DUAL FUNCTION PROCESS FOR ISOMERIZATION AND RING OPENING OF A FEED STREAM CONTAINING PARAFFINS AND CYCLIC HYDROCARBONS

Abstract: A C₄-C₆ feed containing low octane paraffins and substantial amounts of cyclic hydrocarbons in contacted with hydrogen and a high chloride, platinum alumina catalyst under conditions selected simultaneously to open cyclic hydrocarbon rings and isomerize paraffins to more highly branched paraffins in order to produce a high octane product stream which has a relatively low cyclic content. The process is operated at relatively low severity conditions that provide favourable equilibrium conditions for isoparaffin conversion, comprising a temperature of 40 to 260°C (105 to 500°F), a pressure of 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of 0.5 to 12 hr⁻¹, while maintaining a chloride concentration in the feed stream of 30 to 300 wt ppm. The ring opening is also obtained without excessive generation of light hydrocarbons. Multiple stage reaction zones may be used to operate the first stage at slightly higher severity (higher temperature) than the second stage to maximize ring opening and obtain favourable equilibrium of iso- to normal -paraffins.

Description: This invention relates generally to a novel dual function process that can simultaneously accomplish the isomerization of light paraffins and the opening of cyclic hydrocarbon rings, with isomerization of the resulting acyclic products, to produce a high octane product stream enriched in isoparaffin hydrocarbons. High octane gasoline is required for modern gasoline engines. Formerly it was common to accomplish octane number improvement by the use of various lead-containing additives. As lead is phased out of gasoline for environmental reasons, it has become increasingly necessary to rearrange the structure of the hydrocarbons used in gasoline blending in order to achieve high octane ratings. Catalytic reforming and catalytic isomerization are two widely used processes for this upgrading. A gasoline blending pool normally includes C₄ and heavier hydrocarbons having boiling points of less than 205°C (395°F) at atmospheric pressure. This range of hydrocarbon includes C₄-C₆ paraffins, and especially the C₅ and C₆ normal paraffins which have relatively low octane numbers. The C₄-C₆ hydrocarbons have the greatest susceptibility to octane improvement by lead addition, and were formerly upgraded in this manner. Octane improvement can also be obtained by catalytically isomerizing the paraffinic hydrocarbons, to rearrange their structure into branch-chained paraffins, or reforming to convert the C₆ and heavier hydrocarbons into aromatic compounds. Normal C₅ hydrocarbons are not readily converted into aromatics, so the common practice has been to isomerize these lighter hydrocarbons into corresponding branch-chained isoparaffins. Although the C₆ and heavier hydrocarbons can be upgraded into aromatics through dehydrocyclization, the conversion of C₆ hydrocarbons into aromatics creates products of higher density and increases gas yields, with both effects leading to a reduction in liquid volume yields. Therefore, it is common practice to charge the C₆ paraffins to an isomerization unit to obtain C₆ isoparaffin hydrocarbons. Consequently, octane upgrading commonly uses isomerization to convert C₆ and lighter boiling hydrocarbons, and reforming to convert C₇ and higher boiling hydrocarbons. Converting C₆ and cyclic hydrocarbons into isoparaffins instead of aromatics can also improve overall octane ratings. Octane ratings in the US and elsewhere represent a blend of research and motor octane values. The difference, sometimes referred to as octane sensitivity, between motor and research octane values is high for aromatics and C₆ cyclics, with motor octane being less than research octane by as much as 10 numbers. On the other hand, the octane sensitivity for isohexanes varies by no more than a few numbers. The relatively higher motor octane number and reduced octane sensitivity again favours the conversion of C₆ cyclic paraffins into isoparaffins. The isomerization of paraffins is a reversible first order reaction. The reaction is limited by thermodynamic equilibrium. The basic types of catalyst system that are used in effecting the reaction are a hydrochloric acid-promoted aluminium chloride system, and a supported aluminium chloride catalyst. Both catalysts are very reactive, and can generate undesirable side reactions, such as disproportionation and cracking. These side reactions not only decrease the product yield, but can form olefinic fragments that combine with the catalyst and shorten its life. One commonly practiced method of controlling these undesired reactions has been to carry out the reaction in the presence of hydrogen. A large percentage of the C₄-C₆ paraffin fractions that are available as feedstocks for C₄-C₆ isomerization processes include cyclic hydrocarbons. These cyclic hydrocarbons tend to be adsorbed on the isomerization catalysts. Absorption of the cyclic compounds blocks active sites on the catalyst and thereby excludes the isomerizable paraffins from the catalyst. This exclusion diminishes the overall conversion of the process. As a result, removal of cyclic hydrocarbons from an isomerization process will increase conversion of the paraffins into more highly branched paraffins, and rearrangement of the cyclic hydrocarbons into branched paraffins will increase volume yield. Complete removal of cyclic hydrocarbons by ordinary separation cannot be achieved, due to the boiling points of the C₆ paraffins and many of the cyclic hydrocarbons, in particular, normal hexane and methylcyclopentane. US-A-2915571 teaches the reduction of naphthenes in an isomerization feed fraction by contact with a ring opening catalyst containing an iron group metal in a first reaction zone, and subsequent isomerization of the feed fraction by contact with a different catalyst in an isomerization zone. Opening of the cyclic hydrocarbons has the twofold advantage of eliminating the cyclic hydrocarbons that can cause catalyst fouling, and increasing the volume of lower density isomerizable hydrocarbons that in turn increases product yields. The use of different catalysts for ring opening and isomerization imposes a major drawback on the process of US-A-2915571, since it requires at least one additional reaction zone. US-A-3631117 describes a process for the hydroisomerization of cyclic hydrocarbons that uses a zeolite-supported Group VIII metal, as a ring opening catalyst at high severity conditions, and as an isomerization catalyst at low severity conditions, to obtain cyclic isomers having at least one fewer carbon atom per ring than the unconverted cyclic hydrocarbons. When high severity operating conditions are used to open rings, substantial cracking of C₄-C₆ hydrocarbons to light ends will also occur. Therefore, high severity conditions to open rings in C₄-C₆ hydrocarbon feedstocks are usually avoided. The disadvantages of dual catalyst systems, additional reaction zones and production of light ends have provided substantial obstacles to the conversion of cyclic hydrocarbons in isomerizable feedstocks of C₄-C₆ hydrocarbons. It has now been discovered that cyclic hydrocarbons can be converted into branched chain isomers in a paraffin isomerization process using a single catalyst system, at low severity conditions. The present invention provides a process for the isomerization and ring opening of a feed stream comprising C₄-C₆ isomerizable hydrocarbons and at least 2 wt % of cyclic hydrocarbons, to produce a product having an increased octane number relative to the feed stream and a concentration of cyclic hydrocarbons at least 40 weight % lower than in said feed stream, which comprises contacting the feed stream in a reaction zone with hydrogen and a catalyst comprising alumina in combination with 0.1 to 0.25 wt % of a platinum component, and 2 to 10 wt % of a chloride component at isomerization and ring opening conditions including a temperature of 40 to 260°C (105 to 500°F), a pressure of 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of 0.5 to 12 hr⁻¹; while maintaining a chloride concentration equivalent to from 30 to 300 wt ppm of the feed stream in the reactants entering said reaction zone, the amount of hydrogen being such as to provide a hydrogen to hydrocarbon molar ratio of from 0.01:1 to 10:1 in the effluent from the isomerization zone. Preferably, the feed stream comprises C₅-C₆ hydrocarbons and the isomerization conditions include a temperature of 120 to 180°C (250 to 360°F), a pressure of 25 to 60 barsg (2.6 to 6.1 MPa) and a space velocity of 0.1 to 3 hr⁻¹. According to one embodiment of the invention, the reaction zone comprises at least two reactors in series, operating within the temperature range of 40 to 260°C (105 to 500°F), the first reactor having a higher temperature than the second. For instance, in the first of the reactors, the ring opening and isomerization conditions can comprise a temperature of 100 to 260°C (160 to 500°F), a pressure of 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of 0.1 to 10 hr⁻¹, producing a first product stream having a reduced concentration of cyclic hydrocarbons relative to the feed stream, which is passed into the second reactor, operated at isomerization conditions comprising a temperature of 40 to 200°C (105 to 390°F), a pressure of 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of 0.1 to 10 hr⁻¹, to produce a second product stream having an increased octane number relative to the feed stream and a concentration of cyclic hydrocarbons at least 40 weight % lower than said feed stream. Preferably, the space velocity in the reactors is less than 3 hr⁻¹, and the pressure in said reaction zones is at lest 30 barsg (3.1 MPa), the temperature in the first reactor being at least 180°C (360°F) and the temperature in the second reactor being less than 180°C (360°F). The results achieved by practising the process according to the present invention are illustrated in the accompanying Drawings, in which Figures 1 and 2 are graphs of performance parameters for the process, plotted as a function of reaction temperature. This invention is a dual function process for isomerizing and ring opening a feedstock comprising normal paraffins having 4 to 6 carbon atoms and at least 2 wt % of cyclic hydrocarbons, that achieves high conversion and good stability by opening the rings of the cyclic hydrocarbons without appreciable chain shortening. The invention uses a highly active chlorided platinum/aluminium catalyst in the isomerization reaction which has been discovered to open the rings of cyclic hydrocarbons at temperatures at or slightly greater than typical isomerization temperatures without generating light gases by subsequent cracking of opened rings. Eliminating the cyclic hydrocarbons by ring cleavage offers the dual advantages of increasing the activity and stability of the catalyst while also raising the liquid volume yields. The feedstocks that can be used in this invention include hydrocarbon fractions rich in C₄ to C₆ normal paraffins. The term "rich" means a stream having more than 50% of the mentioned component. In addition the feedstock will include cyclic hydrocarbons. In order to realize the advantages of this invention, the concentration of cyclics in the feedstock will at least equal that which would reduce the activity of an isomerization catalyst by adsorption of the cyclics thereon or which, due to its higher density in contrast to branched chain paraffins, would represent a significant loss of liquid volume yield. The minimum concentration is 2 wt %. There is no upper limit on the concentration of cyclic hydrocarbons in the feed, since the process of this invention can be used for processing feedstocks composed primarily of cyclic hydrocarbons. The feedstock will, however, usually contain from 2 to 30 wt % of cyclic hydrocarbons. Possible types of cyclic hydrocarbons in the feed include alicyclic and aromatic hydrocarbons. If unsaturated cyclic hydrocarbons, including benzene or benzene derivatives, enter the process, they are rapidly saturated therein and effectively serve as additional cycloalkane components. Typically, the cyclic components will have 5 to 7 carbon atoms. The feed components will usually comprise C₄ to C₇ cyclic and paraffinic hydrocarbons, with n-hexane and n-pentane providing most of the paraffinic components. Useful feedstocks that will contain cyclic components include light natural gasoline, light straight run naphtha, gas oil condensate, light raffinates, light reformate, light hydrocarbons, field butanes, and straight run distillates having distillation end points of 77°C (170°F) and containing substantial quantities of C₄-C₆ paraffins. As mentioned, the feed stream may also contain low concentrations of unsaturated hydrocarbons, such as benzene or olefins, as well as hydrocarbons having more than 6 carbon atoms. The concentration of these materials should be limited to 10 wt % for unsaturated compounds, and 20 wt % for heavier hydrocarbons, in order to restrict hydrogen consumption and cracking reactions. Hydrogen is mixed with the feed in an amount that will provide a hydrogen to hydrocarbon molar ratio of from 0.01:1 to 10:1 in the effluent from the isomerization zone. Preferably, the hydrogen to hydrocarbon ratio is in the range of 0.05:1 to 5:1. Although no net hydrogen is consumed in the isomerization reaction, the isomerization zone will have a net consumption of hydrogen, often referred to as the stoichiometric hydrogen requirement, which is associated with a number of side reactions that occur. These side reactions include saturation of olefins and aromatics, cracking and disproportionation. For feeds having a high level of unsaturates, satisfying the stoichiometric hydrogen will require a higher hydrogen to hydrocarbon ratio for the feed at the inlet of the isomerization zone. Hydrogen in excess of the stoichiometric amounts for the side reactions is maintained in the reaction zone, to provide good stability and conversion by compensating for variations in feed stream compositions that alter the stoichiometric hydrogen requirements, and to prolong catalyst life by suppressing side reactions such as cracking and disproportionation. If left unchecked, the side reactions reduce conversion, and lead to the formation of carbonaceous materials, usually referred to as coke, that foul the catalyst. When the hydrogen to hydrocarbon ratio exceeds 0.05:1, it is not economically desirable to operate the isomerization process without the recycle of hydrogen to the isomerization zone. Thus, recovery facilities for hydrogen from the effluent will be provided. Hydrogen may be added to the feed mixture in any manner that provides the necessary control for the addition of the hydrogen quantities. The hydrogen and hydrocarbon feed mixture is contacted in the reaction zone with an isomerization catalyst. The isomerization catalyst comprises a high chloride catalyst on an alumina base containing a platinum component. The alumina is preferably an anhydrous gamma-alumina with a high degree of purity. The catalyst may also contain other platinum group metals. The term platinum group metals means noble metals, excluding silver and gold, which are selected from the group consisting of platinum, palladium, ruthenium, rhodium, osmium, and iridium. These metals demonstrate differences in activity and selectivity such that platinum has now been found to be the most suitable for this process. The catalyst will contain from 0.1 to 0.25 wt % of the platinum component. Other platinum group metals may be present in a concentration of from 0.1 to 0.25 wt %. The platinum component may exist within the final catalytic composite as an oxide or halide or as an elemental metal. The presence of the platinum component in its reduced state has been found most suitable for this process. The catalyst also contains a chloride component. The chloride component, termed in the art "a combined chloride", is resent in an amount from 2 to 10 wt %, based upon the dry support material. The use of chloride in amounts greater than 5 wt % has been found to be the most beneficial for this process. There are a variety of ways for preparing the catalyst composite and incorporating the platinum metal and the chloride therein. The method that has shown the best results in this invention prepares the catalyst by impregnating the carrier material through contact with an aqueous solution of a water-soluble decomposable compound of the platinum group metal. For best results, the impregnation is carried out by dipping the carrier material in a solution of chloroplatinic acid. Additional solutions that may be used include ammonium chloroplatinate, bromoplatinic acid or platinum dichloride. Use of platinum chloride serves the dual function of incorporating the platinum component and at least part of the chloride into the catalyst. Additional amounts of the chloride must be incorporated into the catalyst by the addition of aluminium chloride to or formation of aluminium chloride on the platinum-aluminium catalyst base. An alternative method of increasing the chloride concentration in the final catalyst composite is to use an aluminium hydrosol to form the alumina carrier material, such that the carrier material also contains at least a portion of the chloride. Chloride may also be added to the carrier material by contacting the calcined carrier material with an aqueous solution of hydrogen chloride. It is generally known that high chloride platinum-alumina catalysts of this type are highly sensitive to sulphur and oxygen-containing compounds. Therefore, the feedstock must be relatively free of such compounds. A sulphur concentration no greater than 0.5 wt ppm is generally required. The presence of sulphur in the feedstock serves to deactivate the catalyst temporarily by poisoning the platinum. Activity of the catalyst may be restored by hot hydrogen stripping of sulphur from the catalyst composite, or by lowering the sulphur concentration in the incoming feed to below 0.5 wt ppm so that the hydrocarbon will desorb the sulphur that has been adsorbed on the catalyst. Water can act to deactivate the catalyst permanently by removing high activity chloride from the catalyst and replacing it with inactive aluminium hydroxide. Therefore, water, as well as oxygenates, in particular C₁-C₅ oxygenates, that can decompose to form water, can only be tolerated in very low concentrations. In general, this requires a limitation of oxygenates in the feed to 0.1 wt ppm or less. The feedstock may be treated by any method that will remove water and sulphur compounds. Sulphur may be removed from the feed stream by hydrotreating. A variety of commercial dryers are available to remove water from the feed components. Adsorption processes for the removal of sulphur and water from hydrocarbon streams are also well known to those skilled in the art. In this invention, it is also recognized that cyclic hydrocarbons, especially C₆ cyclics such as benzene, cyclohexane and methylcyclopentane, adversely affect the degree of paraffin isomerization. The adverse effect is believed to be caused by preferential adsorption of the cyclic hydrocarbons on the catalyst surface and the resulting exclusion of the paraffinic hydrocarbons. The process of this invention uses the aforementioned catalyst at selected operating conditions to eliminate the cyclics by their contact therewith while converting the cyclics to provide additional isomerization product. It is not necessary to achieve a complete elimination of the rings in order to enjoy the benefits of this invention. Conversion of only a small percentage of the rings in the entering feed will provide a substantial increase in the isoparaffin yield. Generally, the process will be operated to open at least 40 wt % of the rings in the entering feed. When the cyclic hydrocarbon concentration of the feed exceeds 15 wt %, a greater degree of ring opening may be sought, such that the cyclic hydrocarbon concentration in the effluent from the reaction zone is kept below 7 wt %. Temperature and pressure conditions directly affect the degree of ring opening. Operating conditions within the isomerization zone are selected to maximize the production of isoalkane product from the feed components. Temperatures within the reaction zone will be from 40 to 260°C (105 to 500°F). Lower reaction temperatures are preferred for purposes of isomerization conversion, since they favour isoalkanes over normal alkanes in equilibrium mixtures, but maximizing ring opening sometimes requires temperatures in excess of those that are most favourable from an equilibrium standpoint. For example, when the feed mixture is primarily C₅ and C₆ alkanes, temperatures of 60 to 160°C are desired from a normal-/iso-alkane equilibrium standpoint, but due to ring opening considerations, the preferred temperature range for this invention is from 100 to 200°C. When it is desired to isomerize significant amounts of C₄ hydrocarbons, higher reaction temperatures are required to maintain catalyst activity. Thus, when the feed mixture contains significant portions of C₄ to C₆ alkanes, the most suitable operating temperatures for ring opening and isoalkane equilibrium coincide and are in the range from 145 to 225°C. The reaction zone may be maintained over a wide range of pressures. Pressure conditions in the isomerization of C₄-C₆ paraffins range from 7 to 70 barsg (0.8 to 7.1 MPa). Higher pressures favour ring opening, so the preferred pressures for this process are from 25 to 60 barsg (2.6 to 6.1 MPa). The feed rate to the reaction zone can also vary over a wide range. These conditions include liquid hourly space velocities from 0.5 to 12 hr⁻¹, space velocities from 0.5 to 3 hr⁻¹ being preferred. Operation of the reaction zone also requires the presence of a small amount of an organic chloride promoter. The organic chloride promoter serves to maintain a high level of active chloride on the catalyst as small amounts of chloride are continuously stripped off the catalyst by the hydrocarbon feed. The concentration of promoter in the reaction zone is maintained in an amount equivalent to 30 to 300 wt ppm of the feed. The preferred promoter compound is carbon tetrachloride. Other suitable promoter compounds include oxygen-free decomposable organic chlorides such as propyldichloride, butylchloride, and chloroform to name only a few of such compounds. The need to keep the reactants dry is reinforced by the presence of the organic chloride compound which may be converted, in part, into hydrogen chloride. As long as the process streams are kept dry, there will be no adverse effect from the presence of small amounts of hydrogen chloride. A preferred manner of operating the process is in a two-reactor system. The catalyst used in the process can be distributed equally or in varying proportions between the two reactors. The use of two reactors permits a variation of the operating conditions between the two reactors to enhance cyclic hydrocarbon conversion in one reactor and normal paraffin isomerization in the other. In this manner, the first reactor operates at higher temperature and pressure conditions that favour ring opening and performs only a portion of the normal to isoparaffin conversion. The likelihood of exothermic reactions, such as the hydrogenation of unsaturates, occurring in the first reactor facilitates the use of higher temperatures therein. Once the rings have been opened by initial contact with the catalyst, the final reactor stage may operate at temperature conditions that are more favourable for isoalkane equilibrium. Another benefit of using two reactors is that it allows partial replacement of the catalyst system without taking the isomerization unit off stream. For short periods, during which the replacement of catalyst may be necessary, the entire flow of reactants may be processed through only one reaction vessel while catalyst is replaced in the other. Whether operated with one or two reactors, the effluent of the process will enter separation facilities in the recovery of a high octane isoalkane product. At minimum, the separation facilities divide the reaction zone effluent into a product stream comprising C₄ and heavier hydrocarbons, and a gas stream which is made up of lighter hydrocarbons and hydrogen. Suitable designs for rectification columns and separator vessels are well known to those skilled in the art. The separation section may also include facilities for recovery of normal alkanes. Normal alkanes recovered from the separation facilities may be recycled to the isomerization reaction zone to increase the conversion of normal alkanes into isoalkanes. Typical separation facilities will comprise a stabilizer section, that receives the effluent from the reaction and includes at least one stabilizer column. The stabilizer column is operated to deliver a bottoms fraction containing C₄ and heavier hydrocarbons, and an overhead fraction of C₃ hydrocarbons and lighter boiling compounds. The heavier hydrocarbons recovered from the bottom of the stabilizer column are cooled, and may be further separated into a product stream and a reflux stream. C₃ and lighter hydrocarbons taken overhead from the stabilizer column are cooled, condensed and separated into a reflux stream, which is returned to the process, and a net gas stream. The net gas stream enters a scrubber section that contacts the gas with a suitable treatment solution for neutralizing and/or removing acidic components that may have originated with the chloride addition to the isomerization zone and may be present in the gas stream. EXAMPLES The process of this invention is characterized by substantial ring opening, high conversion, high selectivity and low production of C₃ and lighter gases, as can be seen from the following Examples. In these Examples, the reactions were carried out in the presence of an alumina catalyst having 0.25 wt of % platinum and 5.5 wt % of chlorine, which was prepared by vacuum impregnating an alumina base in a solution of chloroplatinic acid, 20% of hydrochloric acid, and 3.5% of nitric acid, in a volume ratio of 9 parts solution to 10 parts base, to obtain a material having a platinum to base ratio of approximately 0.9. The resulting mixture was cold-rolled for approximately 1 hour and evaporated until dry. Afterwards, the catalyst was oxidized and the chloride content was adjusted by contact with a 1M hydrochloric acid solution at 525°C at a rate of 45 cm³/hour for 2 hours. The catalyst was then reduced in electrolytic hydrogen at 565°C for 1 hour and was found to contain approximately 0.25 wt % of Pt and approximately 1 wt % of chloride. Impregnation of active chloride to a level of approximately 5.5 wt % was accomplished by subliming aluminium chloride with hydrogen and contacting the catalyst with the subliming aluminium chloride for approximately 45 minutes at 550°C. EXAMPLE 1 A synthetic feedstock having the composition given in Table 1 was prepared. The feedstock was passed through a single reaction zone containing the previously described catalyst at a liquid hourly space velocity of 2 hr⁻¹ and a hydrogen to hydrocarbon molar ratio of 2:1. For a first series of runs, the pressure was maintained at 21 barsg (2.2 MPa) while the temperature was periodically increased over the range from 140 to 200°C. This procedure was repeated at pressures of 31 barsg (3.2 MPa) and 70 barsg (7.1 MPa). The reaction zone effluent of each run was analyzed to determine the percentage of ring opening, the isopentane to C₅ hydrocarbon ratio, the 2,2 dimethylbutane to C₆ hydrocarbon ratio, and the concentration of C₁-C₄ hydrocarbons contained therein. These various properties were plotted as a function of temperature at the three different pressure levels and are shown in Figure 1. Looking first at the plot for ring opening, the process of this invention provides a high degree of ring opening. Ring openings in excess of 40 percent were achieved at pressures as low as 21 bars (2.2 MPa) for a temperature of 180°C, and temperatures as low as 135°C for a pressure of 70 barsg (7.1 MPa). As the plot of C₁-C₄ hydrocarbon concentration shows, only a small concentration of light materials was generated by the ring opening and isomerization reactions. Higher temperatures and pressures promoted additional cracking to lighter hydrocarbons; however, even at 70 barsg (7.1 MPa) and 180°C, which conditions provided the highest ring opening, and are well above the conditions at which the process would be operated, the effluent concentration of C₁-C₄ hydrocarbons did not exceed 4 wt %. The remaining two plots demonstrate the overall ability of the process to achieve a high conversion of C₅ and C₆ hydrocarbons to corresponding isoparaffins. TYPICAL FEEDSTOCK WT % i-C₅ 0 n-C₅ 44.0 i-C₆ 0 n-C₆ 45.6 methyl cyclopentane (MCP) 4.0 cyclohexane (CH) 4.4 benzene (BZ) 2.0 C₇+ 0 TOTAL 100.0 EXAMPLE 2 The synthetic feedstock of Example 1 was again passed through the reaction zone of Example 1 at a hydrogen to hydrocarbon molar ratio of 2:1 and a liquid hourly space velocity of 4 hr⁻¹. In substantially the same manner as in Example 1, the temperature in the reaction zone was varied periodically at pressure levels of 21, 31 and 70 barsg (2.2, 3.2 and 7.1 MPa). The effluent from the reaction zone was monitored to provide data for the plots of Figure 2 which show the ring opening percentage, C₁-C₄ hydrocarbon concentration, isopentane to C₅ hydrocarbon ratio, and the 2,2 dimethylbutane to C₆ hydrocarbon ratio, as a function of temperature. The plots shown in Figure 1 again demonstrate the ability of the process to open rings while obtaining a good conversion of normal paraffins into isoparaffins, without generating excessive amounts of light hydrocarbons. Looking specifically at the plots for ring opening and C₁-C₄ hydrocarbon concentration, the overall effect of the higher space velocity is a rightward shifting of the performance profiles relative to Figure 1, such that higher temperatures are required to obtain the percentage losses and conversions. The plots for isopentane and dimethylbutane conversion show a loss of conversion for Example 2 relative to Example 1. EXAMPLES 3 to 5 In these Examples, commercial feedstocks were contacted with the previously described catalyst. The feedstock was passed through two reaction zones. The feed composition and the effluent properties after each reaction stage are listed in Tables 2 to 4, along with processing conditions for each reaction stage. In addition to verifying the ability of the process to open rings, achieve high conversion and not produce excessive light material, the data demonstrate that most of the ring opening occurs in the first stage. The data related to benzene also show that any unsaturates that enter the process are rapidly hydrogenated. EXAMPLE 6 Example 6 shows the operation of the process in the isomerization of C₄ hydrocarbons through a single reaction zone. In order to isomerize the C₄ hydrocarbons, the reaction zone operated at higher severity including an average reaction temperature of 220°C, a pressure of 31 barsg (3.2 MPa) and a liquid hourly space velocity of 2 hr⁻¹. Throughout the test, a hydrogen to hydrocarbon molar ratio of 2 was maintained. The feed composition and effluent properties for this test appear in Table 5. Table 5 illustrates the effect of higher severity on increasing the percentage of ring opening. YIELDS wt.% FEED FIRST STAGE PRODUCT SECOND STAGE PRODUCT C₃ 0.6 0.7 I-C₄ 0.1 1.8 2.3 N-C₄ 0.4 0.6 0.7 C₄ Total 0.5 2.4 3.0 I-C₅ 9.5 21.5 21.9 N-C₅ 18.4 7.5 7.1 Cyclopentane 2.9 2.3 2.0 C₅ Total 30.8 31.3 31.0 2,2-DMB 3.2 14.9 17.2 2,3-DMB 4.2 6.2 6.1 2-MP 20.0 19.0 18.4 3-MP 14.4 11.1 10.8 MCP 6.0 3.4 2.5 N-Hexane 16.9 7.6 7.4 Cyclohexane 0.9 2.2 1.7 Benzene 1.7 0.0 0.0 C₆ Total 67.3 64.4 64.0 C₇+ Total 1.4 1.3 1.3 TOTAL 100.0 100.0 100.0 Reaction Conditions LHSV, hr.⁻¹ 2.0 2.0 Ave. Bed Temp., °C 177 160 ΔT 18.9 7.7 Pressure psig/MPa 400/2.86 400/2.86 Liquid Product Octanes RON-C 69.8 81.7 82.2 MON-C 67.4 79.5 80.2 Product Ratios iC₅/C₅P 34.0 74.1 75.5 2,2-DMB/C₆P 5.5 25.3 28.7 2,3-DMB/C₆P 7.1 10.5 10.2 % Ring Opening 35 51 YIELDS wt.% FEED FIRST STAGE PRODUCT SECOND STAGE PRODUCT C₃ 0.1 0.4 0.4 I-C₄ 0.6 2.0 2.4 N-C₄ 1.1 1.1 1.1 C₄ Total 1.7 3.1 3.5 I-C₅ 16.0 28.2 29.5 N-C₅ 21.7 9.4 8.4 Cyclopentane 2.6 2.1 1.7 C₅ Total 40.3 39.7 39.6 2,2-DMB 2.3 13.5 17.2 2,3-DMB 2.8 5.0 5.0 2-MP 15.4 15.0 14.5 3-MP 9.4 8.6 8.0 MCP 5.3 4.1 2.7 N-Hexane 15.7 6.0 5.2 Cyclohexane 1.7 3.2 2.4 Benzene 3.7 0.0 0.0 C₆ Total 56.3 55.4 55.0 C₇+ Total 1.6 1.4 1.5 TOTAL 100.0 100.0 100.0 Reaction Conditions LHSV, hr.⁻¹ 2.0 2.0 Ave. Bed Temp. 160 135 ΔT 22.2 5.5 Pressure psig/MPa 450/3.20 450/3.20 Liquid Product Octanes RON-C 70.9 82.3 83.3 MON-C 69.0 80.9 82.2 Product Ratios iC₅/C₅P 42.4 75.0 77.8 2,2-DMB/C₆P 5.0 28.1 34.5 2,3-DMB/C₆P 6.1 10.4 10.0 % Ring Opening 32 52 YIELDS wt.% FEED FIRST STAGE PRODUCT SECOND STAGE PRODUCT C₃ 0.0 2.2 2.7 I-C₄ 0.2 4.7 5.4 N-C₄ 0.6 1.1 1.3 C₄ Total 0.8 5.8 6.7 I-C₅ 9.3 20.1 21.5 N-C₅ 18.1 7.6 6.8 Cyclopentane 2.5 2.1 1.9 C₅ Total 29.9 29.8 30.2 2,2-DMB 2.7 11.2 13.9 2,3-DMB 3.4 5.6 5.3 2-MP 16.8 17.4 16.0 3-MP 12.0 10.4 9.2 MCP 5.6 3.8 2.8 N-Hexane 15.4 7.3 6.8 Cyclohexane 1.4 2.2 2.3 Benzene 1.7 0.0 0.0 C₆ Total 59.0 57.9 56.3 C₇+ Total 10.3 4.3 4.1 TOTAL 100.0 100.0 100.0 Reaction Conditions LHSV, hr.⁻¹ 2.0 2.0 Ave. Bed Temp., °C 182 166 ΔT 26.1 8.9 Pressure psig/MPa 450/3.20 450/3.20 Liquid Product Octanes RON-C 70.3 82.7 83.8 MON-C 67.9 81.1 82.0 Product Ratios iC₅/C₅P 33.9 72.6 76.0 2,2-DMB/C₆P 5.4 21.6 27.2 2,3-DMB/C₆P 6.8 10.8 10.4 % Ring Opening 31 41 Composition Wt.% Feed Product C₁ 0.2 C₂ 0.3 C₃ 1.7 i-C₄ 18.5 n-NC₄ 33.6 16.7 i-C₅ 21.5 n-C₅ 7.7 CP 0.1 2,2-DMB 8.6 2,3-DMB 2.9 2-MP 10.6 3-MP 6.3 n-C₆ 32.0 4.5 MCP 2.6 0.2 CH 2.7 0.1 Benzene 2.3 C₇+ 0.1 TOTAL 100.0 100.0 i-C₄/C₄P 53 i-C₅/C₅P 74 2,2-DMB/C₆P 26 Ring Opening, % 96

Claims: A process for the isomerization and ring opening of a feed stream comprising C₄-C₆ isomerizable hydrocarbons and at least 2 wt % of cyclic hydrocarbons, to produce a product having an increased octane number relative to the feed stream and a concentration of cyclic hydrocarbons at least 40 wt % lower than said feed stream, characterized by contacting the feed stream in a reaction zone with hydrogen and a catalyst comprising alumina in combination with 0.1 to 0.25 wt % of a platinum component, and with 2 to 10 wt % of a chloride component at isomerization and ring opening conditions including a temperature of 40 to 260°C (105 to 500°F), a pressure of 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of 0.5 to 12 hr⁻¹, while maintaining a chloride concentration equivalent from 30 to 300 wt ppm of the feed stream in the reactants entering said reaction zone, the amount of hydrogen being such as to provide a hydrogen to hydrocarbon molar ratio of from 0.01:1 to 10:1 in the effluent from the isomerization zone. A process according to claim 1 characterized in that the feed stream comprises C₅-C₆ hydrocarbons and the isomerization conditions include a temperature of 120 to 180°C (250 to 360°F), a pressure of 25 to 60 barsg (2.6 to 6.1 MPa) and a space velocity of 0.1 to 3 hr⁻¹. A process according to claim 1 characterized in that the reaction zone comprises at least two reactors in series, operating within the temperature range of 40 to 260°C (105 to 500°F), the first reactor having a higher temperature than the second. A process according to claim 3 characterized in that the first reactor is operated at ring opening and isomerization conditions comprising a temperature of 100 to 260°C (160 to 500°F), a pressure of from 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of from 0.1 to 10 hr⁻¹, to form a first product stream having a reduced concentration of cyclic hydrocarbons relative to the feed stream, the first product stream being passed into the second reactor, operated at isomerization conditions comprising a temperature of 40 to 200°C (105 to 390°F), a pressure of 7 to 70 barsg (0.8 to 7.1 MPa) and a space velocity of from 0.1 to 10 hr⁻¹, to produce a second product stream having an increased octane number relative to the feed stream and a weight percentage concentration of cyclic hydrocarbons at least 40% lower than said feed stream. A process according to claim 4 characterized in that the space velocity in said reactors is less than 3 hr⁻¹, the pressure is at least 30 barsg (3.1 MPa), the temperature in the first reactor is at least 180°C (360°F) and the temperature in the second reactor is less than 180°C (360°F).

Inventors: SCHMIDT, ROBERT J., STINE, LAURENCE O.
Applicants: UOP
Application year: 1988
Main classification: C10G35
IPC codes: B01J27, C10G47, C10G45, C07C5, C07C67, C07C1, C07B61, C10G35