CA1127583A - Catalytic reforming with rhenium-platinum catalyst containing more rhenium than platinum - Google Patents
Catalytic reforming with rhenium-platinum catalyst containing more rhenium than platinumInfo
- Publication number
- CA1127583A CA1127583A CA325,146A CA325146A CA1127583A CA 1127583 A CA1127583 A CA 1127583A CA 325146 A CA325146 A CA 325146A CA 1127583 A CA1127583 A CA 1127583A
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- CA
- Canada
- Prior art keywords
- platinum
- rhenium
- range
- reforming
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
Abstract
CATALYTIC REFORMING WITH RHENIUM-PLATINUM
CATALYST CONTAINING MORE RHENIUM THAN PLATINUM
ABSTRACT
A new reforming process employs a new rhenium-platinum catalytic composite having a rhenium to platinum weight ratio in the range of not less than 2 to about 5, whereby longer relative cycle length is obtained when reforming a naphtha having less than about 0.5 ppm by weight of sulfur than if the rhenium-platinum ratio is outside of such range.
CATALYST CONTAINING MORE RHENIUM THAN PLATINUM
ABSTRACT
A new reforming process employs a new rhenium-platinum catalytic composite having a rhenium to platinum weight ratio in the range of not less than 2 to about 5, whereby longer relative cycle length is obtained when reforming a naphtha having less than about 0.5 ppm by weight of sulfur than if the rhenium-platinum ratio is outside of such range.
Description
1~27S83 BACKGROUND OF THE INVENTION ~
This invention relates to a new process of catalytically reforming naphtha, and a new catalytic composite to be employed therein.
Catalytic reforming of naphtha is widely employed in the petroleum refining industry to manufacture motor fuel blending stock having a greatly increased octane number, relative to the naphtha feedstock, and to manufacturing aromatics, especially benzene, toluene and xylenes. The improvement in octane number is especially important when metal-containing additives, such as tetraethyl lead (TEL), are not employed for environmental reasons. The research octane number of a blending ' stock or motor fuel which is free of such additives is determined i by ASTM test No. D-2699, and is often referred to as the "clear" I
or F-l octane number. Improvements in the manufacture of no-lead !
motor fuel are of particular environmental-importance.
Most reforming catalysts employ platinum as a catalytic agent. Some aiso employ rhenium together with platinum. Both are expensive, although platinum is about 7-10 times as expensive i as rhenium, and hence reforming catalyst is one of the most .' .
. . .
11 11275~33 l !expensive catalysts employed in petroleum refining. Any
This invention relates to a new process of catalytically reforming naphtha, and a new catalytic composite to be employed therein.
Catalytic reforming of naphtha is widely employed in the petroleum refining industry to manufacture motor fuel blending stock having a greatly increased octane number, relative to the naphtha feedstock, and to manufacturing aromatics, especially benzene, toluene and xylenes. The improvement in octane number is especially important when metal-containing additives, such as tetraethyl lead (TEL), are not employed for environmental reasons. The research octane number of a blending ' stock or motor fuel which is free of such additives is determined i by ASTM test No. D-2699, and is often referred to as the "clear" I
or F-l octane number. Improvements in the manufacture of no-lead !
motor fuel are of particular environmental-importance.
Most reforming catalysts employ platinum as a catalytic agent. Some aiso employ rhenium together with platinum. Both are expensive, although platinum is about 7-10 times as expensive i as rhenium, and hence reforming catalyst is one of the most .' .
. . .
11 11275~33 l !expensive catalysts employed in petroleum refining. Any
2 improvements which reduce catalytic cost per barrel of naphtha
3 reformed, such as by increasing the catalyst life (i.e.,
4 'increasing the number of barrels of naphtha which can be reformed per pound of catalyst before the catalyst becomes 6' so deactivated as to require replacement) is advantageous.
7 ;This is also true in respect of increasing the cycle length 8 of the catalyst, i.e., increasing the number of barrels of 9 naphtha which can be reformed per pound of catalyst before the catalyst requires regeneration.
11 In addition, Russia and South Africa are the source 12 of more than 95% of the free world's supply of platinum. Any 13 improvements which decrease the amount of platinum required 14 by industry, again, for example, by increasing the life of platinum-containing reforming catalysts, while still accomplish-16 ing the industrial purpose is a contribution to national 17 security and also to economic independence.
1 18 ; The original precious commercial catalysts employed 19 ' a platinum-group metal, preferably platinum itself, as the catalytic agent; see, for example, Haensel's patents Nos.
21 l 2,479,109-110, granted in 1949 and assigned to the Universal 22 Oil Products Company. About 1968, the use of rhenium together 23 1l with platinum was introduced. A number of references refer to 24 Irhenium-platinum catalysts. Kluksdhal's patent No. 3,415,737, 25 ¦assigned to Chevron Research Corporation, teaches that 26 "It is preferred that the rhenium to platinum atom ratio be from about 0.2 to about 2Ø More particularly, it is 27 preferred that the atom ratio of rhenium to platinum does not exceed one. Higher ratios (i.e. greater than one) of 28 rhenium to platinum can be used but generally no further 29 ¦ significant improvement is obtained." (Col. 5, lines 51-56) Within that criterion, the amount of platinum and rhenium employed may be varied, according to the patent, respectively . _. " . , Il 1127583 I, .
il :
l ,within the range of 0.01 to 3, and 0.01 to 5, per cent of the 2 catalytic composite. (Col. 5, lines 35-48) The reasons for 31,employing a low ratio of rhenium to platinum are stated in 4 ,column 4 of the patent. The patent also teaches that the
7 ;This is also true in respect of increasing the cycle length 8 of the catalyst, i.e., increasing the number of barrels of 9 naphtha which can be reformed per pound of catalyst before the catalyst requires regeneration.
11 In addition, Russia and South Africa are the source 12 of more than 95% of the free world's supply of platinum. Any 13 improvements which decrease the amount of platinum required 14 by industry, again, for example, by increasing the life of platinum-containing reforming catalysts, while still accomplish-16 ing the industrial purpose is a contribution to national 17 security and also to economic independence.
1 18 ; The original precious commercial catalysts employed 19 ' a platinum-group metal, preferably platinum itself, as the catalytic agent; see, for example, Haensel's patents Nos.
21 l 2,479,109-110, granted in 1949 and assigned to the Universal 22 Oil Products Company. About 1968, the use of rhenium together 23 1l with platinum was introduced. A number of references refer to 24 Irhenium-platinum catalysts. Kluksdhal's patent No. 3,415,737, 25 ¦assigned to Chevron Research Corporation, teaches that 26 "It is preferred that the rhenium to platinum atom ratio be from about 0.2 to about 2Ø More particularly, it is 27 preferred that the atom ratio of rhenium to platinum does not exceed one. Higher ratios (i.e. greater than one) of 28 rhenium to platinum can be used but generally no further 29 ¦ significant improvement is obtained." (Col. 5, lines 51-56) Within that criterion, the amount of platinum and rhenium employed may be varied, according to the patent, respectively . _. " . , Il 1127583 I, .
il :
l ,within the range of 0.01 to 3, and 0.01 to 5, per cent of the 2 catalytic composite. (Col. 5, lines 35-48) The reasons for 31,employing a low ratio of rhenium to platinum are stated in 4 ,column 4 of the patent. The patent also teaches that the
5 lnaphtha feed should be essentially free of sulfur, more
6 1I preferably less than 5 ppm, and still more preferably less
7 ; than 1 ppm. (Col. 7, lines 67-69)
8 (As employed herein, all compositions expressed in
9 percentages or parts per million are by weight unless otherwise noted. Because the atomic weights of rhenium and platinum 11 differ only slightly, an atomic ratio of 1 is the same as a 12 rhenium to platinum weight ratio of 0.955.) 13 Kluksdhal's patent No. 3,558,477 teaches that:
14 "It is essential for purposes of the present invention that the atomic ratio of the rhenium to platinum be not greater than 1Ø That is, the rhenium to platinum atom ratio should be 1.0 or less than 1Ø More preferably, 16 the atom ratio of rhenium to platinum should be less than about 0.7. Inasmuch as rhenium and platinum have almost 17 the same atomic weight, the atomic ratio is essentially the same as the weight ratio." (Col. 3, lines 26-33) The patent also discloses the same amounts of rhenium and platinum in the catalytic composite, and of sulfur in the 20' linaphtha, as does patent No. 3,415,737; see col. 1, line 62, !! and col. 7, lines 48-51.
23 The ~eachings in respect of the rhenium to platinum 24 ratio and the total amount of rhenium as stated in the above- ¦
quoted Kluksdahl's patent No. 3,415,737 are either repeated or 26 expressly incorporated by reference in Jacobson and Spurlock's l patent No. 3,449,237, at col. 3, lines 1-24; in Jacobson and 27 Vanselow's patent No. 3,558,479, at col. 5, lines 50-69; and 28 ¦in Jacobson's pate~t No. 3,578,582, at col. 1, line 45. Patent 29 ¦NO. 3,578,582 also teaches that rhenium-platinum reforming :, ~1 llZ~583 I I .
1 catalysts may be presulfided, by treating fresh catalyst, before 2 1l use in reforming, with hydrogen sulfide or an alkyl mercaptan in 3 lan amount sufficient to add 0.05 to 2 mols, preferably 0.1 to 1 4 mol, of sulfur per mol of rhenium and platinum; see col. 2, 5 ~line 58 to col. 3, line 12.
6 I Buss' patent No. 3,578,583 teaches the inclusion of a 7 'minor amount, up to 0.1 per cent, or iridium in a catalyst 8 having up to 0.3 per cent e~ach of rhenium and platinum.
9 An article entitled "New Developments In Reforming"
by Messrs. Haensel, Pollitzer & Hayes (of Universal Oil Products 11 Company), Proceedings of the Eighth World Petroleum Congress, 12 Vol. 4, pages 255-261 (1971) teaches that the yield of Cs+
13 liquid product reformate reaches a maximum when the rhenium 14 constitutes 50 per cent of the total catalytic metal (i.e., a rhenium to platinum weight ratio of 1), and that thereafter 16 the yield of liquid product reformate declines as the relative 17 weight of rhenium to platinum is either increased or decreased.
18 It states that "The relationship shown [in Fig. 5 of the article]
19 holds true over a fairly wide range of platinum content, indicating that the modifying effect of rhénium is indeed 21 exerted on the platinum." Id. at pp. 259-60.
22 I Thus the art of reforming with rhenium-platinum 23 Icatalysts has insistently taught that the rhenium to platinum 24 ratio should be less than 2, and preferably about 1 or less.
THE INVENTION
It has now been surprisingly discovered that the 28 Icycle length of a rhenium-platinum reforming catalyst is 29 substantially increasèd when the rhenium-platinum ratio is in 3o the range of from not less than 2 to about 5, preferably in the range of from about 2-1/4 to about 4, and more preferably in the range of from about 2-1/2 to 3-1~2, when employing a naphtha .
., , 1 feedstock having less than about 0.5 ppm, and preferably not 2 more than about 0.25 ppm, of sulfur. This improvement is not 3 only outside the teachings of the prior art, but is a unique 4 l'optinum since at very high rhenium/platinum ratios, approximately 5 'labove 5, the cycle length also decreases. The new catalyst is a 6 '`catalytic composite comprising rhenium and platinum on a support, 7 wherein the weight ratio of rhenium to platinum is in the range 8 as stated above. The new process for reforming a naphtha g fraction com?rises subjecting naphtha having a sulfur content of less than about 0.5 ppm by weight of sulfur, to contact under 11 reforming conditions and in the presence of gaseous hydrogen with 12 a catalytic composite comprising a support, rhenium and platinum, 13 the weight ratio of rhenium to platinum being in the range of 14 from not less than 2 to about 5, whereby the relative cycle length of the catalytic composite is greater than if the rhenium 16 to platinum ratio were to be outside the range stated. The 17 preferred weight ratio of rhenium to platinum is in the range 18 of from about 2-1/4 to about 3-1/2.
19 Except for the increased rhenium-platinum weight ratio, the new catalytic composite may be made in the same manner as 21 has been known heretofore for making catalysts having a lower 22 ~Irhenium-platinum ratio. The amount of platinum may be in the 23 ¦'range of from about 0.1 to about 2 per cent, preferably in the 24 ¦range of about 0.1 to 0.4 per cent, with the rhenium content 25 Ibeing adjusted to furnish the desired rhenium-platinum ratio 26 within the stated range. The support is typically eta or gamma 27 ¦,alumina, and may optionally contain silica, magnesia, oxides 28 !f rare earth metals, and synthetic zeolites, which are sometimes 29 ~Ireferred to as molecular sieves. Typically, up to about 1 per 3o l¦cent of the catalytic composite comprises halides, especially 5-.
112758~
i ' 1 chloride or fluoride.
2 The catalyst is preferably presulfided prior to use 3 in reforming in order to avoid excessive hydrocracking when the 4 l,catalyst is initially on stream. Tne presulfiding treatment 5 1i is conducted by contacting the catalyst with a gaseous stream 6 j containing hydrogen sulfide, an alkyl mercaptan or carbon 7 disulfide, preferably admixed with gaseous hydrogen, until the 8 catalyst contains in the range of about 0.1 to about 0.5 parts 9 by weight of sulfur per part of rhenium, i.e., in the range of about 0.6 to about 3 mols of sulfur per mol of rhenium.
11 Preferably not more than about 0.25 parts of sulfur per part 12 of~rhenium is applied to the catalyst in the presulfiding step, 13 e.g., about 0.17 parts of sulfur per part of rhenium.
14 The process of reforming with the new catalyst is essentially the same as with the prior art catalyst having a 16 lower rhenium-platinum ratio, except that the naphtha feed 17 should have a sulfur contént of less than about 0.5 ppm, and 18 preferably not more than about 0.25 ppm, in order to achieve 19 the superior catalyst life and about an equivalent yield of C5+ liquid reformate obtainable with a catalyst having a 21 ' rhenium-platinum ratio in the range of about 2-1/4 to about 5.
22 Normally the naphtha feedstock will be hydrotreated or otherwise 23 desulfurized by processes known in the art. Although the prior 24 i art teaches the use of naphthas having less than 1 ppm of 25 Isulfur, the catalysts of this invention require naphthas having 26 Ithe very low sulfur levels identified above.
27 Halides may be added to the reaction zone during 28 i reforming, such as by injecting hydrogen chloride, carbon- ¦
29 jtetrachloride or an alkyl halide into the naphtha feed and/or 3o linto the recycle hydrogen gas stream entering the reaction zone ~ -6-I . 1.
, ,.,, . I
- 11275~33 of the reformer. The amount of water in the reaction zone should be adjusted to maintain a molar ratio of water to chloride in the range of about 20 to 80, preferably about 40:1.
After the activity of the catalytic composite has declined by reason of an accumulation of carbonaceous deposits, generally referred to as "coke", the catalyst may be regenerated by procedures known in the art. However, it is a characteristic of the catalyst having a rhenium-platinum ratio within the range described herein that a greater amount of coke may be accumulated thereon before the activity declines to an unsatisfactory level, as indicated by a reduction in the yield of C5~ reformate and/or the clear octane number of the reformate, than is the case for catalysts having a rhenium-platinum ratio of less than 2. Hence, the regeneration procedure will require somewhat more time, and precautions, known in the art, should be taken to avoid excessive flame front temperatures during the regeneration operation, to the end of avoiding damage to the catalyst be reason of localized overheating.
Therefore, in accordance with the present invention ; there is provided a process for reforming a naphtha fraction which process comprises subjecting a naphtha having a sulfur content of less than about 0.5 ppm by weight of sulfur, to contact at reforming conditions and in the presence of gaseous hydrogen with a catalytic composite comprising a support, rhenium and platinum,-the weight ratio of rhenium to platinum being in the range of from not less than 2 to about 5, and the amount of platinum is in the range of about 0.1 to about 2 per cent, whereby the relative cycle length of the catalytic composite is greater than if the rhenium to platinum ratio is outside the range.
llZ75~3 The remarkable improvement in catalyst cycle length has been established by laboratory pilot plant data described in the following examples. The examples are given to illustrate the preparation of the catalysts to be utilized in the process of this invention and their use in the catalytic reforming of naphtha. However, the examples are not presented for purposes of limiting the scope of this invention but in order to further illustrate its various embodiments.
- 7a -.
'1, llZ7583 "
1, .
1~' EXAMPLE I
2 1 A series of reforming catalysts were prepared having 3 ¦~varying weight ratios of rhenium to platinum. The catalyst 5 ¦preparation procedure employed is known in the prior art and is only briefly described hereinafter on a generalized basis. The 6 preparation procedure comprised adding to a beaker the 7 stoichiometrically desired amounts of ammonium rhenate (NH4ReO4) 8 and diammonium chloroplatinate ((NH4)2PtC16), and de-ionized 9 water. Aqueous ammonium hydroxide was added and the reaction mixture heated with hand stirring to a temperature in the range 11 of 81-83 C and until all of the ingredients were dissolved in 12 solution and a light straw-yellow color appeared. A 10% aqueous 13 HCl solution and more de-ionized water were added. The solution 14 was then heated to 90-94 C. The mixture was poured over the desired amount of 1~16th inch gamma alumina extrudates 16 disposed in a rapidly rotating dish. After about one minute 17 or less, the alumina extrudates were removed from the dish and 18 covered with a watch glass. The extrudates were maintained for 19 one hour by means of an infrared lamp at a temperature of at 20 , least 40 C and up to a maximum of about 65 C, with occasional 21 ,'stirring by hand. The catalyst was then dried with air at 2? ' 105-115 C. Thereafter the catalyst was calcined in dry air 23 Iflowing at a rate of about 1,000 V/V/hour for two hours at 24 ~210 F and then for two hours at 900 F.
25 I The analyses of Catalysts A-H is shown in Table I.
26 I I, 27 I ;
28 I , 29 I ' 3 i ___ _ ... . . I ... ..
~: 11275~3 , , 1' .
TABLE I
2 Composition, wt. % Wt. Ratio, 3 ! Catalyst Pt Re Cl Re/Pt 'j A 0.334 0.362 0.91 1.08 4 ~¦ B 0.3g4 0.510 0.80 1.48 5 , C 0.340 0.849 0.93 2.50 6~
D 0.248 0.516 0.99 2.08 ;~ E 0.236 0.860 0.97 3.64 `~ 8 -F 0.150 0.366 0.98 2.44 G 0.155 0.875 0.98 5.65 11 H 0.05 0.85 1.0 17 The foregoing catalysts were employed in reforming pilot plant runs under accelerated aging conditions to establish ', the relative cycle length per unit weight of platinum as a function of the rhenium/platinum weight ratio. A naphtha from a Mid-Continent crude oil was employed, the naphtha having been hydrotreated to a sulfur content of 0.21 ppm by weight. The 7 properties of the naphtha are tabulated:
18 Gravity, API 54.8 9 Distillation IBP, F 230
14 "It is essential for purposes of the present invention that the atomic ratio of the rhenium to platinum be not greater than 1Ø That is, the rhenium to platinum atom ratio should be 1.0 or less than 1Ø More preferably, 16 the atom ratio of rhenium to platinum should be less than about 0.7. Inasmuch as rhenium and platinum have almost 17 the same atomic weight, the atomic ratio is essentially the same as the weight ratio." (Col. 3, lines 26-33) The patent also discloses the same amounts of rhenium and platinum in the catalytic composite, and of sulfur in the 20' linaphtha, as does patent No. 3,415,737; see col. 1, line 62, !! and col. 7, lines 48-51.
23 The ~eachings in respect of the rhenium to platinum 24 ratio and the total amount of rhenium as stated in the above- ¦
quoted Kluksdahl's patent No. 3,415,737 are either repeated or 26 expressly incorporated by reference in Jacobson and Spurlock's l patent No. 3,449,237, at col. 3, lines 1-24; in Jacobson and 27 Vanselow's patent No. 3,558,479, at col. 5, lines 50-69; and 28 ¦in Jacobson's pate~t No. 3,578,582, at col. 1, line 45. Patent 29 ¦NO. 3,578,582 also teaches that rhenium-platinum reforming :, ~1 llZ~583 I I .
1 catalysts may be presulfided, by treating fresh catalyst, before 2 1l use in reforming, with hydrogen sulfide or an alkyl mercaptan in 3 lan amount sufficient to add 0.05 to 2 mols, preferably 0.1 to 1 4 mol, of sulfur per mol of rhenium and platinum; see col. 2, 5 ~line 58 to col. 3, line 12.
6 I Buss' patent No. 3,578,583 teaches the inclusion of a 7 'minor amount, up to 0.1 per cent, or iridium in a catalyst 8 having up to 0.3 per cent e~ach of rhenium and platinum.
9 An article entitled "New Developments In Reforming"
by Messrs. Haensel, Pollitzer & Hayes (of Universal Oil Products 11 Company), Proceedings of the Eighth World Petroleum Congress, 12 Vol. 4, pages 255-261 (1971) teaches that the yield of Cs+
13 liquid product reformate reaches a maximum when the rhenium 14 constitutes 50 per cent of the total catalytic metal (i.e., a rhenium to platinum weight ratio of 1), and that thereafter 16 the yield of liquid product reformate declines as the relative 17 weight of rhenium to platinum is either increased or decreased.
18 It states that "The relationship shown [in Fig. 5 of the article]
19 holds true over a fairly wide range of platinum content, indicating that the modifying effect of rhénium is indeed 21 exerted on the platinum." Id. at pp. 259-60.
22 I Thus the art of reforming with rhenium-platinum 23 Icatalysts has insistently taught that the rhenium to platinum 24 ratio should be less than 2, and preferably about 1 or less.
THE INVENTION
It has now been surprisingly discovered that the 28 Icycle length of a rhenium-platinum reforming catalyst is 29 substantially increasèd when the rhenium-platinum ratio is in 3o the range of from not less than 2 to about 5, preferably in the range of from about 2-1/4 to about 4, and more preferably in the range of from about 2-1/2 to 3-1~2, when employing a naphtha .
., , 1 feedstock having less than about 0.5 ppm, and preferably not 2 more than about 0.25 ppm, of sulfur. This improvement is not 3 only outside the teachings of the prior art, but is a unique 4 l'optinum since at very high rhenium/platinum ratios, approximately 5 'labove 5, the cycle length also decreases. The new catalyst is a 6 '`catalytic composite comprising rhenium and platinum on a support, 7 wherein the weight ratio of rhenium to platinum is in the range 8 as stated above. The new process for reforming a naphtha g fraction com?rises subjecting naphtha having a sulfur content of less than about 0.5 ppm by weight of sulfur, to contact under 11 reforming conditions and in the presence of gaseous hydrogen with 12 a catalytic composite comprising a support, rhenium and platinum, 13 the weight ratio of rhenium to platinum being in the range of 14 from not less than 2 to about 5, whereby the relative cycle length of the catalytic composite is greater than if the rhenium 16 to platinum ratio were to be outside the range stated. The 17 preferred weight ratio of rhenium to platinum is in the range 18 of from about 2-1/4 to about 3-1/2.
19 Except for the increased rhenium-platinum weight ratio, the new catalytic composite may be made in the same manner as 21 has been known heretofore for making catalysts having a lower 22 ~Irhenium-platinum ratio. The amount of platinum may be in the 23 ¦'range of from about 0.1 to about 2 per cent, preferably in the 24 ¦range of about 0.1 to 0.4 per cent, with the rhenium content 25 Ibeing adjusted to furnish the desired rhenium-platinum ratio 26 within the stated range. The support is typically eta or gamma 27 ¦,alumina, and may optionally contain silica, magnesia, oxides 28 !f rare earth metals, and synthetic zeolites, which are sometimes 29 ~Ireferred to as molecular sieves. Typically, up to about 1 per 3o l¦cent of the catalytic composite comprises halides, especially 5-.
112758~
i ' 1 chloride or fluoride.
2 The catalyst is preferably presulfided prior to use 3 in reforming in order to avoid excessive hydrocracking when the 4 l,catalyst is initially on stream. Tne presulfiding treatment 5 1i is conducted by contacting the catalyst with a gaseous stream 6 j containing hydrogen sulfide, an alkyl mercaptan or carbon 7 disulfide, preferably admixed with gaseous hydrogen, until the 8 catalyst contains in the range of about 0.1 to about 0.5 parts 9 by weight of sulfur per part of rhenium, i.e., in the range of about 0.6 to about 3 mols of sulfur per mol of rhenium.
11 Preferably not more than about 0.25 parts of sulfur per part 12 of~rhenium is applied to the catalyst in the presulfiding step, 13 e.g., about 0.17 parts of sulfur per part of rhenium.
14 The process of reforming with the new catalyst is essentially the same as with the prior art catalyst having a 16 lower rhenium-platinum ratio, except that the naphtha feed 17 should have a sulfur contént of less than about 0.5 ppm, and 18 preferably not more than about 0.25 ppm, in order to achieve 19 the superior catalyst life and about an equivalent yield of C5+ liquid reformate obtainable with a catalyst having a 21 ' rhenium-platinum ratio in the range of about 2-1/4 to about 5.
22 Normally the naphtha feedstock will be hydrotreated or otherwise 23 desulfurized by processes known in the art. Although the prior 24 i art teaches the use of naphthas having less than 1 ppm of 25 Isulfur, the catalysts of this invention require naphthas having 26 Ithe very low sulfur levels identified above.
27 Halides may be added to the reaction zone during 28 i reforming, such as by injecting hydrogen chloride, carbon- ¦
29 jtetrachloride or an alkyl halide into the naphtha feed and/or 3o linto the recycle hydrogen gas stream entering the reaction zone ~ -6-I . 1.
, ,.,, . I
- 11275~33 of the reformer. The amount of water in the reaction zone should be adjusted to maintain a molar ratio of water to chloride in the range of about 20 to 80, preferably about 40:1.
After the activity of the catalytic composite has declined by reason of an accumulation of carbonaceous deposits, generally referred to as "coke", the catalyst may be regenerated by procedures known in the art. However, it is a characteristic of the catalyst having a rhenium-platinum ratio within the range described herein that a greater amount of coke may be accumulated thereon before the activity declines to an unsatisfactory level, as indicated by a reduction in the yield of C5~ reformate and/or the clear octane number of the reformate, than is the case for catalysts having a rhenium-platinum ratio of less than 2. Hence, the regeneration procedure will require somewhat more time, and precautions, known in the art, should be taken to avoid excessive flame front temperatures during the regeneration operation, to the end of avoiding damage to the catalyst be reason of localized overheating.
Therefore, in accordance with the present invention ; there is provided a process for reforming a naphtha fraction which process comprises subjecting a naphtha having a sulfur content of less than about 0.5 ppm by weight of sulfur, to contact at reforming conditions and in the presence of gaseous hydrogen with a catalytic composite comprising a support, rhenium and platinum,-the weight ratio of rhenium to platinum being in the range of from not less than 2 to about 5, and the amount of platinum is in the range of about 0.1 to about 2 per cent, whereby the relative cycle length of the catalytic composite is greater than if the rhenium to platinum ratio is outside the range.
llZ75~3 The remarkable improvement in catalyst cycle length has been established by laboratory pilot plant data described in the following examples. The examples are given to illustrate the preparation of the catalysts to be utilized in the process of this invention and their use in the catalytic reforming of naphtha. However, the examples are not presented for purposes of limiting the scope of this invention but in order to further illustrate its various embodiments.
- 7a -.
'1, llZ7583 "
1, .
1~' EXAMPLE I
2 1 A series of reforming catalysts were prepared having 3 ¦~varying weight ratios of rhenium to platinum. The catalyst 5 ¦preparation procedure employed is known in the prior art and is only briefly described hereinafter on a generalized basis. The 6 preparation procedure comprised adding to a beaker the 7 stoichiometrically desired amounts of ammonium rhenate (NH4ReO4) 8 and diammonium chloroplatinate ((NH4)2PtC16), and de-ionized 9 water. Aqueous ammonium hydroxide was added and the reaction mixture heated with hand stirring to a temperature in the range 11 of 81-83 C and until all of the ingredients were dissolved in 12 solution and a light straw-yellow color appeared. A 10% aqueous 13 HCl solution and more de-ionized water were added. The solution 14 was then heated to 90-94 C. The mixture was poured over the desired amount of 1~16th inch gamma alumina extrudates 16 disposed in a rapidly rotating dish. After about one minute 17 or less, the alumina extrudates were removed from the dish and 18 covered with a watch glass. The extrudates were maintained for 19 one hour by means of an infrared lamp at a temperature of at 20 , least 40 C and up to a maximum of about 65 C, with occasional 21 ,'stirring by hand. The catalyst was then dried with air at 2? ' 105-115 C. Thereafter the catalyst was calcined in dry air 23 Iflowing at a rate of about 1,000 V/V/hour for two hours at 24 ~210 F and then for two hours at 900 F.
25 I The analyses of Catalysts A-H is shown in Table I.
26 I I, 27 I ;
28 I , 29 I ' 3 i ___ _ ... . . I ... ..
~: 11275~3 , , 1' .
TABLE I
2 Composition, wt. % Wt. Ratio, 3 ! Catalyst Pt Re Cl Re/Pt 'j A 0.334 0.362 0.91 1.08 4 ~¦ B 0.3g4 0.510 0.80 1.48 5 , C 0.340 0.849 0.93 2.50 6~
D 0.248 0.516 0.99 2.08 ;~ E 0.236 0.860 0.97 3.64 `~ 8 -F 0.150 0.366 0.98 2.44 G 0.155 0.875 0.98 5.65 11 H 0.05 0.85 1.0 17 The foregoing catalysts were employed in reforming pilot plant runs under accelerated aging conditions to establish ', the relative cycle length per unit weight of platinum as a function of the rhenium/platinum weight ratio. A naphtha from a Mid-Continent crude oil was employed, the naphtha having been hydrotreated to a sulfur content of 0.21 ppm by weight. The 7 properties of the naphtha are tabulated:
18 Gravity, API 54.8 9 Distillation IBP, F 230
10% 246 21 50% 267 ;! 90% 315 22 95% 325 , CP 370 23 ~ Sulfur, ppm 0.21 24 ¦ Nitrogen, ppm 0.3 Type Analysis (By Mass Spectrometer) Paraffins 45.4%
26 Naphthenes 42.6%
Aromatics 12.0%
27 ¦ The pilot plant comprised a single tubular reactor of ¦nominal one-inch i.d. stainless steel operated isothermally.
29 ¦It was loaded with about 40 grams of catalyst for the reforming ! _g_ .
.~ .
Il 1127583 . . .
, 1 j runs. After a freshly-prepared catalyst was loaded into the 2 ¦ reactor, the catalyst was chemically reduced by passing hydrogen 3 lat 900 F through the catalyst bed. The temperature was then 4 llowered to 800 F and the catalyst was presulfided by passing 5 la mixture of 0.7 vol.% hydrogen sulfide in hydrogen through 6 !the catalyst bed, to a constant sulfur level for each sample 7 of about 0.05% by weight on catalyst. The pre-heated naphtha 8 feedstock was introduced initially at a reactor temperature of 9 800 F, after which the temperature was increased to 925 F and held constant for the duration of the 300-hour aging runs. The
26 Naphthenes 42.6%
Aromatics 12.0%
27 ¦ The pilot plant comprised a single tubular reactor of ¦nominal one-inch i.d. stainless steel operated isothermally.
29 ¦It was loaded with about 40 grams of catalyst for the reforming ! _g_ .
.~ .
Il 1127583 . . .
, 1 j runs. After a freshly-prepared catalyst was loaded into the 2 ¦ reactor, the catalyst was chemically reduced by passing hydrogen 3 lat 900 F through the catalyst bed. The temperature was then 4 llowered to 800 F and the catalyst was presulfided by passing 5 la mixture of 0.7 vol.% hydrogen sulfide in hydrogen through 6 !the catalyst bed, to a constant sulfur level for each sample 7 of about 0.05% by weight on catalyst. The pre-heated naphtha 8 feedstock was introduced initially at a reactor temperature of 9 800 F, after which the temperature was increased to 925 F and held constant for the duration of the 300-hour aging runs. The
11 reforming run conditions were a temperature of 925 F, a weight
12 hourly space velocity of 4, and hydrogen/hydrocarbon molar
13 ratio of 3, and a pressure of 200 psig. These conditions
14 produced, at the start of the runs, a C5+ reformate of about 100 research octane number without the addition of tetraethyl 16 lead (referred to as RONC), determined by ASTM Procedure No.
17 D-2699. During the reforming runs a mixture of methanol and an ?8 akylchloride was injected into the naphtha feedstock to maintain 19 a constant (i.e., about 1 weight per cent) chloride content on each catalyst.
21 ~ The data from the reforming runs were processed as 22 , follows. During the coursè of the 300-hour reforming runs, 23 the Cs+ liquid product was collected periodically and tested for 24 its octane number. The measured research octane number was plotted against time on stream, and the slope of the octane-26 time curve was adjusted, by means known in the prior art, to 27 icompensate for any difference between the octane number of the 28 ¦! reformate at the start of the run and the intended initial 29 ¦octane number of 100. The compensated research octane number 3o of the C5+ reformate was then plotted against time in hours I
!1 ~ "~"
i!
i .
Ielapsed since the start of the reforming run, often referred 1 to as "time on feed." The slope of the octane-time curve 2 is negative and is the octane decline rate, i.e., the time 3 rate of octane decline. It has the dimensional units of 4 ¦'RONC/hour and for convenience is often referred to as oRONC/100 5 lhours. In catalytic reforming, it is desirable to minimize 6 'the octane decline rate, and therefore a lesser absolute 7 value of the slope of the curve indicates a more desirable 8 catalyst.
g Table II lists the aging rate, in terms of decline of research octane number per 100 hours, for the catalysts 11 tested. Catalyst A, which is representative of the preferred 12 rhenium/platinum catalyst of the prior art, was arbitrarily 13 assigned a relative cycle length of 1.00 and the relative 14 cycle length of all of the remaining catalysts were compared 1~ to it by dividing the aging rate of Catalyst A by the aging 16 rate of the catalyst in question. The relative cycle length 17 per unit weight of platinu~ was determined by dividing the 18 relative cycle length of a catalyst by the weight fraction 19 of platinum (as stated in Table I) of the catalyst. The latter computation is significant because it is indicative of the 21 efficiency with which the expensive platinum is being utilized.
22 ~The data of Table II show that employing rheniumtplatinum ratios 23 li of not less than 2 enables a refiner to obtain a longer cycle 24 1l length and/or better efficiency in utilizing platinum, than 25 l¦with catalysts having a lower Re/Pt ratio. The data also 26 ¦¦establlsh that, surprisingly, this invention permits the use 27 il of catalyst containing a lower weight fraction of platinum 28 ~I(about 0.15%, in Catalysts F and G) than has been employed 29 ¦,commercially heretofore.
1! --11-- .
Il . , _ ~ .. . . .. I I .... . .
1i1 ' .
, Relative Cycle Relative, Length Per Unit Wt. Ratio, Aging Rate, Cycle Weight of , 4 I,Catalyst Re/Pt ~ONC/100 Hrs. Length Platinum 5 1 A 1.08 2.8 1.00 2.99 6 ! B 1.48 2.1 1.33 3.87 7 C 2.50 1.7 1.65 4.85 8 D 2.08 - 2.2 1.27 5.12 g E 3.64 1.9 1.47 6.23 F 2.44 2.5 1.12 7.47 11 G 5.65 3.4 0.82 5.47 12 H 17 33 0.08 1.60 Catalyst C was compared with Catalyst A when employing 16 naphtha feedstocks of d1fferent sulfur content. The test 17 conditions were the same as those referred to in Example I, 18 except that the sulfur content of the feedstock naphtha was 19 adjusted by adding thiophene to increase the sulfur content to 1 20 10 ppm by weight. The results of the aging,test employing 21 ,',naphtha feedstocks having sulfur contents of 0.2 and 10 ppm ~ lare stated in Table III. As was illustrated in Example I, 22 ;
23 ICatalyst C of this invention has a slower aging rate than 24 Catalyst A of the prior art. The relative cycle length, and also the relative cycle length per unit weight of platinum, of 26 Catalyst C of this invetion is greater than that of Catalyst A
27 ¦of the prior art when the sulfur content of the feedstock is 28 10.2 ppm, but conversely if the sulfur content is 10 ppm. These 29 ¦data establish that for optimum utilization of the invent1on, . . , :
11275~33 ;.
, 1 the sulfur content of the naphtha feedstock should be reduced 2 to less than 0.5, and preferably to less than 0.25, ppm.
i~
~ TABLE III
4 .! __ lli Relative Cycle 5 1 Aging Rate, Relative Length Per Feedstock aRONC Cycle Unit Weight of 6 ! Catalyst Sulfur, ppm per 100 hrs. Length Platinum 7 A 0.21 2.8 1.00 2.99 8 A 10 4.0 0.70 2.10 g C 0.21 1.7 1.65 4.85 C 10 6.2 0.45 1.32 EXAMPLE III
Catalysts A, C and G were employed in reforming pilot plant runs which further illustrate the process of this invention.
The hydrotreated naphtha from a Mid-Continent crude oil had the properties tabulated below:
Gravity, AP~ 54.7 Distillation - -18 IBP, F 217 10% 242 19 50% - 268 9o% 322 95% 344 Sulfur 0.57 ppm 22 Nitrogen 0.77 ppm I
23 1I Type Analysis (by Mass Spectrometer) I Paraffins 45.5 24 j! Naphthenes 42.8 Il Aromatics 11.7 25 i . I The reforming pilot plant, and the processes of ¦!reducing and pre-sulfiding the fresh catalyst, were the same llas described in Example I, except that the amount of sulfur 28 jj ladded to each catalyst was varied to furnish about 0.17 parts 29 ¦of sulfur per part by weight of rhenium, according to the il -13-¦~ !
11 .
!
1 following table:
2 Sulfur on Wt. Ratio, Ca~alyst Catalyst, wt. % S/Re i A 0.06 0.166 C 0.15 0.177 ' G 0.15 0.171 Each such catalyst was employed for reforming at a temperature of 900 F, a pressure of 175 psig, a hydrogen-hydrocarbon molar ratio of 9, and a space velocity in the range of 2 to 12, which was varied to adjust the octane level of the Cs+ reformate to 91 RONC. The runs were terminated after about two barrels of naphtha per pound of catalyst had been processed, and the used catalyst was analyzed for carbon content. The pertinent data are tabulated below:
Average Yield of Carbon on Used Catalyst Wt. Ratio, WHSV at Reformate Wt. % of % Per Unit Catalyst Re/Pt 91 RONC at 91 RONC Catalyst Wt. of Pt A 1.08 7.0 87.6 1.15 3.44 C 2.5 6.7 85.8 0.49 1.44 G 5.65 6.0 85.6 0.28 1.81 . ' 19 The activities of the catalysts, as indicated by the weight hour space velocities and the yields of Cs+ reformate, were about equal for the catalysts although the initial sulfur llevels differed. In addition, the reduction in the amount of ; llcarbon (often referred to as coke) on the used catalysts as the ¦¦rhenium/platinum ratio is increased is indicative that the 6 ~! rhenium exerts an on-stream cleansing effect, which is consistent iwith the greater relative cycle length obtainable with catalysts 8 ,Ihaving an increased rhenium/platinum ratio relative to catalysts llof the prior art.
3o l¦ Having thus described the invention, what is claimed l! is 1l -14-..
17 D-2699. During the reforming runs a mixture of methanol and an ?8 akylchloride was injected into the naphtha feedstock to maintain 19 a constant (i.e., about 1 weight per cent) chloride content on each catalyst.
21 ~ The data from the reforming runs were processed as 22 , follows. During the coursè of the 300-hour reforming runs, 23 the Cs+ liquid product was collected periodically and tested for 24 its octane number. The measured research octane number was plotted against time on stream, and the slope of the octane-26 time curve was adjusted, by means known in the prior art, to 27 icompensate for any difference between the octane number of the 28 ¦! reformate at the start of the run and the intended initial 29 ¦octane number of 100. The compensated research octane number 3o of the C5+ reformate was then plotted against time in hours I
!1 ~ "~"
i!
i .
Ielapsed since the start of the reforming run, often referred 1 to as "time on feed." The slope of the octane-time curve 2 is negative and is the octane decline rate, i.e., the time 3 rate of octane decline. It has the dimensional units of 4 ¦'RONC/hour and for convenience is often referred to as oRONC/100 5 lhours. In catalytic reforming, it is desirable to minimize 6 'the octane decline rate, and therefore a lesser absolute 7 value of the slope of the curve indicates a more desirable 8 catalyst.
g Table II lists the aging rate, in terms of decline of research octane number per 100 hours, for the catalysts 11 tested. Catalyst A, which is representative of the preferred 12 rhenium/platinum catalyst of the prior art, was arbitrarily 13 assigned a relative cycle length of 1.00 and the relative 14 cycle length of all of the remaining catalysts were compared 1~ to it by dividing the aging rate of Catalyst A by the aging 16 rate of the catalyst in question. The relative cycle length 17 per unit weight of platinu~ was determined by dividing the 18 relative cycle length of a catalyst by the weight fraction 19 of platinum (as stated in Table I) of the catalyst. The latter computation is significant because it is indicative of the 21 efficiency with which the expensive platinum is being utilized.
22 ~The data of Table II show that employing rheniumtplatinum ratios 23 li of not less than 2 enables a refiner to obtain a longer cycle 24 1l length and/or better efficiency in utilizing platinum, than 25 l¦with catalysts having a lower Re/Pt ratio. The data also 26 ¦¦establlsh that, surprisingly, this invention permits the use 27 il of catalyst containing a lower weight fraction of platinum 28 ~I(about 0.15%, in Catalysts F and G) than has been employed 29 ¦,commercially heretofore.
1! --11-- .
Il . , _ ~ .. . . .. I I .... . .
1i1 ' .
, Relative Cycle Relative, Length Per Unit Wt. Ratio, Aging Rate, Cycle Weight of , 4 I,Catalyst Re/Pt ~ONC/100 Hrs. Length Platinum 5 1 A 1.08 2.8 1.00 2.99 6 ! B 1.48 2.1 1.33 3.87 7 C 2.50 1.7 1.65 4.85 8 D 2.08 - 2.2 1.27 5.12 g E 3.64 1.9 1.47 6.23 F 2.44 2.5 1.12 7.47 11 G 5.65 3.4 0.82 5.47 12 H 17 33 0.08 1.60 Catalyst C was compared with Catalyst A when employing 16 naphtha feedstocks of d1fferent sulfur content. The test 17 conditions were the same as those referred to in Example I, 18 except that the sulfur content of the feedstock naphtha was 19 adjusted by adding thiophene to increase the sulfur content to 1 20 10 ppm by weight. The results of the aging,test employing 21 ,',naphtha feedstocks having sulfur contents of 0.2 and 10 ppm ~ lare stated in Table III. As was illustrated in Example I, 22 ;
23 ICatalyst C of this invention has a slower aging rate than 24 Catalyst A of the prior art. The relative cycle length, and also the relative cycle length per unit weight of platinum, of 26 Catalyst C of this invetion is greater than that of Catalyst A
27 ¦of the prior art when the sulfur content of the feedstock is 28 10.2 ppm, but conversely if the sulfur content is 10 ppm. These 29 ¦data establish that for optimum utilization of the invent1on, . . , :
11275~33 ;.
, 1 the sulfur content of the naphtha feedstock should be reduced 2 to less than 0.5, and preferably to less than 0.25, ppm.
i~
~ TABLE III
4 .! __ lli Relative Cycle 5 1 Aging Rate, Relative Length Per Feedstock aRONC Cycle Unit Weight of 6 ! Catalyst Sulfur, ppm per 100 hrs. Length Platinum 7 A 0.21 2.8 1.00 2.99 8 A 10 4.0 0.70 2.10 g C 0.21 1.7 1.65 4.85 C 10 6.2 0.45 1.32 EXAMPLE III
Catalysts A, C and G were employed in reforming pilot plant runs which further illustrate the process of this invention.
The hydrotreated naphtha from a Mid-Continent crude oil had the properties tabulated below:
Gravity, AP~ 54.7 Distillation - -18 IBP, F 217 10% 242 19 50% - 268 9o% 322 95% 344 Sulfur 0.57 ppm 22 Nitrogen 0.77 ppm I
23 1I Type Analysis (by Mass Spectrometer) I Paraffins 45.5 24 j! Naphthenes 42.8 Il Aromatics 11.7 25 i . I The reforming pilot plant, and the processes of ¦!reducing and pre-sulfiding the fresh catalyst, were the same llas described in Example I, except that the amount of sulfur 28 jj ladded to each catalyst was varied to furnish about 0.17 parts 29 ¦of sulfur per part by weight of rhenium, according to the il -13-¦~ !
11 .
!
1 following table:
2 Sulfur on Wt. Ratio, Ca~alyst Catalyst, wt. % S/Re i A 0.06 0.166 C 0.15 0.177 ' G 0.15 0.171 Each such catalyst was employed for reforming at a temperature of 900 F, a pressure of 175 psig, a hydrogen-hydrocarbon molar ratio of 9, and a space velocity in the range of 2 to 12, which was varied to adjust the octane level of the Cs+ reformate to 91 RONC. The runs were terminated after about two barrels of naphtha per pound of catalyst had been processed, and the used catalyst was analyzed for carbon content. The pertinent data are tabulated below:
Average Yield of Carbon on Used Catalyst Wt. Ratio, WHSV at Reformate Wt. % of % Per Unit Catalyst Re/Pt 91 RONC at 91 RONC Catalyst Wt. of Pt A 1.08 7.0 87.6 1.15 3.44 C 2.5 6.7 85.8 0.49 1.44 G 5.65 6.0 85.6 0.28 1.81 . ' 19 The activities of the catalysts, as indicated by the weight hour space velocities and the yields of Cs+ reformate, were about equal for the catalysts although the initial sulfur llevels differed. In addition, the reduction in the amount of ; llcarbon (often referred to as coke) on the used catalysts as the ¦¦rhenium/platinum ratio is increased is indicative that the 6 ~! rhenium exerts an on-stream cleansing effect, which is consistent iwith the greater relative cycle length obtainable with catalysts 8 ,Ihaving an increased rhenium/platinum ratio relative to catalysts llof the prior art.
3o l¦ Having thus described the invention, what is claimed l! is 1l -14-..
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for reforming a naphtha fraction, which process comprises subjecting a naphtha having a sulfur content of less than about 0.5 ppm by weight of sulfur, to contact at reforming conditions and in the presence of gaseous hydrogen with a catalytic composite comprising a support, rhenium and platinum, the weight ratio of rhenium to platinum being in the range of from not less than 2 to about 5, and the amount of platinum is in the range of about 0.1 to about 2 per cent, whereby the relative cycle length of said catalytic composite is greater than if the rhenium to platinum ratio is outside said range.
2. The process of claim 1, wherein the weight ratio of rhenium to platinum is in the range of about 2-1/4 to about 4.
3. The process of claim 1, wherein the catalyst composite is presulfided prior to the reforming cycle sufficiently to impart thereto between about 0.1 and about 0.5 parts by weight of sulfur per part of rhenium.
4. The process of claim 1, wherein the sulfur content of the naphtha feedstock is not more than about 0.25 ppm by weight.
5. In a process of catalytically reforming naphtha over a catalytic composite comprising rhenium and plantinum on a support, disposed in a reforming zone, the improvement wherein the weight ratio of rhenium to platinum of said catalytic composition is in the range of not less than 2 to about 5, and the amount of platinum is in the range of about 0.1 to about 2 per cent, and wherein the sulfur content of the naphtha introduced into the reforming zone is less than about 0.5 ppm by weight, whereby the relative cycle length of the catalyst is greater than if the weight ratio of rhenium to platinum is less than said range.
6. A catalytic composite adopted for use in reforming naphtha, said composite comprising a support, rhenium, and platinum, wherein the rhenium to platinum weight ratio is in the range of from about not less than 2 to about 5.
7. The composite of claim 6, wherein said ratio is in the range of about 2-1/4 to about 4.
8. The composite of claim 6, wherein said support comprises predominantly eta and/or gamma alumina and comprises about 1% halide.
9. In a process of catalytically reforming naphtha over a catalytic composite comprising rhenium and platinum on a support, disposed in a reforming zone, the improvement wherein the weight ratio of rhenium to platinum of said catalytic composition is in the range of not less than 2 to about 4, and the amount of platinum is in the range of about 0.1 to about 2 per cent, and wherein the sulfur content of the naphtha introduced into the reforming zone is less than about 0.5 ppm by weight, whereby the absolute value of the time rate of octane decline is less than if the weight ratio of rhenium to platinum is less than said range.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US89489078A | 1978-04-10 | 1978-04-10 | |
| US894,890 | 1978-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127583A true CA1127583A (en) | 1982-07-13 |
Family
ID=25403638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA325,146A Expired CA1127583A (en) | 1978-04-10 | 1979-04-09 | Catalytic reforming with rhenium-platinum catalyst containing more rhenium than platinum |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS54145707A (en) |
| AU (2) | AU537495B2 (en) |
| BE (1) | BE875386A (en) |
| BR (1) | BR7902106A (en) |
| CA (1) | CA1127583A (en) |
| DE (1) | DE2913183A1 (en) |
| DK (1) | DK149692C (en) |
| EG (1) | EG13933A (en) |
| FI (1) | FI65798C (en) |
| FR (1) | FR2422711B1 (en) |
| GB (1) | GB2018278B (en) |
| IT (1) | IT1116165B (en) |
| MX (1) | MX151766A (en) |
| NL (1) | NL7902617A (en) |
| NO (1) | NO791160L (en) |
| SE (1) | SE432604B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1223836A (en) * | 1981-12-31 | 1987-07-07 | William E. Winter | Catalytic reforming process |
| RU2206599C1 (en) * | 2002-04-25 | 2003-06-20 | Макаров Павел Алексеевич | Aromatic hydrocarbon production process |
| FR2840548B1 (en) * | 2002-06-07 | 2005-03-18 | Inst Francais Du Petrole | HOMOGENEOUS CATALYST BED AND PROCESS FOR PROCESSING HYDROCARBONS INTO AROMATIC COMPOUNDS WITH SUCH BED |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3415737A (en) * | 1966-06-24 | 1968-12-10 | Chevron Res | Reforming a sulfur-free naphtha with a platinum-rhenium catalyst |
| GB1256000A (en) * | 1968-04-24 | 1971-12-08 | Universal Oil Prod Co | Hydrocarbon conversion catalyst and processes for the manufacture and use thereof |
| CA949544A (en) * | 1970-02-13 | 1974-06-18 | Henry Erickson | Rhenium and platinum series metal-containing catalysts |
| FR2125126A1 (en) * | 1971-02-12 | 1972-09-29 | Universal Oil Prod Co | Hydrocarbon conversion - with a catalyst contg a platinum group metal,rhenium,tin and halogen |
| GB1374863A (en) * | 1972-03-13 | 1974-11-20 | Universal Oil Prod Co | Catalyst and process for the isomerization of hydrocarbons |
| CA1050917A (en) * | 1973-05-07 | 1979-03-20 | Atlantic Richfield Company | Hydrocarbon reforming process |
| FR2286187A1 (en) * | 1974-09-25 | 1976-04-23 | Catalyse Soc Prod Francais | HYDROCONVERSION CATALYSTS FOR HYDROCARBONS |
-
1979
- 1979-03-26 AU AU45470/79A patent/AU537495B2/en not_active Ceased
- 1979-04-02 DE DE19792913183 patent/DE2913183A1/en not_active Ceased
- 1979-04-03 NL NL7902617A patent/NL7902617A/en not_active Application Discontinuation
- 1979-04-03 GB GB7911596A patent/GB2018278B/en not_active Expired
- 1979-04-04 FR FR7908480A patent/FR2422711B1/en not_active Expired
- 1979-04-05 FI FI791128A patent/FI65798C/en not_active IP Right Cessation
- 1979-04-05 DK DK140379A patent/DK149692C/en not_active IP Right Cessation
- 1979-04-05 BR BR7902106A patent/BR7902106A/en unknown
- 1979-04-06 JP JP4118079A patent/JPS54145707A/en active Granted
- 1979-04-06 IT IT48661/79A patent/IT1116165B/en active
- 1979-04-06 NO NO791160A patent/NO791160L/en unknown
- 1979-04-06 BE BE0/194457A patent/BE875386A/en not_active IP Right Cessation
- 1979-04-09 SE SE7903154A patent/SE432604B/en not_active IP Right Cessation
- 1979-04-09 CA CA325,146A patent/CA1127583A/en not_active Expired
- 1979-04-09 EG EG212/79A patent/EG13933A/en active
- 1979-04-10 MX MX177265A patent/MX151766A/en unknown
-
1984
- 1984-04-18 AU AU27076/84A patent/AU2707684A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| SE7903154L (en) | 1979-10-11 |
| FR2422711A1 (en) | 1979-11-09 |
| JPS6353239B2 (en) | 1988-10-21 |
| IT1116165B (en) | 1986-02-10 |
| DE2913183A1 (en) | 1979-10-18 |
| DK140379A (en) | 1979-10-11 |
| FI65798B (en) | 1984-03-30 |
| NL7902617A (en) | 1979-10-12 |
| DK149692B (en) | 1986-09-08 |
| IT7948661A0 (en) | 1979-04-06 |
| AU2707684A (en) | 1984-08-02 |
| FR2422711B1 (en) | 1985-11-29 |
| EG13933A (en) | 1983-03-31 |
| BR7902106A (en) | 1979-11-27 |
| MX151766A (en) | 1985-03-07 |
| SE432604B (en) | 1984-04-09 |
| FI791128A (en) | 1979-10-11 |
| FI65798C (en) | 1984-07-10 |
| AU4547079A (en) | 1979-10-18 |
| BE875386A (en) | 1979-10-08 |
| NO791160L (en) | 1979-10-11 |
| DK149692C (en) | 1987-03-30 |
| GB2018278B (en) | 1982-08-11 |
| GB2018278A (en) | 1979-10-17 |
| JPS54145707A (en) | 1979-11-14 |
| AU537495B2 (en) | 1984-06-28 |
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