and the propylene formed by the reaction of diolefins and acetylenic compounds from the reaction mixture by fractional distillation, and

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 (c) extracting the propylene separated in step (b) (ii) as well as the propane and the lighter compounds, including unreacted hydrogen, from the distillation column reactor as top fractions.

   Optionally, the process may include extracting any C4 or higher boiling compound from the distillation column reactor as bottoms. There is no significant loss of propylene by hydrogenation.



   In an embodiment in Ce, by means of the partial pressure of hydrogen as given, the present invention comprises the introduction of a cut of light naphtha comprising a mixture of hydrocarbons as well as a charge of hydrogen towards a distillation column reactor containing a hydrogenation catalyst which is a component of a structure for the distillation and selective hydrogenation of the diolefins contained in light naphtha. Simultaneously, the lightest compounds, including unreacted hydrogen, are distilled and separated as top fractions of the partially hydrogenated light naphtha product.

   In addition, and simultaneously with selective hydrogenation and distillation, some of the C5 monoolefins are isomerized to a more desirable feedstock for the production of t-amylmethylether (TAME) by the reaction of the iso- olefin with methanol. Essentially all diolefins are converted to mono-olefins with very little hydrogenation of mono-olefins.



   In a further embodiment using light naphtha, the feed stream is predominantly a C5 charge and the light naphtha product is extracted as a tail product. The overheads are passed through a condenser in which all of the condensables are condensed and a portion is passed back to the top of the column. Reflux ratios of 0.5 to 20: 1 can be used for the various embodiments.



   In another embodiment using the

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 stream of introduction of light naphtha and partial pressure of hydrogen as given, the stream of introduction comprises a wider stream of C; at Cg, the Cg are separated from the C6 + components in the lower section of a distillation column reactor. The C6 + components are extracted as bottoms feed while the C5 are boiled in the upper section of the distillation column reactor which contains the catalytic distillation structure, which performs the selective hydrogenation of diolefins.

   The hydrogenated C5s are taken as overheads as well as the excess hydrogen and are passed to the condenser in which all the condensable products are condensed and then separated from the non-condensable products (mainly hydrogen), for example in a separator with reflux drum. Part of the liquid from the separator is returned to the distillation column reactor as reflux and the rest is extracted as product, which can be directly charged to a TAME unit.

   If desired, an additional inert distillation section can be used above the catalytic distillation structure with a lower side draft of the enCg products to remove excess hydrogen as well as any other light component such as air, l , etc., which can cloud the TAME unit downstream.



   In the embodiment with light naphtha, the present invention is a process for the selective hydrogenation of diolefins contained in a light naphtha, comprising the steps of: (a) introduction: (1) of a first charge comprising a naphtha light comprising diolefins, and (2) a second charge containing hydrogen, in a distillation column reactor in an introduction zone;

   (b) simultaneously in the distillation column reactor:

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 (i) bringing the first and second charges into contact in a reaction-distillation zone with a hydrogenation catalyst capable of acting as a distillation structure, to thus react essentially all the diolefins with hydrogen, to form pentenes and other hydrogenated products in a reaction mixture, and (ii) operating the distillation column reactor at a pressure such that part of the mixture is vaporized by the exothermic heat of the reaction;

   (c) extracting part of the liquid from step (b) (ii) from the distillation column reactor as bottom fractions, and (d) extracting the vapors from step (b) (ii) as well that any unreacted hydrogen from the distillation column reactor as overhead.



   The diolefins contained in the Cg cut have a higher boiling point than the other compounds and therefore can be concentrated in the catalytic zone while the mono-olefins are isomerized and eliminated in the upper part of the column. The interesting reactions of the C5 compounds are:
 EMI13.1
 (1) isoprene (2-methylbutadiene-1,3) + hydrogen to make 2-methylbutene-1 and 2-methylbutene-2; (2) cis-and trans-1,3-pentadienes (cis-and transpiperylenes) + hydrogen to make pentene-1 and pentene-2; (3) 3-methylbutene-1 to 2-methylbutene-2 and 2-methylbutene-1; (4) 2-methylbutene-1 to 2-methylbutene-2; (5) 2-methylbutene-2 to 2-methylbutene-1, and (6) 1,3-butadiene to butene-1 and butene-2.



   The first two reactions remove unwanted components while the third is advantageous for introduction into a TAME reactor. 3-methylbutene-1 does not react with methanol to produce TAME on the sulfonic acid catalyst, so

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 that the two 2-methylbutenes do.



   The present invention carries out the process in a column packed with catalyst, which can be assumed to contain a vapor phase and a little liquid phase as in any distillation. The distillation column reactor is operated at a pressure such that the reaction mixture is boiling in the catalyst bed. The present process is carried out at a head pressure of the distillation column reactor in the range between 0 and 2,413,180 Pa manometric (0 and 350 psig), preferably 1,723,700 (250) or less and temperatures in this same reaction zone-
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 distillation in the range of 4, 44 to 148, 89 C (40 to 300 F), preferably 43, 33 to 132, 22 C (110 to 270 F) at the partial pressures of hydrogen required.

   The hourly space velocity of the introductory mass (WHSV), which is defined here by the unit weight of charge per hour entering the distillation-reaction column per unit weight of catalyst in the catalytic distillation structures can vary within a wide range measurement, with the other implementation parameters, for example between 0.1 and 35.



   The advantages of using a distillation column reactor in the present selective hydrogenation process are the better selectivity of the transformation of diolefins into olefins, the conservation of heat and the separation by distillation which can eliminate certain non compounds. desirable, for example heavy sulfur contaminants, feed prior to catalyst exposure and distillation can concentrate the desired compounds in the catalytic zone.



   A "foam rate" is preferably maintained through the catalytic bed by controlling the extraction rates of the bottom and / or overhead products, which improves the efficiency of the catalyst while reducing the necessary weight of catalyst. As can be appreciated, the liquid is boiling and the physical state is

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 actually a foam having a higher density than that which would normally be observed in a filled distillation column, but lower than that of the liquid without the boiling vapors, as described in US Pat. No. 5,221,441 which is incorporated here . Basically, the foam mode called "continuous liquid phase (LPC)" hereinafter means that the flow of liquid from the catalytic distillation part has been restricted, so that the rising vapor creates a foam.

   Indeed, the continuous phase is the liquid rather than the vapor as is usual in a distillation. The result is increased contact of the liquid with the catalytic material during distillation and better selective hydrogenation.



   The temperature in the reactor is determined by the boiling point of the liquid mixture present at any given pressure. The temperature in the lower parts of the column reflects the constitution of the material in this part of the column, which is higher than that in the upper part; that is, at constant pressure, a change in system temperature indicates a change in the composition in the column. To change the temperature, the pressure is varied. The temperature in the reaction zone is therefore controlled by varying the pressure; increasing the pressure increases the system temperature and vice versa.



   As described, the catalytic material used in the hydrogenation process is in a form which serves as a distillation packing. In a vague manner, the catalytic material is a component of a distillation system functioning as a catalyst and distillation packing, namely, a packing for a distillation column having a distillation function as well as a catalytic function.



   The reaction system can be described as heterogeneous, since the catalyst remains as a separate entity. Any suitable hydrogenation catalyst can be used, for example the metals of group VIII of

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 periodic table of the elements, (or group VIII metal compounds) as main catalytic component, alone or with promoters and modifiers such as palladium / gold, palladium / silver, cobalt / zirconium, nickel preferably deposited on a support such as alumina, refractory brick, pumice, carbon, silica, resin or the like.



   A preferred catalytic material comprises palladium oxide, preferably 0.1 to 5.0% by weight, supported on a suitable support such as alumina, carbon or silica, for example extrudates of alumina at 0.32 cm (1/8 "). In a preferred catalytic distillation structure, the particulate catalytic material is placed on a porous pan or screen which contains the catalyst and provides distillation surfaces, in the form of 'a wire mesh structure such as a tubular wire mesh structure or any similar structure.



   A preferred catalytic structure for the present hydrogenation reaction comprising a tubular, flexible, semi-rigid open network material such as a stainless steel mesh, comprises a particulate catalytic material of one of the many embodiments recently developed in association with the present process.



   One of the new catalytic structures developed for use in hydrogenations is described in U.S. Patent No. 5,266,546 which is incorporated herein in its entirety. Briefly, the new catalytic structure is a catalytic distillation structure comprising a flexible, semi-rigid, tubular, open lattice material such as a stainless steel mesh, comprising a particulate catalytic material, the tubular material having two ends and having a length in the range of about one-half to two times the diameter of the tubular material, a first end being fixed along a first axis to form a first joint and a

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 second end being fixed along a second axis to form a second joint,

   where the plane of the first joint along the axis of the tubular material and the plane of the second joint along the axis of the tubular material intersect each other at an angle of about 15 to 900.



   U.S. Patent No. 4,242,530 and US Patent No. 4,443,559 which are incorporated herein describe a catalyst supported in a plurality of pockets of a web belt or lattice tubular structures which are supported in the reactor to distillation column by an open trellis, knotted in stainless steel by twisting them together in a helix. USSN 08/075 328 established June 11, 1993, which is incorporated herein, describes several other structures suitable in the prior art and describes new structures suitable for the present process.



   The particulate catalytic material can be a powder, small irregular pieces or fragments, small beads and the like. The particular shape of the catalytic material of the structure is not critical as long as sufficient specific surface is provided to allow a reasonable reaction rate. The size of the catalytic particles can be predetermined for each catalytic material (since the porosity or the internal specific surface available can vary for different materials and of course, affect the activity of the catalytic material).



   For the present hydrogenations, the preferred catalytic structures for the packing are those using the most open structure of permeable trays or screens.



   Referring now to FIG. 1, there is shown a simplified schematic flowchart of a preferred embodiment in Cg. There is shown a distillation column reactor 10 containing a packing of hydrogenation catalyst suitable as part of a distillation structure 12 such as the device in

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 lattice described above. The column can also have a standard distillation structure 14. The light naphtha is introduced via line 1 into the distillation column reactor 10, below the catalytic packing. The hydrogen is introduced in the form of a gas via the flow pipe 2 at the bottom or near the bottom of the bed of the catalytic lining.



   The C5 introduction stream and hydrogen are preferably introduced into the distillation column reactor separately or they can be mixed before introduction. A mixed introduction stream is introduced below the catalytic bed or at the lower end of the bed. Hydrogen alone is introduced below the catalytic bed and the C charge is preferably introduced below the bed. Although the hydrocarbon is preferably introduced below the bed to keep heavy impurities such as sulfur compounds outside, it can be introduced up to a third of the bed.



  The pressure chosen is such that it keeps dienes and other highly unsaturated compounds in the catalytic bed, while allowing propylene and lighter products to distill in the form of a top fraction.



   Heat is added from below via the flow line 4, by circulation through the reboiler 40 and return to the column via the flow line 13. When the reaction has started, the heat of the reaction which is exothermic causes additional spraying of the mixture into the bed. The vapors are taken as overhead fraction through the flow line 3 and pass to the condenser 20 where substantially all of the condensable materials are condensed up to a temperature of 37.78 C (100OF). The overhead products are then passed to the reflux drum 30 where the condensed material is collected and separated from the non-condensable products such as unreacted hydrogen.

   A portion of condensed material collected in the reflux drum is returned to the top of the reactor

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 to the distillation column 10 via the flow line 6. The distilled product, extracted by the line 9, is an appropriate feedstock by a TAME reactor. The non-condensable material is ventilated from the reflux drum by the flow line 7 and for the purpose of economy, the hydrogen can be recycled to the reactor (not shown).



   The bottoms product containing essentially no C 8 diolefins is extracted via the flow line 8 and can be sent to a gasoline mixer as stable gasoline. The process is advantageous because the high heat of hydrogenation is absorbed by the vaporization of part of the liquid, so that temperature control is achieved by adjusting the system pressure. Any excess hydrogen is extracted from the tail products. In the case of Cet, the non-hydrogenated components are less volatile and tend to remain in the reactor for a longer period of time, which assists in a more complete reaction.



   In Fig. 2, a second embodiment of the invention is presented, in which the light naphtha is introduced into the column 10 above the catalytic distillation structure 12 via the flow line 1 '. Otherwise the arrangement is identical to that of FIG. 1.



  Fig. 3 illustrates a third embodiment in which the column comprises an additional conventional distillation structure 216 above the catalytic distillation structure 12 to separate all C4 and lighter materials, hydrogen and other point components of lower boiling of the Ce which are extracted in the form of lateral load by the flow pipe 209.



  EXAMPLE 1. -
In this example, the hydrocarbon feedstock is rich in propylene such as a C3 cut coming from a gas installation of a catalytic cracking unit

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 fluid or a cracker under pressure. A typical analysis of such a charge is given in Table II below.



   The catalyst is 0.3% by weight PdO on 0.32 cm (1/8 ") Al (alumina) extrudates, a hydrogenation catalyst sold by United Catalysts, Inc., and named G68F. The typical physical and chemical properties of the catalyst are provided by the manufacturer and are as follows:
TABLE I
 EMI20.1
 
 <tb>
 <tb> Appellation <SEP> G68F
 <tb> Shape <SEP> Spheres
 <tb> Size <SEP> nominal <SEP> 3 <SEP> x <SEP> 6
 <tb> Percentage <SEP> in <SEP> weight <SEP> from <SEP> 0.3
 <tb> palladium
 <tb> Support <SEP> Alumina <SEP> from <SEP> purity <SEP> high
 <tb>
 
It is assumed that the catalyst is palladium hydride which is produced during processing.



   The hydrogen flow to the reactor must be sufficient to keep the catalyst in the active form, because hydrogen is lost from the catalyst by hydrogenation. The hydrogen flow rate must be adjusted to the partial pressure described, so that it is sufficient to support the hydrogenation reaction and replace the lost hydrogen from the catalyst, but be kept lower than that necessary for the hydrogenation of propylene and to prevent submersion of the column. Generally, the molar ratio of hydrogen to acetylenic compounds in the feed to the fixed bed is about 1.05 to 2.5, preferably 1.4 to 2.0.

   The presence of a hydrogen charge as described here does not adversely affect the physical operation of the catalytic distillation system.

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  TABLE II
 EMI21.1
 
 <tb>
 <tb> Component <SEP>% <SEP> Mole
 <tb> Methane <SEP> 0,000
 <tb> Ethylene <SEP> 0,000
 <tb> Ethane <SEP> 0.075
 <tb> Propylene <SEP> 82,722
 <tb> Propane <SEP> 11,118
 <tb> Methylacetylene <SEP> 2,368
 <tb> Propadiene <SEP> 1.304
 <tb> cyclo-C3 <SEP> 0.048
 <tb> Isobutane <SEP> 0,000
 <tb> Isobutene <SEP> 0.015
 <tb> Butene-1 <SEP> 0.242
 <tb> Butadiene <SEP> 1.529
 <tb> n-Butane <SEP> 0.112
 <tb> Trans-butene-2 <SEP> 0.008
 <tb> Vinylacetylene <SEP> 0.013
 <tb> Cis-butene-2 <SEP> 0,000
 <tb> Cs <SEP> and <SEP> more <SEP> heavy <SEP> 0,000
 <tb> Total <SEP> 100,000
 <tb> Propylene / propane <SEP> 7.440
 <tb>
 
The feed containing propylene and hydrogen can be introduced into the distillation column reactor separately or they can be mixed before introduction.

   A mixed introduction stream is introduced below the catalytic bed or at the lower end of the bed. Hydrogen alone is introduced below the catalytic bed and the C3 charge is preferably introduced below the bed. The introduction of hydrocarbons into the bed can result in some deactivation of the catalyst by impurities. The pressure chosen is such
 EMI21.2
 that it keeps dienes and acetylenes in the catalytic bed while it allows propylene and the lighter components to be distilled as the top fraction.



  Any unreacted hydrogen is in the top fraction with the C3s.



   The pilot unit used is a laboratory column 2.54 cm (1 inch) and 4.57 m (15 feet) high. The catalyst, 240 g of 0.3% by weight PdO, is placed on 0.32 cm (1/8 ") alumina extrudates in

  <Desc / Clms Page number 22>

 pockets of a distillation liner in the form of a lattice to form the catalytic distillation structures described in U.S. Patent No. 5,266,546 incorporated herein. The distillation catalytic structures are placed at the center of the column 3.08 m (10 feet), the lower and upper 0.77 m (2.5 feet) being loaded with an inert distillation packing. The charge rich in propylene and hydrogen are brought to the column and the heat added to initiate the reaction.

   The head pressure is maintained between 1 654 752 and 2 413 180 Pa manometric (240 and 315 psig). In the pilot unit, no tail is taken and an equilibrium amount of C4 + of approximately 15% by volume is present in the lower part of the column, as indicated by a constant temperature of approximately 600C (140 F). The constant temperature also indicates that there is no formation of heavier materials, produced as a result of any oligomerization. If there were residual dienes, the tail temperature would increase by the formation of heavier products, indicating a selective total elimination of the dienes and acetylenes.

   In industrial units or on a larger scale, a draft of the tail fractions should probably be understood in order to separate the C4 + from the propylene product. Table III below gives the results of the pilot unit.

  <Desc / Clms Page number 23>

 



  TABLE III
 EMI23.1
 
 <tb>
 <tb> Period <SEP> from <SEP> charge, <SEP> h <SEP> 220 <SEP> 221 <SEP> 237 <SEP> 239 <SEP> 241 <SEP> 335 <SEP> 336
 <tb> Pressure, <SEP> psig <SEP> 315 <SEP> 315 <SEP> 300 <SEP> 280 <SEP> 280 <SEP> 280 <SEP> 280
 <tb> Temperature <SEP> from <SEP> low, <SEP> F <SEP> 140 <SEP> 140 <SEP> 140 <SEP> 140 <SEP> 140 <SEP> 140 <SEP> 140
 <tb> Charge
 <tb> Debit, <SEP> pounds / h <SEP> (liquid) <SEP> 6.0 <SEP> 6, <SEP> 0 <SEP> 6, <SEP> 0 <SEP> 5, <SEP> 9 <SEP> 5, <SEP> 9 <SEP> 11, <SEP> 0 <SEP> 11.0
 <tb> Debit <SEP> from <SEP> H2, <SEP> SCF / h <SEP> (gas) <SEP> 4.0 <SEP> 4.0 <SEP> 4.0 <SEP> 4.0 <SEP> 5.0 <SEP> 8.0 <SEP> 10.0
 <tb> Report <SEP> "2 <SEP> acetylene <SEP> 1, <SEP> 4S2 <SEP> 1, <SEP> 451 <SEP> 1.468 <SEP> 1.493 <SEP> 1, <SEP> 867 <SEP> 1.602 <SEP> 2.002
 <tb> MA¯ + <SEP> PO <SEP> in <SEP> your <SEP> charge, <SEP> X <SEP> in <SEP> moles <SEP> 3,

    <SEP> 708 <SEP> 3, <SEP> 708 <SEP> 3,690 <SEP> 3, <SEP> 690 <SEP> 3, <SEP> 690 <SEP> 3,690 <SEP> 3, <SEP> 690
 <tb> C'82, <SEP> 3740 <SEP> 82, <SEP> 3740 <SEP> 82.3740 <SEP> 82, <SEP> 3740 <SEP> 82, <SEP> 3740 <SEP> 82, <SEP> 3740 <SEP> 82, <SEP> 3740
 <tb> C <SEP> + MA + PD <SEP> 86,082 <SEP> 86, <SEP> 082 <SEP> 86,064 <SEP> 86,064 <SEP> 86,064 <SEP> 86,064 <SEP> 86, <SEP> 064
 <tb> of <SEP> 2.7 <SEP> 2.7 <SEP> 2.6 <SEP> 2.6 <SEP> 2.7 <SEP> 2.6 <SEP> 2.6
 <tb> Analysis <SEP> from <SEP> product <SEP> from <SEP> head, <SEP> X <SEP> in <SEP> moles
 <tb> Ethane <SEP> 0, <SEP> 065 <SEP> 0, <SEP> 030 <SEP> 0.080 <SEP> 0, <SEP> 052 <SEP> 0.052 <SEP> 0.068 <SEP> 0, <SEP> 069
 <tb> Propylene <SEP> 86, <SEP> 460 <SEP> 86, <SEP> 184 <SEP> 87,221 <SEP> 86,379 <SEP> 85, <SEP> 583 <SEP> 87, <SEP> 355 <SEP> 87, <SEP> 421
 <tb> Propane <SEP> 11, <SEP> 717 <SEP> 11, <SEP> 304 <SEP> 11,074 <SEP> 12,

    <SEP> 041 <SEP> 12, <SEP> 353 <SEP> 10, <SEP> 687 <SEP> 10, <SEP> 957
 <tb> Methylacetylene <SEP> 0, <SEP> 000 <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0.212 <SEP> 0.013
 <tb> Propadiene <SEP> 0,000 <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0.470 <SEP> 0, <SEP> 064
 <tb> Cyclo-C3 <SEP> 0.049 <SEP> 0, <SEP> 054 <SEP> 0, <SEP> 045 <SEP> 0, <SEP> 044 <SEP> 0, <SEP> 051 <SEP> 0, <SEP> 043 <SEP> 0, <SEP> 045
 <tb> Isobutane <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0,000
 <tb> Isobutene <SEP> 0.014 <SEP> 0, <SEP> 016 <SEP> 0, <SEP> 010 <SEP> 0, <SEP> 007 <SEP> 0, <SEP> 012 <SEP> 0, <SEP> 009 <SEP> 0, <SEP> 085
 <tb> Butene-1 <SEP> 0, <SEP> 845 <SEP> 1, <SEP> 369 <SEP> 0, <SEP> 831 <SEP> 0, <SEP> 781 <SEP> 0, <SEP> 856 <SEP> 0, <SEP> 394 <SEP> 0,

    <SEP> 739
 <tb> n-Butane <SEP> 0, <SEP> 127 <SEP> 0, <SEP> 207 <SEP> 0.117 <SEP> 0, <SEP> 105 <SEP> 0, <SEP> 151 <SEP> 0.077 <SEP> 0, <SEP> 076
 <tb> Trans-butene-2 <SEP> 0, <SEP> 544 <SEP> 0, <SEP> 950 <SEP> 0.472 <SEP> 0.466 <SEP> 0, <SEP> 600 <SEP> 0, <SEP> 116 <SEP> 0.292
 <tb> Vinylacetylene <SEP> 0,000 <SEP> 0,000 <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0,000 <SEP> 0, <SEP> 000
 <tb> Cis-butene-2 <SEP> 0, <SEP> 185 <SEP> 0.327 <SEP> 0.144 <SEP> 0. <SEP> 155 <SEP> 0, <SEP> 237 <SEP> 0, <SEP> 031 <SEP> 0.

    <SEP> 056
 <tb> C5 <SEP> and <SEP> more <SEP> heavy <SEP> 0,000 <SEP> 0,000 <SEP> 0,000 <SEP> 0,000 <SEP> 0,000 <SEP> 0,000 <SEP> 0,000
 <tb> X <SEP> KAPO <SEP> 0,000 <SEP> 0,000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0, <SEP> 000 <SEP> 0.682 <SEP> 0.077
 <tb>
 

  <Desc / Clms Page number 24>

 EXAMPLE 2.-
The catalyst is 0.34% palladium on spheres of Al 2 O 3 (alumina) from 3 to 8, sold by United Catalysts Inc., and named G68C.

   The typical physical and chemical properties of the catalyst as supplied by the manufacturer are as follows:
TABLE IV
 EMI24.1
 
 <tb>
 <tb> Appellation <SEP> G68C
 <tb> Shape <SEP> Sphere
 <tb> Size <SEP> nominal <SEP> 5 <SEP> x <SEP> 8
 <tb> Percentage <SEP> in <SEP> weight <SEP> from <SEP> 0.3 <SEP> (0.27-0, <SEP> 33)
 <tb> palladium
 <tb> Support <SEP> Alumina <SEP> from <SEP> purity <SEP> high
 <tb>
 
It is assumed that the catalyst is palladium hydride which is produced during processing. The flow of hydrogen to the reactor must be sufficient to keep the catalyst in its active form because hydrogen is lost from the catalyst by hydrogenation.

   The "quantity of hydrogen used", the term used here, is determined by considering that the C, must be at least 1.0, preferably more than 2.0, for example about 10 moles of hydrogen. per mole of diolefin.



   A steel column 310, 7.62 cm (3 inches) in diameter and 9.14 m (30 feet) high, with a reboiler 340, a condenser 320 and a reflux system 330 and 306 is used as shown in Fig. 4. The central 4.57 m (15 feet) are lined with a distillation catalytic structure 312 comprising the catalyst, palladium at 0.34% by weight on spherical alumina of 0.32 cm (1/811 ), which is contained in the pockets of a fiberglass strap and twisted with a stainless steel mesh. The column is purged with nitrogen and

  <Desc / Clms Page number 25>

 the pressure increased to 137 896 Pa manometric (20 psig). The charge of light naphtha which has been prefractionated to remove the majority of the C6 + materials is introduced into the column via line 301 at 50 pounds per hour.

   When a lower rate is obtained and the liquid is at the desired level in the column, we start to take a fraction of the tail through line 308 and the circulation of the reboiler begins through lines 304 and 313. We add heat to reboiler 340 until steam is observed at the top of the column, evidenced by a uniform temperature of 176.4 C (130 F) throughout the column. The flow of hydrogen is started down the column, at approximately 8 to 10 SCFH via line 302. The pressure of the column is then controlled to maintain a
 EMI25.1
 temperature at the bottom of approximately 518.4 C (320 F) and a temperature of the catalytic bed of approximately 410.4 C (260 F).



  The pressure of the top fraction is therefore maintained at approximately 1,378,960 Pa absolute (200 psig). The overhead fraction is taken off through line 303 and partially condensed in condenser 320 and all the condensable materials are collected in the reflux drum 330 and returned to the top of the column as reflux through line 306. The non-condensable products are ventilated from the drum by line 307. The fraction of liquid tail is extracted by line 308. The results are given in Table V below, in which the load and tail analyzes are compared.

  <Desc / Clms Page number 26>

 



  TABLE V
 EMI26.1
 
 <tb>
 <tb> Component, <SEP>% <SEP> in <SEP> weight <SEP> Charge <SEP> Product <SEP> from <SEP> tail <SEP>% <SEP> from <SEP> variation
 <tb> Light <SEP> 0.073 <SEP> 0, <SEP> 000-100
 <tb> Dimethylether <SEP> 0.003 <SEP> 0, <SEP> 002-36
 <tb> Isobutane <SEP> 0.488 <SEP> 0, <SEP> 093-81
 <tb> Methanol <SEP> 0, <SEP> 058 <SEP> 0, <SEP> 000-100
 <tb> Others <SEP> C4 <SEP> 4,573 <SEP> 3, <SEP> 304-28
 <tb> 3-Methylbutene-l <SEP> 1.026 <SEP> 0.270-74
 <tb> Isopentane <SEP> 31,974 <SEP> 32,066 <SEP> 0
 <tb> Pentene-1 <SEP> 2.708 <SEP> 0, <SEP> 962-64
 <tb> 2-Methylbutene-1 <SEP> 6.496 <SEP> 4,012-38
 <tb> n-Pentane <SEP> 3,848 <SEP> 4,061 <SEP> 6
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0.147 <SEP> 0, <SEP> 002-99
 <tb> Trans-pentene-2 <SEP> 6, <SEP> 995 <SEP> 9.066 <SEP> 30
 <tb>
 

  <Desc / Clms Page number 27>

 
 EMI27.1
 
 <tb>
 <tb> Component,

    <SEP>% <SEP> in <SEP> weight <SEP> Charge <SEP> Product <SEP> from <SEP> tail <SEP>% <SEP> from <SEP> variation
 <tb> Unknown <SEP> 1 <SEP> 0.138 <SEP> 0, <SEP> 094-32
 <tb> Cis-pentene-2 <SEP> 3,886 <SEP> 3, <SEP> 723-4
 <tb> 2-Methylbutene-2 <SEP> 11, <SEP> 634 <SEP> 14,083 <SEP> 21
 <tb> Trans-piperylene <SEP> 0.142 <SEP> 0, <SEP> 002-98
 <tb> cis-piperylene <SEP> 0.095 <SEP> 0, <SEP> 003-97
 <tb> Cyclo-C5 <SEP> 0.001 <SEP> 0.058-47
 <tb> C6 + <SEP> 25.603 <SEP> 28,198 <SEP> 10
 <tb> Total <SEP> 100, <SEP> 000 <SEP> 100, <SEP> 000
 <tb>
 

  <Desc / Clms Page number 28>

 EXAMPLE 3.-
During the experiment of Example 2, the upper pressure is adjusted to vary the temperature of the catalyst bed.

   At lower temperatures, the conversion of diolefins is lower, but the main difference is that the isomerization of 3-methylbutene-1 is affected more dramatically. Table VI below compares the conversions of diolefins and 3-methylbutene-1 with respect to the processing temperature.

  <Desc / Clms Page number 29>

 



  TABLE VI
 EMI29.1
 
 <tb>
 <tb> Temperature <SEP> Pressure <SEP> Hours <SEP> Conversion, <SEP>% <SEP> in <SEP> moles
 <tb> medium <SEP> OF <SEP> superior <SEP> STM
 <tb> psig <SEP> Isoprene <SEP> t-Pip <SEP> c-Pip <SEP> 3-Methylbutene-1
 <tb> 230 <SEP> 130 <SEP> 200 <SEP> 65 <SEP> 57 <SEP> 65 <SEP> 17
 <tb> 250 <SEP> 145 <SEP> 300 <SEP> 97 <SEP> 95 <SEP> 95 <SEP> 55
 <tb> 265 <SEP> 200 <SEP> 600 <SEP> 100 <SEP> 99 <SEP> 99 <SEP> 80
 <tb>
 

  <Desc / Clms Page number 30>

 EXAMPLE 4 Charges of C4.



   This series of experiments demonstrates the unexpected elimination of dienes from C4 streams at extremely low partial pressures of hydrogen. It also demonstrates that lower total pressures are also appropriate. The experiments are carried out according to two modes. In one mode, a conventional distillation, a continuous vapor phase is used. In the other mode, a preferred liquid continuous phase mode "LPC" is used.



   The reactor used for Experiment 1 is a column of 7.62 cm (3 inches) in diameter containing a catalyst packing on 6.09 m (20 feet), containing 28.317 dm3 (1 cubic foot) of catalytic material (of the 0.5% palladium on alumina 8 to 12, product E144SDU of Calcicat, Catalyst and Performance Chemicals Division, Mallinckrodt, Inc.), with 1.40 m (4.5 feet) of steel ring of 1 , 59 cm (5/8 ") above and 4.72 m (15.5 feet) of Pall steel ring 1.59 cm (5/8") below the catalytic bed.

   In Experiment 2, a 7.62 cm (3 inch) diameter column was used containing 6.09 m (20 feet) of catalyst packing, containing 28.317 dm3 (1 cubic foot) of catalytic material (0.5% palladium on alumina 8 to 12, product E144SDU from Calcicat, Catalyst and Performance Chemicals Division, Mallinckrodt, Inc.), with 1.40 m (4.5 feet) of Pall steel ring 1.59 cm (5/8 ") above and 7.62 m (25 feet) of anti-fog wire and 15.24 m (50 feet) of Pall steel ring 1.59 cm (5/8 ") below the catalytic bed. The catalyst is loaded into 2.54 cm (1 inch) tubular wire liners placed diagonally on the anti-fog wire and surrounded around a balloon about 7.62 cm (3 inches) in diameter.



   The hydrocarbon is introduced into the column below the catalyst. To start, the top pressure is set at 827,376 Pa manometric (120 psig)

  <Desc / Clms Page number 31>

 and the reboiler is loaded with the hydrocarbon charge to about 9.07 kg (20 pounds) per hour, the reboiler being set at 10%, which is kept for 15 minutes, then the introduction rate is adjusted to maintain lower rates of 50 to 75% until the head temperature is 200 to the tail temperature, then the rate of hydrocarbon addition is increased to 45.35 kg (100 pounds) per hour. When the differential pressure reaches 6894.8 Pa (1.0 psi), the hydrogen flow begins at 424.76 standard dm3 per hour (15 scfh).

   The lower fractions are heated to a uniform temperature of 71.11 C (1600F), then a medium reflux flow is started. The higher pressure is chosen and the distillation-reaction is carried out. The conditions and results of loading of C4 hydrocarbons for each experiment are given in Tables VII and VIII.



   The experiments carried out according to the LPC mode allow the elimination of all the dienes, whereas a conventional distillation leaves a few parts per million under the same conditions. The internal reflux flow is reported as the ratio of the liquid immediately below the catalyst lining to the distillate (L / D). The data show that LPC mode leads to better elimination of dienes.

  <Desc / Clms Page number 32>

 



   TABLE VII
Example 4, experiment 1, part 1.



  41 hours charge.



  Conditions.
 EMI32.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 2, <SEP> 3
 <tb> Source <SEP> from <SEP> charge <SEP> Cracked <SEP> catalytic <SEP> fluid <SEP> (FCC) <SEP> from
 <tb> refinery
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 100
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 15
 <tb> Pressure, <SEP> psig <SEP> 120
 <tb> Distillate, <SEP> pound / h <SEP> 93
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 0, <SEP> 73
 <tb> Mode <SEP> Classic
 <tb>
 

  <Desc / Clms Page number 33>

 Results.
 EMI33.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Ethylene <SEP> 0, <SEP> 02 <SEP> 0.01 <SEP> 0, <SEP> 00 <SEP> 0.00
 <tb> Ethane <SEP> 0, <SEP> 20 <SEP> 0.01 <SEP> 0.00 <SEP> 0.69
 <tb> Propylene <SEP> 0, <SEP> 27 <SEP> 0, <SEP> 22 <SEP> 0.00 <SEP> 2.61
 <tb> Propane <SEP> 0.48 <SEP> 0.44 <SEP> 0.00 <SEP> 3.34
 <tb> Isobutane <SEP> 31.38 <SEP> 32.63 <SEP> 0.18 <SEP> 31.70
 <tb> Isobutene <SEP> 14.21 <SEP> 14.77 <SEP> 0.74 <SEP> 11, <SEP> 41
 <tb> Butene-l <SEP> 12.82 <SEP> 4.59 <SEP> 1.07 <SEP> 3.25
 <tb> 1, <SEP> 3-Butadiene <SEP> 0, <SEP> 2788 <SEP> 0.0030 <SEP> 0, <SEP> 0199 <SEP> 0.0000
 <tb> n-Butane <SEP> 9, <SEP> 37 <SEP> 10.13 <SEP> 8.55 <SEP> 4.95
 <tb> Trans-butene-2 <SEP> 17.13 <SEP> 24.69 <SEP> 25, <SEP> 56 <SEP> 11, <SEP> 49
 <tb> 2,

  2-Dimethylpropane <SEP> 0.00 <SEP> 0.00 <SEP> 0.08
 <tb> Methylcyclopropane <SEP> 0.02 <SEP> 0.02 <SEP> 0.02
 <tb> Cis-butene-2 <SEP> 12.50 <SEP> 12.20 <SEP> 53.01 <SEP> 4.91
 <tb> Cg <SEP> 1.26 <SEP> 0, <SEP> 27 <SEP> 10.58 <SEP> 0.06
 <tb> More <SEP> heavy <SEP> 0, <SEP> 01 <SEP> 0.01 <SEP> 0.18 <SEP> 0.21
 <tb> Total <SEP> 100, <SEP> 00 <SEP> 100.0 <SEP> 100.0
 <tb> Pounds / h <SEP> 100, <SEP> 0 <SEP> 93.0 <SEP> 5 <SEP> 1.8
 <tb> Temperature, <SEP> OF <SEP> 155 <SEP> 188
 <tb>
 

  <Desc / Clms Page number 34>

 Transformation of components.
 EMI34.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.28 <SEP> 30 <SEP> ppm
 <tb> Isobutane <SEP> 31.4 <SEP> 31.0
 <tb> n-Butènes <SEP> 42.5 <SEP> 43.0
 <tb> n-Butane <SEP> 9.4 <SEP> 10.0
 <tb>% <SEP> from <SEP> butene-1 <SEP> from <SEP> total <SEP> of <SEP> n-butenes <SEP> 30.2 <SEP> 10, <SEP> 2
 <tb>
 

  <Desc / Clms Page number 35>

 
TABLE VII (continued)
Example 4, experiment 1. part 2.



  102 hours of charging.



  Conditions.
 EMI35.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 1.5
 <tb> Source <SEP> from <SEP> charge <SEP> Cracked <SEP> catalytic <SEP> fluid <SEP> (FCC) <SEP> from
 <tb> refinery
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 100
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 10
 <tb> Pressure, <SEP> psig <SEP> 120
 <tb> Distillate, <SEP> pound / h <SEP> 93
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 0.74
 <tb> Mode <SEP> LPC
 <tb> I
 <tb>
 

  <Desc / Clms Page number 36>

 Results.
 EMI36.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Ethylene <SEP> 0.02 <SEP> 0, <SEP> 01 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 00
 <tb> Ethane <SEP> 0.20 <SEP> 0.02 <SEP> 0.00 <SEP> 0.70
 <tb> Propylene <SEP> 0.27 <SEP> 0.25 <SEP> 0.00 <SEP> 2.13
 <tb> Propane <SEP> 0.48 <SEP> 0.47 <SEP> 0, <SEP> 00 <SEP> 2.52
 <tb> Isobutane <SEP> 31.38 <SEP> 32.97 <SEP> 0.21 <SEP> 23.22
 <tb> Isobutene <SEP> 14.21 <SEP> 14.82 <SEP> 0.81 <SEP> 8.18
 <tb> Butene-1 <SEP> 12.82 <SEP> 3.67 <SEP> 1.15 <SEP> 1.92
 <tb> 1,3-Butadiene <SEP> 0.2788 <SEP> 0.0000 <SEP> 0.0211 <SEP> 0.0000
 <tb> n-Butane <SEP> 9.37 <SEP> 9.93 <SEP> 8.84 <SEP> 3.43
 <tb> Trans-butene-2 <SEP> 17.13 <SEP> 25.37 <SEP> 25.71 <SEP> 8.29
 <tb> 2,2-Dimethylpropane <SEP> 0.00 <SEP> 0.00 <SEP> 0,

  08
 <tb> Methylcyclopropane <SEP> 0, <SEP> 02 <SEP> 0.02 <SEP> 0.02
 <tb> Cis-butene-2 <SEP> 12.50 <SEP> 12.20 <SEP> 52.25 <SEP> 3.46
 <tb> C <SEP> 1.26 <SEP> 0.28 <SEP> 10.70 <SEP> 0.00
 <tb> More <SEP> heavy <SEP> 0.01 <SEP> 0.00 <SEP> 0.20 <SEP> 0.00
 <tb> Total <SEP> 100.00 <SEP> 100.0 <SEP> 100.0
 <tb> Pounds / h <SEP> 100, <SEP> 0 <SEP> 93, <SEP> 1 <SEP> 5 <SEP> 2.0
 <tb> Temperature, <SEP> OF <SEP> 155 <SEP> 188
 <tb>
 

  <Desc / Clms Page number 37>

 Transformation of components.
 EMI37.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.28 <SEP> 0 <SEP> ppm
 <tb> Isobutane <SEP> 31.4 <SEP> 31.2
 <tb> n-Butènes <SEP> 42.5 <SEP> 42.6
 <tb> n-Butane <SEP> 9.4 <SEP> 9.8
 <tb>% <SEP> from <SEP> butene-1 <SEP> from <SEP> total <SEP> of <SEP> n-butenes <SEP> 30.2 <SEP> 8, <SEP> 2
 <tb>
 

  <Desc / Clms Page number 38>

 
TABLE VII (continued)
Example 4, experiment 1, part 3.



  161 hours of charging.



  Conditions.
 EMI38.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 0, <SEP> 8
 <tb> Source <SEP> from <SEP> charge <SEP> Cracked <SEP> catalytic <SEP> fluid <SEP> (FCC) <SEP> from
 <tb> refinery
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 100
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 5
 <tb> Pressure, <SEP> psig <SEP> 120
 <tb> Distillate, <SEP> pound / h <SEP> 93
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 0, <SEP> 74
 <tb> Mode <SEP> Classic
 <tb>
 

  <Desc / Clms Page number 39>

 Results.
 EMI39.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Ethylene <SEP> 0, <SEP> 02 <SEP> 0, <SEP> 01 <SEP> 0.00 <SEP> 0.00
 <tb> Ethane <SEP> 0, <SEP> 20 <SEP> 0, <SEP> 01 <SEP> 0.00 <SEP> 0.64
 <tb> Propylene <SEP> 0, <SEP> 27 <SEP> 0.25 <SEP> 0.00 <SEP> 1.96
 <tb> Propane <SEP> 0, <SEP> 48 <SEP> 0.46 <SEP> 0.00 <SEP> 2.24
 <tb> Isobutane <SEP> 31.38 <SEP> 32.84 <SEP> 0.47 <SEP> 20.08
 <tb> Isobutene <SEP> 14.21 <SEP> 14.87 <SEP> 0.87 <SEP> 7.12
 <tb> Butene-1 <SEP> 12.82 <SEP> 10.32 <SEP> 1.20 <SEP> 4.26
 <tb> 1,3-Butadiene <SEP> 0, <SEP> 2788 <SEP> 0.0262 <SEP> 0.0227 <SEP> 0, <SEP> 0000
 <tb> n-Butane <SEP> 9.37 <SEP> 9.52 <SEP> 8.71 <SEP> 2.87
 <tb> Trans-butene-2 <SEP> 17.13 <SEP> 19.35 <SEP> 25, <SEP> 66 <SEP> 5.71
 <tb> 2,2-Dimethylpropane <SEP> 0,

  00 <SEP> 0, <SEP> 00 <SEP> 0.08
 <tb> Methylcyclopropane <SEP> 0.02 <SEP> 0, <SEP> 02 <SEP> 0.02
 <tb> Cis-butene-2 <SEP> 12.50 <SEP> 12.08 <SEP> 52.60 <SEP> 2.96
 <tb> C <SEP> 1.26 <SEP> 0.24 <SEP> 10.23 <SEP> 0.00
 <tb> More <SEP> heavy <SEP> 0.01 <SEP> 0.00 <SEP> 0.12 <SEP> 0.00
 <tb> Total <SEP> 100.00 <SEP> 100.0 <SEP> 100.0
 <tb> Pounds / h <SEP> 100, <SEP> 0 <SEP> 92.7 <SEP> 5 <SEP> 2, <SEP> 3
 <tb> Temperature, <SEP> OF <SEP> 156 <SEP> 188
 <tb>
 

  <Desc / Clms Page number 40>

 Transformation of components.
 EMI40.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.28 <SEP> 262 <SEP> ppm
 <tb> Isobutane <SEP> 31, <SEP> 4 <SEP> 30, <SEP> 9
 <tb> n-Butènes <SEP> 42.5 <SEP> 43.0
 <tb> n-Butane <SEP> 9.4 <SEP> 9.3
 <tb>% <SEP> from <SEP> butene-1 <SEP> from <SEP> total <SEP> of <SEP> n-butenes <SEP> 30.2 <SEP> 22.6
 <tb>
 

  <Desc / Clms Page number 41>

 
TABLE VII (continued)
Example 4, experience 1. part 4.



  198 hours of charging.



  Conditions.
 EMI41.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 1.5
 <tb> Source <SEP> from <SEP> charge <SEP> Cracked <SEP> catalytic <SEP> fluid <SEP> (FCC) <SEP> from
 <tb> refinery
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 100
 <tb> Debit <SEP> from <SEP> H, <SEP> scfh <SEP> 10
 <tb> Pressure, <SEP> psig <SEP> 120
 <tb> Distillate, <SEP> pound / h <SEP> 93
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 0.74
 <tb> Mode <SEP> Classic
 <tb>
 

  <Desc / Clms Page number 42>

 Results.
 EMI42.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Ethylene <SEP> 0.02 <SEP> 0.01 <SEP> 0.00 <SEP> 0, <SEP> 00
 <tb> Ethane <SEP> 0.20 <SEP> 0.01 <SEP> 0.02 <SEP> 0, <SEP> 64
 <tb> Propylene <SEP> 0.27 <SEP> 0.25 <SEP> 0.03 <SEP> 2, <SEP> 08
 <tb> Propane <SEP> 0.48 <SEP> 0.46 <SEP> 0.05 <SEP> 2.42
 <tb> Isobutane <SEP> 31.38 <SEP> 32.97 <SEP> 3.92 <SEP> 20.74
 <tb> Isobutene <SEP> 14, <SEP> 21 <SEP> 14.90 <SEP> 2.43 <SEP> 7.27
 <tb> Butene-l <SEP> 12.82 <SEP> 7, <SEP> 29 <SEP> 2, <SEP> 61 <SEP> 3.26
 <tb> 1,3-Butadiene <SEP> 0.2788 <SEP> 0.0105 <SEP> 0.0509 <SEP> 0, <SEP> 0000
 <tb> n-Butane <SEP> 9.37 <SEP> 9.64 <SEP> 8.81 <SEP> 2.90
 <tb> Trans-butene-2 <SEP> 17.13 <SEP> 21.91 <SEP> 24.64 <SEP> 6.32
 <tb> 2,2-Dimethylpropane <SEP> 0.00 <SEP> 0,

  00 <SEP> 0.07
 <tb> Methylcyclopropane <SEP> 0.02 <SEP> 0.02 <SEP> 0.02
 <tb> Cis-butene-2 <SEP> 12.50 <SEP> 12.29 <SEP> 47.97 <SEP> 2.97
 <tb> C <SEP> 1.26 <SEP> 0.23 <SEP> 9.22 <SEP> 0.00
 <tb> More <SEP> heavy <SEP> 0.01 <SEP> 0.01 <SEP> 0.17 <SEP> 0.00
 <tb> Total <SEP> 100.00 <SEP> 100, <SEP> 0 <SEP> 100, <SEP> 00
 <tb> Pounds / h <SEP> 100, <SEP> 0 <SEP> 93.0 <SEP> 5 <SEP> 2, <SEP> 1
 <tb> Temperature, <SEP> OF <SEP> 156 <SEP> 188
 <tb>
 

  <Desc / Clms Page number 43>

 Transformation of components.
 EMI43.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.28 <SEP> 105 <SEP> ppm
 <tb> Isobutane <SEP> 31.4 <SEP> 31.3
 <tb> n-Butènes <SEP> 42.5 <SEP> 42.6
 <tb> n-Butane <SEP> 9.4 <SEP> 9.5
 <tb>% <SEP> from <SEP> butene-1 <SEP> from <SEP> total <SEP> of <SEP> n-butenes <SEP> 30, <SEP> 2 <SEP> 16, <SEP> 4
 <tb>
 

  <Desc / Clms Page number 44>

 
TABLE VIII
Example 4. experience 2. part 1.



  138 hours of charging.



  Conditions.
 EMI44.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 1.5
 <tb> Source <SEP> from <SEP> charge <SEP> Cracked <SEP> catalytic <SEP> fluid <SEP> (FCC) <SEP> from
 <tb> refinery
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 56
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 15
 <tb> Pressure, <SEP> psig <SEP> 125
 <tb> Distillate, <SEP> pound / h <SEP> 37
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 4.72
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 45>

 Results.
 EMI45.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Ethylene <SEP> 0.03 <SEP> 0.03 <SEP> 0.00 <SEP> 0, <SEP> 00
 <tb> Ethane <SEP> 0.22 <SEP> 0.11 <SEP> 0.00 <SEP> 0, <SEP> 14
 <tb> Propylene <SEP> 0.24 <SEP> 0, <SEP> 31 <SEP> 0.00 <SEP> 0.68
 <tb> Propane <SEP> 0.53 <SEP> 0.68 <SEP> 0.00 <SEP> 1.18
 <tb> Isobutane <SEP> 28.17 <SEP> 39.45 <SEP> 0.01 <SEP> 33.16
 <tb> Isobutene <SEP> 15, <SEP> 05 <SEP> 21.03 <SEP> 0.0032 <SEP> 16.91
 <tb> Butene-1 <SEP> 13.91 <SEP> 7.81 <SEP> 0.01 <SEP> 5.99
 <tb> 1,3-Butadiene <SEP> 0.3441 <SEP> 0.0000 <SEP> 0.0000 <SEP> 0, <SEP> 0000
 <tb> n-Butane <SEP> 8.65 <SEP> 7.34 <SEP> 12.86 <SEP> 5.04
 <tb> Trans-butene-2 <SEP> 17.76 <SEP> 16, <SEP> 71 <SEP> 40.71 <SEP> 11.43
 <tb> 2,2-Dimethylpropane <SEP> 0.00 <SEP> 0,

    <SEP> 00 <SEP> 0.04
 <tb> Methylcyclopropane <SEP> 0.02 <SEP> 0.01 <SEP> 0, <SEP> 03
 <tb> Cis-butene-2 <SEP> 13, <SEP> 55 <SEP> 6, <SEP> 51 <SEP> 40.84 <SEP> 4.26
 <tb> Cg <SEP> 1, <SEP> 53 <SEP> 0.02 <SEP> 5.47 <SEP> 0.00
 <tb> More <SEP> heavy <SEP> 0, <SEP> 00 <SEP> 0.00 <SEP> 0.01 <SEP> 0, <SEP> 05
 <tb> Total <SEP> 100, <SEP> 00 <SEP> 100.0 <SEP> 100.00
 <tb> Pounds / h <SEP> 56, <SEP> 0 <SEP> 37, <SEP> 1 <SEP> 15 <SEP> 4.0
 <tb> Temperature, <SEP> OF <SEP> 164 <SEP> 182
 <tb>
 

  <Desc / Clms Page number 46>

 Transformation of components.
 EMI46.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0, <SEP> 3 <SEP> 0 <SEP> ppm
 <tb> Isobutane <SEP> 28.2 <SEP> 28.5
 <tb> n-Butènes <SEP> 45.2 <SEP> 43.9
 <tb> n-Butane <SEP> 8.7 <SEP> 8.7
 <tb>% <SEP> from <SEP> butene-1 <SEP> from <SEP> total <SEP> of <SEP> n-butenes <SEP> 30, <SEP> 8 <SEP> 12, <SEP> 8
 <tb>
 

  <Desc / Clms Page number 47>

 
TABLE VIII (continued)
Example 4, experiment 2, part 2.



  173 hours of charging.



  Conditions.
 EMI47.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 1.5
 <tb> Source <SEP> from <SEP> charge <SEP> Cracked <SEP> catalytic <SEP> fluid <SEP> (FCC) <SEP> from
 <tb> refinery
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 56
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 15
 <tb> Pressure, <SEP> psig <SEP> 125
 <tb> Distillate, <SEP> pound / h <SEP> 32
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 5.46
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 48>

 Results.
 EMI48.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Ethylene <SEP> 0.03 <SEP> 0.03 <SEP> 0, <SEP> 00 <SEP> 0.02
 <tb> Ethane <SEP> 0, <SEP> 22 <SEP> 0, <SEP> 09 <SEP> 0, <SEP> 00 <SEP> 0.29
 <tb> Propylene <SEP> 0.24 <SEP> 0.33 <SEP> 0.00 <SEP> 0.77
 <tb> Propane <SEP> 0.53 <SEP> 0, <SEP> 74 <SEP> 0.00 <SEP> 2.56
 <tb> Isobutane <SEP> 28.17 <SEP> 43.97 <SEP> 0.01 <SEP> 43.60
 <tb> Isobutene <SEP> 15, <SEP> 05 <SEP> 23.39 <SEP> 0.0541 <SEP> 5.45
 <tb> Butene-l <SEP> 13.91 <SEP> 7.20 <SEP> 0.22 <SEP> 19.75
 <tb> 1,3-Butadiene <SEP> 0.3441 <SEP> 0, <SEP> 0000 <SEP> 0.0024 <SEP> 0, <SEP> 0000
 <tb> n-Butane <SEP> 8.65 <SEP> 5.24 <SEP> 15.64 <SEP> 3.88
 <tb> Trans-butene-2 <SEP> 17.76 <SEP> 13.92 <SEP> 42.32 <SEP> 8.80
 <tb> 2,2-Dimethylpropane <SEP> 0,

    <SEP> 00 <SEP> 0.00 <SEP> 0, <SEP> 03
 <tb> Methylcyclopropane <SEP> 0.02 <SEP> 0, <SEP> 01 <SEP> 0.03
 <tb> Cis-butene-2 <SEP> 13.55 <SEP> 5.07 <SEP> 37.33 <SEP> 3.22
 <tb> C <SEP> 1.53 <SEP> 0.00 <SEP> 4.35 <SEP> 0.00
 <tb> More <SEP> heavy <SEP> 0.00 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 01 <SEP> 0, <SEP> 00
 <tb> Total <SEP> 100, <SEP> 00 <SEP> 100.0 <SEP> 100.00
 <tb> Pounds / h <SEP> 56, <SEP> 0 <SEP> 32, <SEP> 2 <SEP> 19 <SEP> 4.9
 <tb> Temperature, <SEP> OF <SEP> 164 <SEP> 182
 <tb>
 

  <Desc / Clms Page number 49>

 Transformation of components.
 EMI49.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.3 <SEP> 0 <SEP> ppm
 <tb> Isobutane <SEP> 28.2 <SEP> 29.1
 <tb> n-Butènes <SEP> 45.2 <SEP> 44.9
 <tb> n-Butane <SEP> 8.7 <SEP> 8.6
 <tb>% <SEP> from <SEP> butene-1 <SEP> from <SEP> total <SEP> of <SEP> n-butenes <SEP> 30.8 <SEP> 13, <SEP> 3
 <tb>
 

  <Desc / Clms Page number 50>

 EXAMPLE 5 Light FCC Naphtha Currents.



   The same methods are used as those described in Example 4, however, the catalyst is G68C-1, a product containing 0.4% palladium on alumina 7 to 12 from United Catalyst, Inc. Charges 9 , 14 m (30 feet) of catalytic packing [42, 47 dm3 (1.5 cubic feet) of catalytic material prepared in the form of a distillation structure as described in Example 4, in a column of 7.62 cm (3 inches), with 1.52 m (5 feet) of Pall steel rings 1.59 cm (5/811) and 3.05 m (10 feet) of free space above and 0.91 m (3 feet) of anti-fog wire and 15.24 m (50 feet) of Pall steel rings 1.59 cm (5/8 ") below. Distillation is carried out to remove a head of hydrotreated C. and the components the heaviest as a tail.

   The charges, conditions and results for each of the three experiments are given in Tables IX to XI.



   The results of the 3 to 74 hour charge experiment, which is carried out at a low hydrogen partial pressure and at a high WHSV of 20, are lower than those expected. By increasing the partial pressure of hydrogen to only 30,337.12 Pa absolute (4.4 psia) at 272 hours of charge in a conventional distillation mode, the elimination of the diene is improved by 10 times.

  <Desc / Clms Page number 51>

 



   TABLE IX
Example 5, experiment 1.



  99 hours of charging.



  Conditions.
 EMI51.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 4.5
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 219
 <tb> Debit <SEP> from <SEP> H2, <SEP> scfh <SEP> 20
 <tb> Pressure, <SEP> psig <SEP> 125
 <tb> Distillate, <SEP> pound / h <SEP> 47
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 2.11
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 52>

 Results.
 EMI52.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> C4 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 00
 <tb> Isobutane <SEP> 0.00 <SEP> 0.02 <SEP> 0.00 <SEP> 0.02
 <tb> Others <SEP> C4 <SEP> 0.33 <SEP> 1.52 <SEP> 0.04
 <tb> 3-Methylbutene-1 <SEP> 0.28 <SEP> 0, <SEP> 27 <SEP> 0, <SEP> 06
 <tb> Isopentane <SEP> 7.40 <SEP> 32.40 <SEP> 2.32 <SEP> 33.23
 <tb> Pentene-l <SEP> 1.07 <SEP> 1.47 <SEP> 0, <SEP> 34
 <tb> 2-Methylbutene-l <SEP> 1.81 <SEP> 4, <SEP> 09 <SEP> 0, <SEP> 60
 <tb> n-Pentane <SEP> 3.82 <SEP> 17.65 <SEP> 1, <SEP> 62
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0.1761 <SEP> 0.0000 <SEP> 0, <SEP> 0595
 <tb> Trans-pentene-2 <SEP> 2.45 <SEP> 14.99 <SEP> 1, <SEP> 02
 <tb> Unknown <SEP> 1 <SEP> 0.02 <SEP> 0.04 <SEP> 0, <SEP> 02 <SEP> 21,

  62
 <tb> Cis-pentene-2 <SEP> 1.36 <SEP> 4.86 <SEP> 0, <SEP> 59
 <tb> 2-Methylbutene-2 <SEP> 3.28 <SEP> 17.93 <SEP> 1, <SEP> 69
 <tb> Trans-piperylene <SEP> 0.18 <SEP> 0.00 <SEP> 0, <SEP> 10
 <tb> Cis-piperylene <SEP> 0, <SEP> 06 <SEP> 0.00 <SEP> 0, <SEP> 04
 <tb> Cyclopentene <SEP> 0.29 <SEP> 0, <SEP> 26 <SEP> 0.26
 <tb> Unknown <SEP> 2 <SEP> 5.12 <SEP> 4.12 <SEP> 11.26
 <tb> More <SEP> heavy <SEP> 72.36 <SEP> 0.38 <SEP> 79, <SEP> 97
 <tb> Total <SEP> 100.00 <SEP> 100.0 <SEP> 100, <SEP> 00
 <tb> Pounds / h <SEP> 218.8 <SEP> 47.0 <SEP> 171.9 <SEP> 0.00
 <tb> Temperature, <SEP> OF <SEP> 256 <SEP> 417
 <tb>
 

  <Desc / Clms Page number 53>

 Transformation of components.
 EMI53.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 1.91 <SEP> 17 <SEP> ppm
 <tb> 2MB1 <SEP> + <SEP> 2MB2 <SEP> 22.9 <SEP> 24.2
 <tb> Isopentane <SEP> 33.4 <SEP> 32.5
 <tb> Pentenes <SEP> 22.0 <SEP> 22.6
 <tb> n-Pentane <SEP> 17.2 <SEP> 18.8
 <tb>% <SEP> from <SEP> 3-MB-l <SEP> from <SEP> total <SEP> of <SEP> isoamylenes <SEP> 5.23 <SEP> 1.63
 <tb>% <SEP> from <SEP> pentene-l <SEP> from <SEP> total <SEP> of <SEP> n-pentenes <SEP> 22, <SEP> 0 <SEP> 9, <SEP> 5
 <tb>
 

  <Desc / Clms Page number 54>

 
PAINTINGS
Example 5. experiment 2, part 1.



  45 hours charge.



  Conditions.
 EMI54.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 4.8
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 217
 <tb> Debit <SEP> from <SEP> H2, <SEP> scfh <SEP> 20
 <tb> Pressure, <SEP> psig <SEP> 125
 <tb> Distillate, <SEP> pound / h <SEP> 42
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 2.22
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 55>

 Results.
 EMI55.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> C4 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 00
 <tb> Isobutane <SEP> 0.03 <SEP> 0.16 <SEP> 0, <SEP> 00 <SEP> 0.32
 <tb> Others <SEP> C4 <SEP> 1.46 <SEP> 7.33 <SEP> 0.00
 <tb> 3-Methylbutene-l <SEP> 0.21 <SEP> 0.20 <SEP> 0.00
 <tb> Isopentane <SEP> 7.85 <SEP> 38.92 <SEP> 0.08 <SEP> 34.49
 <tb> Pentene-1 <SEP> 0.76 <SEP> 1.04 <SEP> 0.02
 <tb> 2-Methylbutene-1 <SEP> 1.37 <SEP> 3.08 <SEP> 0.06
 <tb> n-Pentane <SEP> 3.56 <SEP> 13.79 <SEP> 0.73
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0, <SEP> 101 <SEP> 0.0000 <SEP> 0.0110
 <tb> Trans-pentene-2 <SEP> 2, <SEP> 08 <SEP> 10.77 <SEP> 0.42
 <tb> Unknown <SEP> 1 <SEP> 0.02 <SEP> 0, <SEP> 04 <SEP> 0, <SEP> 01
 <tb> Cis-pentene-2 <SEP> 1.15 <SEP> 3,

  50 <SEP> 0.29 <SEP> 16.97
 <tb> 2-Methylbutene-2 <SEP> 2.87 <SEP> 13.90 <SEP> 0.91
 <tb> Trans-piperylene <SEP> 0.11 <SEP> 0.00 <SEP> 0.04
 <tb> Cis-piperylene <SEP> 0.04 <SEP> 0.00 <SEP> 0.01
 <tb> Cyclopentene <SEP> 0.31 <SEP> 0.43 <SEP> 0.23
 <tb> Unknown <SEP> 2 <SEP> 6, <SEP> 49 <SEP> 6.01 <SEP> 6.46
 <tb> More <SEP> heavy <SEP> 71.58 <SEP> 0, <SEP> 83 <SEP> 90.71
 <tb> Total <SEP> 100, <SEP> 00 <SEP> 100.0 <SEP> 100.00
 <tb> Pounds / h <SEP> 217, <SEP> 3 <SEP> 41.9 <SEP> 175.4 <SEP> 0.00
 <tb> 1
 <tb> Temperature, <SEP> F <SEP> 260 <SEP> 406
 <tb>
 

  <Desc / Clms Page number 56>

 Transformation of components.
 EMI56.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 1.21 <SEP> 0 <SEP> ppm
 <tb> 2MB1 <SEP> + <SEP> 2MB2 <SEP> 20.8 <SEP> 21.6
 <tb> Isopentane <SEP> 38.4 <SEP> 40.3
 <tb> Pentenes <SEP> 19.6 <SEP> 18, <SEP> 9
 <tb> n-Pentane <SEP> 17.4 <SEP> 17.3
 <tb>% <SEP> from <SEP> 3-MB-l <SEP> from <SEP> total <SEP> of <SEP> isoamylenes <SEP> 4.80 <SEP> 0.94
 <tb>% <SEP> from <SEP> pentene-1 <SEP> from <SEP> total <SEP> of <SEP> n-pentenes <SEP> 19, <SEP> 0 <SEP> 6, <SEP> 1
 <tb>
 

  <Desc / Clms Page number 57>

 
TABLE X (continued)
Example 5, experiment 2, part 2.



  201 hours of charging.



  Conditions.
 EMI57.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 2.9
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 219
 <tb> Debit <SEP> from <SEP> H2, <SEP> scfh <SEP> 20
 <tb> Pressure, <SEP> psig <SEP> 75
 <tb> Distillate, <SEP> pound / h <SEP> 41
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 2.50
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 58>

 Results.
 EMI58.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> C4 <SEP> 0.00 <SEP> 0.02 <SEP> 0, <SEP> 00
 <tb> Isobutane <SEP> 0, <SEP> 03 <SEP> 0.15 <SEP> 0, <SEP> 00 <SEP> 0.30
 <tb> Others <SEP> C4 <SEP> 1, <SEP> 48 <SEP> 6.85 <SEP> 0, <SEP> 00
 <tb> 3-Methylbutene-l <SEP> 0, <SEP> 21 <SEP> 0.32 <SEP> 0.00
 <tb> Isopentane <SEP> 7.85 <SEP> 36.28 <SEP> 0.03 <SEP> 42.53
 <tb> Pentene-1 <SEP> 0.76 <SEP> 1, <SEP> 18 <SEP> 0, <SEP> 01
 <tb> 2-Methylbutene-1 <SEP> 1.37 <SEP> 3.94 <SEP> 0, <SEP> 04
 <tb> n-Pentane <SEP> 3.56 <SEP> 15.98 <SEP> 0.58
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0.1013 <SEP> 0, <SEP> 0000 <SEP> 0.0085
 <tb> Trans-pentene-2 <SEP> 2.08 <SEP> 12.08 <SEP> 0.33
 <tb> Unknown <SEP> 1 <SEP> 0, <SEP> 02 <SEP> 0.05 <SEP> 0,

    <SEP> 00
 <tb> Cis-pentene-2 <SEP> 1.15 <SEP> 3.88 <SEP> 0.23 <SEP> 18.14
 <tb> 2-Methylbutene-2 <SEP> 2.87 <SEP> 13.81 <SEP> 0.76
 <tb> Trans-piperylene <SEP> 0.11 <SEP> 0.00 <SEP> 0.04
 <tb> Cis-piperylene <SEP> 0, <SEP> 04 <SEP> 0.00 <SEP> 0.01
 <tb> Cyclopentene <SEP> 0, <SEP> 31 <SEP> 0.42 <SEP> 0.20
 <tb> Unknown <SEP> 2 <SEP> 6.49 <SEP> 4.49 <SEP> 6.35
 <tb> More <SEP> heavy <SEP> 71.58 <SEP> 0.54 <SEP> 91.42
 <tb> Total <SEP> 100.00 <SEP> 100.0 <SEP> 100.00
 <tb> Pounds / h <SEP> 219.0 <SEP> 41.0 <SEP> 175.7 <SEP> 2.6
 <tb> Temperature, <SEP> OF <SEP> 212 <SEP> 359
 <tb>
 

  <Desc / Clms Page number 59>

 Transformation of components.
 EMI59.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 1.21 <SEP> 0 <SEP> ppm
 <tb> 2MB1 <SEP> + <SEP> 2MB2 <SEP> 20, <SEP> 8 <SEP> 20.9
 <tb> Isopentane <SEP> 38.4 <SEP> 38.6
 <tb> Pentenes <SEP> 19.6 <SEP> 20.5
 <tb> n-Pentane <SEP> 17.4 <SEP> 18.2
 <tb>% <SEP> from <SEP> 3-MB-l <SEP> from <SEP> total <SEP> of <SEP> isoamylenes <SEP> 4.80 <SEP> 1.50
 <tb>% <SEP> from <SEP> pentene-1 <SEP> from <SEP> total <SEP> of <SEP> n-pentenes <SEP> 19.0 <SEP> 6, <SEP> 0
 <tb>
 

  <Desc / Clms Page number 60>

 
TABLE XI
Example 5, experiment 3. part 1.



  44 hours charge.



  Conditions.
 EMI60.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 2.7
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 295
 <tb> Debit <SEP> from <SEP> H <SEP> scfh <SEP> 20
 <tb> Pressure, <SEP> psig <SEP> 100
 <tb> Distillate, <SEP> pound / h <SEP> 55
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 2.65
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 61>

 Results.
 EMI61.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> C4 <SEP> 0.02 <SEP> 0.07 <SEP> 0.00
 <tb> Isobutane <SEP> 0.07 <SEP> 0.27 <SEP> 0.00 <SEP> 0.49
 <tb> Others <SEP> C4 <SEP> 1.41 <SEP> 0.00 <SEP> 0.00
 <tb> 3-Methylbutene-l <SEP> 0.25 <SEP> 0.73 <SEP> 0.00
 <tb> Isopentane <SEP> 8, <SEP> 66 <SEP> 36.35 <SEP> 0.20 <SEP> 26.57
 <tb> Pentenes-l <SEP> 0.87 <SEP> 2.09 <SEP> 0.02
 <tb> 2-Methylbutene-l <SEP> 1.83 <SEP> 6.60 <SEP> 0.05
 <tb> n-Pentane <SEP> 1.51 <SEP> 6.42 <SEP> 0.12
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0, <SEP> 0537 <SEP> 0.0024 <SEP> 0.0000
 <tb> Trans-pentene-2 <SEP> 2.58 <SEP> 13.00 <SEP> 0.21
 <tb> Unknown <SEP> 1 <SEP> 0.03 <SEP> 0, <SEP> 07 <SEP> 0, <SEP> 02
 <tb> Cis-pentene-2 <SEP> 1.42 <SEP> 5.13 <SEP> 0.22 <SEP> 28,

  45
 <tb> 2-Methylbutene-2 <SEP> 3.93 <SEP> 15.45 <SEP> 1.12
 <tb> Trans-piperylene <SEP> 0.06 <SEP> 0.00 <SEP> 0.02
 <tb> cis-piperylene <SEP> 0.03 <SEP> 0.00 <SEP> 0.01
 <tb> Cyclopentene <SEP> 0, <SEP> 06 <SEP> 0.05 <SEP> 0.04
 <tb> Unknown <SEP> 2 <SEP> 7, <SEP> 50 <SEP> 6.65 <SEP> 7.69
 <tb> More <SEP> heavy <SEP> 69.71 <SEP> 7.12 <SEP> 90.28
 <tb> Total <SEP> 100.00 <SEP> 100, <SEP> 00 <SEP> 100.00
 <tb> Pounds / h <SEP> 294.9 <SEP> 55, <SEP> 0 <SEP> 236, <SEP> 9 <SEP> 3.1
 <tb> Temperature, <SEP> OF <SEP> 240 <SEP> 388
 <tb>
 

  <Desc / Clms Page number 62>

 Transformation of components.
 EMI62.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.68 <SEP> 53 <SEP> ppm
 <tb> 2MB1 <SEP> + <SEP> 2MB2 <SEP> 27.1 <SEP> 27.7
 <tb> Isopentane <SEP> 40.7 <SEP> 39.7
 <tb> Pentenes <SEP> 22.9 <SEP> 24.4
 <tb> n-Pentane <SEP> 7.1 <SEP> 7.1
 <tb>% <SEP> from <SEP> 3-MB-l <SEP> from <SEP> total <SEP> of <SEP> isoamylenes <SEP> 4.23 <SEP> 2, <SEP> 61
 <tb>% <SEP> from <SEP> pentene-l <SEP> from <SEP> total <SEP> of <SEP> n-pentenes <SEP> 17, <SEP> 8 <SEP> 9, <SEP> 2
 <tb>
 

  <Desc / Clms Page number 63>

 
TABLE XI (continued)
Example 5. experiment 3, part 2.



  74 hours of charging.



  Conditions.
 EMI63.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 1.5
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 295
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 10
 <tb> Pressure, <SEP> psig <SEP> 100
 <tb> Distillate, <SEP> pound / h <SEP> 52
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 2.56
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 64>

 Results.
 EMI64.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> C4 <SEP> 0.02 <SEP> 0, <SEP> 08 <SEP> 0.00
 <tb> Isobutane <SEP> 0.07 <SEP> 0.29 <SEP> 0.00 <SEP> 0.68
 <tb> Others <SEP> C4 <SEP> 1, <SEP> 41 <SEP> 6.44 <SEP> 0.00
 <tb> 3-Methylbutene-l <SEP> 0.25 <SEP> 1.13 <SEP> 0, <SEP> 00
 <tb> Isopentane <SEP> 8, <SEP> 66 <SEP> 39.14 <SEP> 0.20 <SEP> 32.86
 <tb> Pentenes-l <SEP> 0.87 <SEP> 3.65 <SEP> 0.02
 <tb> 2-Methylbutene-l <SEP> 1.83 <SEP> 8.35 <SEP> 0.05
 <tb> n-Pentane <SEP> 1.51 <SEP> 5.84 <SEP> 0, <SEP> 12
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0, <SEP> 0537 <SEP> 0.0417 <SEP> 0.0000
 <tb> Trans-pentene-2 <SEP> 2.58 <SEP> 10.45 <SEP> 0.21
 <tb> Unknown <SEP> 1 <SEP> 0.03 <SEP> 0.07 <SEP> 0.02
 <tb> Cis-pentene-2 <SEP> 1.42 <SEP> 5.11 <SEP> 0,

  22 <SEP> 0.00
 <tb> 2-Methylbutene-2 <SEP> 3.93 <SEP> 13.09 <SEP> 1.12
 <tb> Trans-piperylene <SEP> 0.06 <SEP> 0.03 <SEP> 0, <SEP> 02
 <tb> Cis-piperylene <SEP> 0, <SEP> 03 <SEP> 0.05 <SEP> 0.01
 <tb> Cyclopentene <SEP> 0.06 <SEP> 0.06 <SEP> 0.04
 <tb> Unknown <SEP> 2 <SEP> 7.50 <SEP> 5.29 <SEP> 7.69
 <tb> More <SEP> heavy <SEP> 69.71 <SEP> 0.90 <SEP> 90.28
 <tb> Total <SEP> 100.00 <SEP> 100.00 <SEP> 100.00
 <tb> Pounds / h <SEP> 295.1 <SEP> 52.0 <SEP> 241.2 <SEP> 2.0
 <tb> Temperature, <SEP> OF <SEP> 236 <SEP> 383
 <tb>
 

  <Desc / Clms Page number 65>

 Transformation of components.
 EMI65.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0.68 <SEP> 1263 <SEP> ppm
 <tb> 2MB1 <SEP> + <SEP> 2MB2 <SEP> 27.1 <SEP> 27, <SEP> 5
 <tb> Isopentane <SEP> 40.7 <SEP> 42, <SEP> 4
 <tb> Pentenes <SEP> 22.9 <SEP> 21.9
 <tb> n-Pentane <SEP> 7, <SEP> 1 <SEP> 6.5
 <tb>% <SEP> from <SEP> 3-MB-l <SEP> from <SEP> total <SEP> of <SEP> isoamylenes <SEP> 4, <SEP> 23 <SEP> 4.02
 <tb>% <SEP> from <SEP> pentene-1 <SEP> from <SEP> total <SEP> of <SEP> n-pentenes <SEP> 17, <SEP> 8 <SEP> 17, <SEP> 6
 <tb>
 

  <Desc / Clms Page number 66>

 
TABLE XI (continued)
Example 5. experiment 3, part 3.



  272 hours of charging.



  Conditions.
 EMI66.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 4.4
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 295
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 30
 <tb> Pressure, <SEP> psig <SEP> 100
 <tb> Distillate, <SEP> pound / h <SEP> 53
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 2.43
 <tb> Mode <SEP> Classic
 <tb>
 

  <Desc / Clms Page number 67>

 Results.
 EMI67.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> C4 <SEP> 0.02 <SEP> 0.08 <SEP> 0.00
 <tb> Isobutane <SEP> 0.07 <SEP> 1.03 <SEP> 0.00 <SEP> 1.58
 <tb> Others <SEP> C4 <SEP> 1, <SEP> 41 <SEP> 11.21 <SEP> 0.00
 <tb> 3-Methylbutene-1 <SEP> 0.25 <SEP> 0.91 <SEP> 0, <SEP> 00
 <tb> Isopentane <SEP> 8.66 <SEP> 42.05 <SEP> 0.60 <SEP> 26.14
 <tb> Pentene-1 <SEP> 0.87 <SEP> 2.11 <SEP> 0, <SEP> 14
 <tb> 2-Methylbutene-1 <SEP> 1.83 <SEP> 6.24 <SEP> 0, <SEP> 36
 <tb> n-Pentane <SEP> 1.51 <SEP> 5.06 <SEP> 0.63
 <tb> 2-Methylbutadiene-1, <SEP> 3 <SEP> 0, <SEP> 0537 <SEP> 0.0057 <SEP> 0, <SEP> 0000
 <tb> Trans-pentene-2 <SEP> 2.58 <SEP> 9.32 <SEP> 0, <SEP> 98
 <tb> Unknown <SEP> 1 <SEP> 0.03 <SEP> 0.06 <SEP> 0.02
 <tb> cis-pentene-2 <SEP> 1.42 <SEP> 3.98 <SEP> 0,

  60 <SEP> 18, <SEP> 29
 <tb> 2-Methylbutene-2 <SEP> 3.93 <SEP> 11.56 <SEP> 1.87
 <tb> Trans-piperylene <SEP> 0.06 <SEP> 0.00 <SEP> 0, <SEP> 03
 <tb> cis-piperylene <SEP> 0, <SEP> 03 <SEP> 0.01 <SEP> 0, <SEP> 01
 <tb> Cyclopentene <SEP> 0.06 <SEP> 0.04 <SEP> 0, <SEP> 04
 <tb> Unknown <SEP> 2 <SEP> 7.50 <SEP> 5.29 <SEP> 13.06
 <tb> More <SEP> heavy <SEP> 69.71 <SEP> 1.11 <SEP> 81.65
 <tb> Total <SEP> 100, <SEP> 00 <SEP> 100.00 <SEP> 100.00
 <tb> Pounds / h <SEP> 295.0 <SEP> 53, <SEP> 0 <SEP> 238.1 <SEP> 4.00
 <tb> Temperature, <SEP> OF <SEP> 233 <SEP> 369
 <tb>
 

  <Desc / Clms Page number 68>

 Transformation of components.
 EMI68.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 0, <SEP> 68 <SEP> 126 <SEP> ppm
 <tb> 2MB1 <SEP> + <SEP> 2MB2 <SEP> 27, <SEP> 1 <SEP> 25.7
 <tb> Isopentane <SEP> 40.7 <SEP> 43.1
 <tb> Pentenes <SEP> 22.9 <SEP> 22.6
 <tb> n-Pentane <SEP> 7.1 <SEP> 7, <SEP> 3
 <tb>% <SEP> from <SEP> 3-MB-1 <SEP> from <SEP> total <SEP> of <SEP> isoamylenes <SEP> 4.23 <SEP> 3.17
 <tb>% <SEP> from <SEP> pentene-1 <SEP> from <SEP> total <SEP> of <SEP> n-pentenes <SEP> 17.8 <SEP> 11.2
 <tb>
 

  <Desc / Clms Page number 69>

 
 EMI69.1
 EXAMPLE 6 C3 'loads
The same methods are used as those described in Example 4, however the catalyst of experiment 1 is G68C, a product containing 0.3% of palladium on alumina 3 to 6, from United Catalyst, Inc.

   6.10 m (20 feet) of catalyst packing [28, 317 dm3 (1.0 cubic feet) of catalytic material is prepared in the form of distillation structures as described in U.S. Patent No. 5,266,546,
 EMI69.2
 which are tubular lattices about 5.08 cm (2 ") long and 5.08 cm (2") in diameter, having the ends fixed at 900 relative to each other. The catalyst packing is placed in a 7.62 cm (3 inch) column, with 1.52 m (5 feet) of Pall steel ring 1.59 cm (5/811) and 3.05 m ( 10 feet) of headroom above and 0.91 m (3 feet) of anti-fog wire and 15.24 m (50 feet) of Pall steel rings 1.59 cm (5/811) below. The same structures and column are used in experiment 2, but the catalyst is G68H from United Catalyst, (0.3% of palladium and 0.3% of silver on alumina).



   Distillation is carried out to take a hydrotreated Ce head and the heavier components as a tail. The charges, conditions and results for each of the three experiments are given in Tables XII and XIII.

  <Desc / Clms Page number 70>

 



   TABLE XII
Example 6, experiment 1.



  213 hours of charging.



  Conditions.
 EMI70.1
 
 <tb>
 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 6.4
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 90
 <tb> Debit <SEP> from <SEP> H2, <SEP> scfh <SEP> 34
 <tb> Pressure, <SEP> psig <SEP> 250
 <tb> Distillate, <SEP> pound / h <SEP> 82
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 0.88
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 71>

 Results.
 EMI71.1
 
 <tb>
 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Methane <SEP> 0.00 <SEP> 0.00 <SEP> 0.00 <SEP> 0.06
 <tb> Ethylene <SEP> 0.00 <SEP> 0.00 <SEP> 0.00 <SEP> 0.45
 <tb> Ethane <SEP> 0.05 <SEP> 0.03 <SEP> 0.00
 <tb> Propene <SEP> 85, <SEP> 43 <SEP> 88.88 <SEP> 22.85 <SEP> 78.94
 <tb> Propane <SEP> 9, <SEP> 93 <SEP> 11.02 <SEP> 8.81 <SEP> 7.20
 <tb> Methylacetylene <SEP> 1.99 <SEP> 0.0000 <SEP> 7.66
 <tb> Propadiene <SEP> 0.81 <SEP> 0.0000 <SEP> 5.45
 <tb> Cyclopropane <SEP> 0, <SEP> 05 <SEP> 0.04 <SEP> 0.34
 <tb> Isobutane <SEP> 0.00 <SEP> 0, <SEP> 00 <SEP> 0.10
 <tb> Isobutene <SEP> 0.01 <SEP> 0, <SEP> 00 <SEP> 0.27
 <tb> Butene-1 <SEP> 0.21 <SEP> 0.00 <SEP> 6, <SEP> 30 <SEP> 0.13
 <tb> Butadiene <SEP> 1.37 <SEP> 0.00 <SEP> 25,

  59
 <tb> n-Butane <SEP> 0.00 <SEP> 0.00 <SEP> 2.56
 <tb> Vinylacetylene <SEP> 0.00 <SEP> 0.00 <SEP> 0.22
 <tb> Trans-butene-2 <SEP> 0.01 <SEP> 0.00 <SEP> 2.34
 <tb> cis-butene-2 <SEP> 0, <SEP> 01 <SEP> 0.00 <SEP> 1.12
 <tb> C <SEP> 0.04 <SEP> 0.00 <SEP> 0.75 <SEP> 0.04
 <tb> C <SEP> 0.00 <SEP> 0, <SEP> 00 <SEP> 13, <SEP> 51
 <tb> More <SEP> heavy <SEP> 0.00 <SEP> 0.00 <SEP> 0.01 <SEP> 0.05
 <tb> Total <SEP> 100.00 <SEP> 100.0 <SEP> 100.00
 <tb> Pounds / h <SEP> 56.0 <SEP> 37.1 <SEP> 15 <SEP> 4, <SEP> 1
 <tb> Temperature, <SEP> OF <SEP> 113 <SEP> 216
 <tb>
 

  <Desc / Clms Page number 72>

 Transformation of components.
 EMI72.1
 
 <tb>
 <tb>



  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 4.2 <SEP> 0 <SEP> ppm
 <tb> Propylene <SEP> 85.4 <SEP> 85.8
 <tb> Propane <SEP> 9.9 <SEP> 10.8
 <tb> C6 <SEP> 0, <SEP> 06 <SEP> 0, <SEP> 65
 <tb>
 

  <Desc / Clms Page number 73>

 
TABLE XIII
Example 6. experience 2.



  152 hours of charging.



  Conditions.
 EMI73.1
 
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 <tb>



  Pressure <SEP> partial <SEP> in <SEP> hydrogen, <SEP> psia <SEP> 5.2
 <tb> Debit <SEP> introduction, <SEP> pound / h <SEP> 90
 <tb> Debit <SEP> from <SEP> H2'scfh <SEP> 34
 <tb> Pressure, <SEP> psig <SEP> 250
 <tb> Distillate, <SEP> pound / h <SEP> 84
 <tb> Debit <SEP> internal <SEP> from <SEP> reflux <SEP> 1.27
 <tb> Mode <SEP> LPC
 <tb>
 

  <Desc / Clms Page number 74>

 Results.
 EMI74.1
 
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 <tb>



  Analysis <SEP> Charge, <SEP>% <SEP> Head, <SEP>% <SEP> in <SEP> Tail, <SEP>% <SEP> Ventilation,
 <tb> in <SEP> weight <SEP> weight <SEP> in <SEP> weight <SEP>% <SEP> in <SEP> weight
 <tb> Methane <SEP> 0.00 <SEP> 0.00 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 01
 <tb> Ethylene <SEP> 0.00 <SEP> 0.00 <SEP> 0, <SEP> 00 <SEP> 0, <SEP> 54
 <tb> Ethane <SEP> 0.05 <SEP> 0.03 <SEP> 0.00
 <tb> Propene <SEP> 85.43 <SEP> 88.94 <SEP> 22.17 <SEP> 74.14
 <tb> Propane <SEP> 9.93 <SEP> 10.12 <SEP> 10.13 <SEP> 6.47
 <tb> Methylacetylene <SEP> 1.99 <SEP> 0, <SEP> 0000 <SEP> 8.70
 <tb> Propadiene <SEP> 0.81 <SEP> 0.0000 <SEP> 5.90
 <tb> Cyclopropane <SEP> 0.05 <SEP> 0.03 <SEP> 0.43
 <tb> Isobutane <SEP> 0, <SEP> 00 <SEP> 0.00 <SEP> 0.39
 <tb> Isobutene <SEP> 0, <SEP> 01 <SEP> 0.00 <SEP> 0.34
 <tb> Butene-1 <SEP> 0.21 <SEP> 0, <SEP> 00 <SEP> 6.08 <SEP> 0.13
 <tb> Butadiene <SEP> 1.37 <SEP> 0.00 <SEP> 30,

    <SEP> 57
 <tb> n-Butane <SEP> 0.00 <SEP> 0.00 <SEP> 3.02
 <tb> Vinylacetylene <SEP> 0.00 <SEP> 0.00 <SEP> 0.25
 <tb> Trans-butene-2 <SEP> 0, <SEP> 01 <SEP> 0.00 <SEP> 0.70
 <tb> Cis-butene-2 <SEP> 0, <SEP> 01 <SEP> 0.00 <SEP> 0.22
 <tb> C5 <SEP> 0.04 <SEP> 0, <SEP> 00 <SEP> 0.83 <SEP> 0.04
 <tb> C <SEP> 0.00 <SEP> 0, <SEP> 00 <SEP> 8.76
 <tb> More <SEP> heavy <SEP> 0.05 <SEP> 0, <SEP> 02 <SEP> 1.52
 <tb> Total <SEP> 100.00 <SEP> 100, <SEP> 0 <SEP> 100.00
 <tb> Pounds / h <SEP> 90.0 <SEP> 83, <SEP> 9 <SEP> 3.5 <SEP> 2.8
 <tb> Temperature, <SEP> OF <SEP> 113 <SEP> 171
 <tb>
 

  <Desc / Clms Page number 75>

 Transformation of components.
 EMI75.1
 
 <tb>
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  Component <SEP> Charge, <SEP>% <SEP> in <SEP> weight <SEP> Product, <SEP>% <SEP> in <SEP> weight
 <tb> Dienes <SEP> 4.2 <SEP> 0 <SEP> ppm
 <tb> Propylene <SEP> 85.4 <SEP> 86.1
 <tb> Propane <SEP> 9.9 <SEP> 10.0
 <tb> C6 <SEP> 0, <SEP> 06 <SEP> 0, <SEP> 42
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Claims (13)

 EMI76.1   CLAIMS CLAIMS 1. - Process for the isomerization of olefins characterized in that it comprises the introduction of a hydrocarbon feed (1.301) containing the olefins as well as a charge of hydrogen (2.302), at a partial pressure in operating hydrogen in the range of at least about 689.48 Pa absolute (0.1 psia) to less than 482,636 Pa absolute (70 psia), in a distillation column reactor (10) containing a hydrogenation catalyst which is a component of a distillation structure (12, 312) and isomerization of part of the isomerizable olefins.  2.-A method according to claim 1, characterized in that the hydrocarbon feed (1.301) comprises aliphatic compounds having from 4 to 9 carbon atoms.  3.-A method according to any one of claims 1 and 2, characterized in that the hydrocarbon has a WHSV in the range of 0.1 to 35.  4.-Method according to any one of the preceding claims, characterized in that the upper pressure is in the range from 0 to  EMI76.2  2413, 180 Pa manometric (0 to 350 psig). 5.-Method according to any one of the preceding claims, characterized in that the partial hydrogen pressure is less than 344,740 Pa absolute (50 psia).  6.-A method according to claim 5, characterized in that the partial hydrogen pressure is less than 68 948 Pa absolute (10 psia).  7.-A method according to claim 6, characterized in that the partial hydrogen pressure is less than 48 263.6 Pa absolute (7 psia).  8.-Method according to any one of the preceding claims, characterized in that the hydrogenation catalyst comprises a metal or a compound  <Desc / Clms Page number 77>  metallic group VIII as main catalyst component.  9.-A method according to claim 8, characterized in that the catalyst comprises palladium.    10. - Method according to any one of the preceding claims, characterized in that the upper pressure is in the range of 344,740 to 1,034,220 manometric kPa (50 to 150 psig).    11. - Method according to any one of the preceding claims, characterized in that the hydrocarbon charge (1,301) comprises a light naphtha.    12.-A method according to claim 11, characterized in that the light naphtha comprises 3-methylbutene-1.  EMI77.1   13.-A method according to claim 12, characterized in that a part of 3-methylbutene-l is isomerized into 2-methylbutene-2 and 2-methylbutene-l.