1. Field of the Invention
The present invention relates to a process for separate steps of fractionation and isomerization of normal heptane in a naphtha stream to branched heptane.
2. Related Information
Petroleum distillate streams contain a variety of organic chemical components. Generally the streams are defined by their boiling ranges which determine the compositions. The processing of the streams also affects the composition. For instance, products from either catalytic cracking or thermal cracking processes contain high concentrations of olefinic materials as well as saturated (alkanes) materials and polyunsaturated-compounds (e.g., diolefins). Additionally, these components may be any of the various isomers of the compounds.
Reformed naphtha or reformate generally requires no further treatment except perhaps distillation or solvent extraction for valuable aromatic product removal. However, reforming of the C7 fraction of the naphtha results in the formation of aromatics, especially benzene, the content, of which in gasoline is being restricted. Isomerization of the C7 portion is thus attractive to take the light fraction of the reformer feed to make high octane fuel with less aromatics. However, the isomerization of the C7's has resulted in the fouling of the isomerization catalyst due to coking caused by cracking of the longer chain compounds. Thus, isomerization has been limited in the past to the lighter C6 fraction.
The advantages of using the isomerization process in a refinery include:
(1) removing the C7 cut reduces the amount of benzene produced in the reformer and eliminates the need for a benzene removal unit downstream of the reformer;
(2) removing the C7 cut allows the reformer to operate at conditions that have improved yields and higher product octane (specifically, at the same inlet temperature and hydrogen production rate, a one octane point gain and one percentage point gain on yield has been observed);
(3) gives more flexibility on the cut that is sent to the C5/C6 isomerization process;
(4) increases the hydrogen/feed production because the C7 paraffins contribute very little hydrogen;
(5) improves the octane of the C7 cut without producing aromatics which reduces the aromatic content in the gasoline blend; and
(6) either the C5/C6 splitter or the C7 splitter can be shut down and by passed without disrupting other refinery operations since the reformer can operate with or without theses streams and the C7 splitter can handle the C5/C6 cut.
Briefly the present invention is a process for the isomerization of normal heptane contained within a naphtha stream comprising the steps of:
fractionating said naphtha stream containing normal heptane into a fraction substantially free of normal heptane and a fraction containing normal heptane;
contacting said fraction containing normal heptane with an isomerization catalyst in an isomerization zone having a single effluent under conditions to isomerize a portion of said normal heptane to branched heptane;
recovering the effluent from said isomerization zone containing unconverted normal heptane and branched heptane and
fractionally distilling said effluent to recover said branched heptane. The unconverted normal heptane is preferably recovered and returned to the isomerization. Preferably the naphtha stream is a C6-C8 naphtha stream which is fractionated into an overheads comprising normal heptane and lighter materials and a bottoms comprising C8 naphtha (the C6-C8 split).
In one embodiment a C6-C8 naphtha stream is fed to a first fractionation to produce a first overheads comprising normal heptane and lighter materials and a first bottoms comprising C8 naphtha. The first overheads containing normal heptane is fed to a second fractionation to produce a second overheads containing lighter materials and a second bottoms containing the normal heptane. Second bottoms containing normal heptane is fed to an isomerization zone having a single effluent containing branched heptane isomerization product and unconverted normal heptane is returned to the first fractionation, where the unconverted normal heptane and the branched heptane isomerization product are taken in the first overheads to the second fractionation. The branched heptane isomerization product is recovered in the second overheads. It can be appreciated that in this embodiment the branched heptanes are low on startup, but after the first pass through the isomerization and the feeding of the isomerization effluent to the C6-C8 split, there will be substantial branched heptanes in first overheads from the C6-C8 split.
In another embodiment a C6-C8 naphtha stream is fed to a first fractionation to produce a first overheads comprising normal heptane and lighter materials and a first bottoms comprising C8 naphtha. The first overheads containing normal heptane is fed to an isomerization zone having a single effluent containing branched heptane isomerization product and unconverted normal heptane is fed to a second fractionation to produce a second overheads containing lighter materials including the branched heptane isomerization product and a second bottoms containing unconverted normal heptane is returned to the first fractionation, where the unconverted normal heptane are returned to the isomerization zone in the first overheads.
The branched heptanes are lower boiling than the normal heptane and are easily separated from the normal heptane in the fractionations.
The particular advantages of the present process using a fixed bed reactor with fractional distillation before and after for the normal heptane isomerization are:
(1) the catalyst can be packed in a vessel that can be operated at conditions ideal for the hydroisomerization and not linked to the conditions ideal for separation;
(2) the fixed bed unit with dumped packing can be smaller and built to handle regenerations more easily than a distillation column with catalyst in structured packing;
(3) the reactor can be bypassed, allowing the split to still occur without the isomerization reactions;
(4) distillation/fixed bed reaction allows for recycle both mono branched and normal heptane back to the reaction zone which increases the yield of higher di-branched product compared to units which only recycle the normal paraffins;
(5) in the distillation/fixed bed reaction the cyclic C7's are still part of the bottom product which is sent to the reformer as compared to a traditional process where the cyclics have to be cut out with the heptanes to be sent to the isomerization unit which results in an overall octane disadvantage, or in the alternative a large fraction of the normal heptane would have to be fed to the reformer; and
(6) the distillation/fixed bed process gives better yield, i.e., produces less over cracked products because the lighter species are removed by distillation, consequently these primary products are less likely to undergo cracking.
Feed is introduced to the first column and the heavy material is removed out the bottom. The second column removes the lighter material. A fixed bed reactor, where the isomerization reactions occur, is included between the first and second columns in one embodiment. The isomerization reactor may use either the vapor phase overhead from the first column, a liquid phase overhead from the first column, or, the liquid phase bottom product from a second column. In each of these cases, the first column may or may not include an overhead condenser, and/or, the second column may or may not include a reboiler.
By operating in this mode if the catalyst requires regenerations during its life, this can be performed easily and at low cost in the fixed bed reactor. Placing the reactor between the columns allows n-heptane to be internally recycled back to the reactor in the second column, while the lighter iso-heptanes are distilled overhead. This improves the octane versus placing the reactor on the overhead product.
This arrangement also isomerizes the dimethylcyclopentanes to methylcyclohexane. This upgrades the bottom product for a reformer by increasing the toluene yield and reducing the benzene make.
The distillation/fixed bed process described here is advantaged over a process where the feed is split and then isomerized (with no further separations afterward) in that:
1) the n-heptane component is separated from the isomers and recycled back to the reactor to achieve a higher conversion;
2) the dimethylpentanes, if present in high concentration, are converted to methylcyclohexane and separated out in the bottom product where they make an upgraded reformer feed. Methylcyclohexane is reformed to toluene, whereas dimethylcyclopentane may crack in the reformer to make fuel gas or partially crack to form benzene;
3) the C7 isomer material is separated out of the reactor. This material cracks more easily and by removing it, allows for longer catalyst life.
Naphthenic compounds inhibit the reaction rate. The cut point between the two columns will be adjusted depending on whether a feed is rich in C6 cyclics (CH and MCP) and poor in C7 cyclics (MCH and DMCP), or vise versa. The cut point can be adjusted to maximize n-heptane conversion and minimize the concentration of naphthenic compounds.
The feed weight hourly space velocity (WHSV), which is herein understood to mean the unit weight of feed per hour entering the reaction distillation column per unit weight of catalyst in the catalytic distillation structures, may vary over a very wide range within the other condition perimeters, e.g., 0.1 to 35, compounds in the reactor. The temperature in the catalyst bed is preferably in the range of 200 to 350° F., preferably around 270° F. at pressures in the range of 60 to 250 psig.
The composition of untreated naphtha as it comes from the crude still, or straight run naphtha, is primarily influenced by the crude source. Naphthas from paraffinic crude sources have more saturated straight chain or cyclic compounds. As a general rule most of the “sweet” (low sulfur) crudes and naphthas are paraffinic. The naphthenic crudes contain more unsaturates and cyclic and polycylic compounds. The higher sulfur content crudes tend to be naphthenic. Treatment of the different straight run naphthas in the present process may be slightly different depending upon their composition due to crude source.
Catalysts which are useful for the isomerization of C7's include non-zeolitic catalyst as disclosed in U.S. Pat. Nos. 5,648,589, 6,706,659 and 6,767,859; and zeolites as disclosed in U.S. Pat. Nos. 6,124,516 and 6,140,547. Sulfonated zirconia oxide catalysts developed by Sudchemie have also been shown to be useful.
A preferred catalyst group for the present isomerization comprises non-zeolite catalytic compounds represented by the generalized formula:
R1/R4/R2—R3
wherein:
R1 is a metal or metal alloy or bimetallic system;
R2 is any metal dopant;
R3 is a metallic oxide or mixtures of any metallic oxide;
R4 is selected from WOx, MoOx, SO42— or PO43−; and
x is a whole or fractional number between and including 2 and 3. Preferably:
R1 is selected from: a Group VIII noble metal or a combination of Group VIII noble metals; such as platinum, palladium, iridium, rhodium, nickel, cobalt or a combination thereof or a Pt—Sn, Pt—Pd, or Pt—Ga alloy, Pt—Ni alloy or bimetallic system:
R2 is selected from the group Al3+, Ga3+, Ce4+, Sb5+, Sc3+, Mg2+, Co2+, Fe3+, Cr3+, Y3+Si4+, and In3+;
R3 is selected from the group zirconium oxide, titanium oxide, tin oxide, ferric oxide, cerium oxide or mixtures thereof;
R4 is selected from SO42−, WOx, MoOx, PO43−, W20O58, W10O29 and anions and mixtures thereof; and
the ratio of metal dopant to metal in the oxide may be less than or equal to about 0.20, such as, less than or equal to about 0.05.
The Pt-sulfonated zirconia catalysts may be activated by heating catalyst in air in the reactor to 250° F. for 1 hour, heating at 840° F. (450° C.) for 1.5 hours, cooling to 220° F. in N2 and reducing with H2 gas.
A hydrogenation catalyst may be included before the isomerization catalyst to saturate any olefins, diolefins or aromatics that may be in the stream. Examples of hydrogenation catalyst include Ni (massive or dispersed on an alumina support) and Pd (dispersed on an alumina support).
The catalyst may be placed in various configurations for conducting the isomerization and separations of the invention. Preferably the catalyst is used in fixed bed reactor where it may be placed dumped in bed, on trays, screens or the like or as structure as describe below.
The use of a structured packing may be desirable to reduce the pressure drop through the fixed bed. A variety of catalyst structures for this use are well known and disclosed in U.S. Pat. Nos. 4,443,559; 4,536,373; 5,057,468; 5,130,102; 5,133,942; 5,189,001; 5,262,012; 5,266,546; 5,348,710; 5,431,890; and 5,730,843.
Multiple reactors may be arranged in series/parallel to allow for periodic regeneration of one reactor, while the other(s) remain on line.
In the drawings the same or equivalent lines and apparatus are given the same numbers. Since the drawings are merely schematic, some conventional elements such as reboilers, condensers, valves, reflux lines, etc are omitted and their inclusion in the apparatus as appropriate would be obvious to those of ordinary skill in the art.
Referring now to the
In
In
A typical reformer feed is split and isomerized by a reactor as show in the
*MCP METHYL CYCLOPENTANE
CH CYCLOHEXANE
223B 2,2,3-TRIMETHYL BUTANE
22MP 2,2-METHYL PENTANE
23MP 2,3-METHYL PENTANE
24MP 2,4-METHYL PENTANE
33MP 3,3-METHYL PENTANE
3EPN 3-ETHYL PENTANE
2MHX 2-METHYL HEXANE
3MHX 3-METHYL HEXANE
1T2C 1,2-TRANS DIMETHYL CYCLOPENTANE
1T3M 1,3-TRANS DIMETHYL CYCLOPENTANE
MCH METHYLCYCLOHEXANE