US3607729A - Production of kerosene jet fuels - Google Patents
Production of kerosene jet fuels Download PDFInfo
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- US3607729A US3607729A US814520A US3607729DA US3607729A US 3607729 A US3607729 A US 3607729A US 814520 A US814520 A US 814520A US 3607729D A US3607729D A US 3607729DA US 3607729 A US3607729 A US 3607729A
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- kerosene
- catalyst
- hydrocarbons
- platinum
- contacted
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- 239000003350 kerosene Substances 0.000 title claims abstract description 33
- 239000000446 fuel Substances 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims description 22
- 230000005484 gravity Effects 0.000 claims description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000779 smoke Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 208000002399 aphthous stomatitis Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
Definitions
- Paraffins including isoparaffins, have a relatively high smoke point and gravity which makes them desirable components. However, they have relatively low heating value (B.t.u./lb.). Moreover, most natural kerosene boiling range fractions contain substantial amounts of aromatics and naphthene compounds making the production of entirely paraffinic fuels economically unattractive.
- Aromatics on the other end of the scale, have low smoke point and API gravity properties but high heating value.
- Naphthenes fall in between. They have relatively high heating value and relatively poor smoke point and gravity properties.
- feasible jet fuels must be a balanced composition containing at least paraffins and naphthenes.
- Aromatics may or may not be included depending on the quality of the other components.
- Polynaphthene compounds are also usually present in the kerosene distillates and are much like aromatics, i.e., have poor gravity and smoke point characteristics.
- the process involves simultaneous aromatic hydrogenation and ring opening in a single reaction zone.
- the present invention is a process for the hydrogenation/ring opening of kerosene boiling range hydrocarbon fractions, having substantial amounts of cyclic compounds, characterized by contacting a kerosene fraction in the presence of hydrogen with a catalyst comprising at least 1 w/o platinum group metal and 0.5 w/o fluoride on alumina, the process being further characterized by maintaining the kerosene feed water content to below about ppm. by weight.
- Kerosene boiling range fractions suitable for the process of the present invention may be derived from a variety of sources. In general, fractions in the boiling range from about 300 to 600 C. are suitable. Examples of suitable feeds are, for example, straight run, catalytically cracked, or hydrocracked fractions and combinations thereof. The fractions for which the present process is advantageous have APl gravities lower than 39 and smoke points which are usually below about 20. Such fractions contain substantial amounts of aromatic and naphthenic ring compounds, i.e., a suitable straight run fraction from a naphthenic crude which may con tain on the order of 10 to percent aromatics and 40 to 70 percent naphthenes. Hydrocracked kerosene fractions usually have higher aromatics content in the range of 30 to 60 percent.
- the kerosene feed contains relatively high contents of heteroatomic impurities such as nitrogen, sulfur or metallic compounds, hydrotreating to reduce or remove these impurities is desirable. Sulfur compounds are especially undesirable since they tend to poison the platinum group metal in the hydrogenation ring opening catalyst.
- Such catalysts generally comprise one or more of the various Group Group V] and Group VIII metals as well as the oxides and sulfides thereof supported on a porous carrier.
- nickel molybdenum sulfide on alumina is an example of a useful, commercially available catalyst.
- Hydrofining can be carried out over a wide range of conditions that depend upon the particular hydrocarbon feed and catalyst used. Temperatures in the range of 625 to 750 F., pressures in the range of 400 to 1,500 p.s.i.g., liquid hourly space velocities of about 0.5 to 5 and hydrogen to oil ratios of about 500 to 10,000 standard cubic feet of H per barrel of feed are customary conditions. Partial hydrogenation of aromatics in the kerosene boiling range may be effected in the hydrotreating reaction but is neither required for nor forms a part of the present invention.
- the present process uses a catalyst composite which has certain critical concentrations of components.
- the predominant portion of the catalyst is a porous alumina support.
- Suitable alumina supports include activated alumina, gamma alumina, eta alumina, pseudo-alumina and the like.
- the catalyst contains at least 1 w/o of a platinum group metal and preferably about 1.5 w/o platinum.
- the catalyst must also contain at least 0.5 w/o fluorine and preferably about 1 percent weight fluorine.
- Fluorine is customarily added to such catalyst composites to promote acid catalyzed reactions.
- the desired hydrogenation/ring opening reactions of the present invention are known to be metal catalyzed.
- the addition of a halogen would not be expected to aid in these reactions but instead to lead to undesirable hydrocracking.
- Platinum metal and fluorine may be added to the alumina support by various means known to the art.
- a convenient method involves competitive ion exchange of discrete particles (spheres, extrudates, etc.) of alumina with an aqueous solution of chloroplatinate ions and ammonium ions such as a dilute solution of chloroplatinic acid and ammonium mitrate.
- Nitrate and chloride ions are removed by washing and the composite is impregnated with a suitable fluoride compound such as a solution of ammonium bifluoride. Calcination decomposes the ammonium ion.
- the process may be carried out in any suitable equipment but preferably in a fixed bed reaction system where the catalyst is disposed as discrete particles in a reaction zone and the hydrocarbon feed passed therethrough in upward, downward or radial flow.
- Reaction conditions for the present invention depend upon the kerosene feed composition properties and the catalyst composition and degree of activation.
- Suitable conditions are temperatures in the range of 500 to 800 F., pressure in the range of 500 to 1,500 p.s.i.g., liquid hourly space velocities of from 0.5 to 5 volumes of feed per volume of catalyst per hour and hydrogen to hydrocarbon mole ratios of about 5 to 20.
- the moisture content of the kerosene feed is especially important and should be maintained below about p.p.m. by weight and preferably at about 2 p.p.m. by weight. The importance of low water content will be demonstrated in the examples.
- EXAMPLE 1 Catalysts were prepared with platinum contents of0.1, 0.68 and 1.5 w/o and 0.6 w/o fluorine by uniformly dispersing platinum on porous alumina. The metal was incorporated by competitive ion exchange of chloroplatinate ions in dilute ammonium nitrate solution. Fluorine was incorporated by impregnation of the catalyst with ammonium bifluoride solution. The catalysts were washed free of unreacted ions, dried, calcined and reduced in dry hydrogen. These catalysts were tested with a hydrotreated naphthenic kerosene fraction (310 to 540 F. boiling range) at 665 F., 1.5 liquid hourly space velocity (LHSV) and 10 H jhydrocarbon mole ratio. The results are shown in table 1.
- LHSV liquid hourly space velocity
- EXAMPLE 2 A catalyst prepared by competitive ion exchange of platinum and impregnation with fluoride of a commercial catalytic reforming catalyst was used to study the effect of moisture in the process. Platinum and fluoride were added as described in example 1 to give a catalyst having 1.5 w/o' platinum and 1 w/o fluorine. Prior to use the catalyst was calcined in a reactor with dry air, purged with nitrogen and reduced with dry hydrogen for 1 hour at atmospheric pressure.
- the catalyst was used for ring opening a kerosene fraction like that in example 1.
- Conditions were 850 p.s.i.g., 660 F., 2 LHSV and 10 H joil ratio (mole).
- the kerosene was dried to a water level of 10 p.p.m. by weight by passing it over molecular sieves. After hours of processing the product AP] gravity was about 39.7. After 200 hours of operation of feed water level was increased to 570 p.p.m. and the product APl gravity immediately fell to 38.8. On returning to 10 p.p.m. water the product API gravity increased to 39.5.
- EXAMPLE 3 A catalyst substantially the same as the 1.5 w/o platinum catalyst described in example 2 was used for ring opening the 310-540 F. kerosene fraction of example 1 at 850 p.s.i.g., 660 F., 2 LHSV and 10 H loil ratio (mole). The kerosene was dried to 2 p.p.m. by weight water with molecular sieves. During 1,000 hours of operation (after which the run was terminated without evidence of catalyst deactivation) the product API gravity was 40 or above. Yield of product during this time was about 96 percent volume of 310 F. plus kerosene.
- a process for hydrogenating/ring-opening a feed consisting essentially of kerosene boiling range hydrocarbons wherein the feed substantially free of heteroatomic impurities is contacted in the presence of hydrogen with a catalyst comprising at least about 1.0 w/o of a platinum group metal and at least 0.5 w/o by weight fluorine on an alumina support at temperature in the range of about 500 to 800 F., a pressure in the range of about 500 to 1,500 p.s.i.g. and a hydrogen to hydrocarbon mole ratio of from about 5 to 20 and wherein the water content of the contacted hydrocarbons is below about 10 p.p.m. by weight.
- the catalyst comprises about 1.5 w/o platinum and about 1 W10 fluorine on the alumina support.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A process for the production of kerosene jet fuels in which kerosene boiling range petroleum fractions are contacted with hydrogen and a catalyst comprising a noble metal and fluoride on alumina, the process being further characterized by control of the kerosene feed water content to a low level (e.g., 10 p.p.m. or lower).
Description
United States Patent inventors Robert E. Robinson;
Apr. 7, 1969 Sept. 2], 1971 Shell Oil New York, N.Y.
App]. No. Filed Patented Assignee PRODUCTION OF KEROSENE JET FUELS 9 Claims, No Drawings US. Cl 208/112, 208/57, 208/89, 208/145, 208/177, 208/187,
Int. Cl ..C 10g 13/02, C07e 5/16, BOlj 11/08 Field of Search 208/15,
William K. Meerbott, both of Houston, Tex.
References Cited Primary ExaminerDelbert E. Gantz Assistant Examiner-G. E. Schmitkons Attorney-Harold L. Denkler ABSTRACT: A process for the production of kerosene jet fuels in which kerosene boiling range petroleum fractions are contacted with hydrogen and a catalyst comprising a noble metal and fluoride on alumina, the process being further characterized by control of the kerosene feed water content to a low level (e.g., l0 p.p.m. or lower).
PRODUCTION OF KEROSENE JET FUELS DISCUSSION OF THE PRIOR ART ln recent years aviation turbine fuels have become a major petroleum product. Acceptable kerosene-type turbine fuels must meet certain specifications which are seldom found in naturally occurring petroleum distillates. In general, such a kerosene fuel must have the following specifications:
APl Gravity-39-51 Smoke PointGreater than 20 Luminometer No.Greater than 45 Aromatic Content-Less than 20 percent.
These fuels have a boiling range from about 300 to 600 F. and must have a reasonable distribution of fractions throughout the boiling range (limits on the distribution are also fixed by specification).
Very few natural distillates possess the necessary combined properties. Consequently, these fuels must be synthetically produced and the various hydrocarbon types (paraffins, naphthenes and aromatics) carefully balanced in the composition to produce the desired properties.
Paraffins, including isoparaffins, have a relatively high smoke point and gravity which makes them desirable components. However, they have relatively low heating value (B.t.u./lb.). Moreover, most natural kerosene boiling range fractions contain substantial amounts of aromatics and naphthene compounds making the production of entirely paraffinic fuels economically unattractive.
Aromatics, on the other end of the scale, have low smoke point and API gravity properties but high heating value.
Naphthenes fall in between. They have relatively high heating value and relatively poor smoke point and gravity properties.
Thus, feasible jet fuels must be a balanced composition containing at least paraffins and naphthenes. Aromatics may or may not be included depending on the quality of the other components.
Polynaphthene compounds are also usually present in the kerosene distillates and are much like aromatics, i.e., have poor gravity and smoke point characteristics.
Numerous proposals have been made in the literature for achieving acceptable jet fuels. For example, various processes which depend on the removal of aromatics by separation or hydrogenation have been described.
We have discovered a new process for the efficient production of jet fuels of specification quality from hydrocarbon distillates which contain substantial amounts of ring structures (aromatics and naphthenes).
The process involves simultaneous aromatic hydrogenation and ring opening in a single reaction zone.
SUMMARY OF THE INVENTION ln broad aspect the present invention is a process for the hydrogenation/ring opening of kerosene boiling range hydrocarbon fractions, having substantial amounts of cyclic compounds, characterized by contacting a kerosene fraction in the presence of hydrogen with a catalyst comprising at least 1 w/o platinum group metal and 0.5 w/o fluoride on alumina, the process being further characterized by maintaining the kerosene feed water content to below about ppm. by weight.
Kerosene boiling range fractions suitable for the process of the present invention may be derived from a variety of sources. In general, fractions in the boiling range from about 300 to 600 C. are suitable. Examples of suitable feeds are, for example, straight run, catalytically cracked, or hydrocracked fractions and combinations thereof. The fractions for which the present process is advantageous have APl gravities lower than 39 and smoke points which are usually below about 20. Such fractions contain substantial amounts of aromatic and naphthenic ring compounds, i.e., a suitable straight run fraction from a naphthenic crude which may con tain on the order of 10 to percent aromatics and 40 to 70 percent naphthenes. Hydrocracked kerosene fractions usually have higher aromatics content in the range of 30 to 60 percent.
When the kerosene feed contains relatively high contents of heteroatomic impurities such as nitrogen, sulfur or metallic compounds, hydrotreating to reduce or remove these impurities is desirable. Sulfur compounds are especially undesirable since they tend to poison the platinum group metal in the hydrogenation ring opening catalyst.
Hydrofining processes and catalysts suitable for use in connection with the present process are well known. Such catalysts generally comprise one or more of the various Group Group V] and Group VIII metals as well as the oxides and sulfides thereof supported on a porous carrier. Thus nickel molybdenum sulfide on alumina is an example of a useful, commercially available catalyst.
Hydrofining can be carried out over a wide range of conditions that depend upon the particular hydrocarbon feed and catalyst used. Temperatures in the range of 625 to 750 F., pressures in the range of 400 to 1,500 p.s.i.g., liquid hourly space velocities of about 0.5 to 5 and hydrogen to oil ratios of about 500 to 10,000 standard cubic feet of H per barrel of feed are customary conditions. Partial hydrogenation of aromatics in the kerosene boiling range may be effected in the hydrotreating reaction but is neither required for nor forms a part of the present invention.
The present process uses a catalyst composite which has certain critical concentrations of components. The predominant portion of the catalyst is a porous alumina support. Suitable alumina supports include activated alumina, gamma alumina, eta alumina, pseudo-alumina and the like. The catalyst contains at least 1 w/o of a platinum group metal and preferably about 1.5 w/o platinum.
The catalyst must also contain at least 0.5 w/o fluorine and preferably about 1 percent weight fluorine.
One of the surprising discoveries in development of the present process was the necessity for the addition of fluorine. Fluorine is customarily added to such catalyst composites to promote acid catalyzed reactions. The desired hydrogenation/ring opening reactions of the present invention are known to be metal catalyzed. Thus, the addition of a halogen would not be expected to aid in these reactions but instead to lead to undesirable hydrocracking.
While not wishing to be bound by the theory it is believed that the function of the fluorine is to aid in the conversion of six member ring structures to isomeric five member ring structures, which are more easily ring-opened by the hydrogenation metal. This theory will be further demonstrated in the examples included herein.
Platinum metal and fluorine may be added to the alumina support by various means known to the art. A convenient method involves competitive ion exchange of discrete particles (spheres, extrudates, etc.) of alumina with an aqueous solution of chloroplatinate ions and ammonium ions such as a dilute solution of chloroplatinic acid and ammonium mitrate. Nitrate and chloride ions are removed by washing and the composite is impregnated with a suitable fluoride compound such as a solution of ammonium bifluoride. Calcination decomposes the ammonium ion.
Competitive ion exchange results in highly dispersed platinum metal. This dispersion is preserved by careful reduction with a hydrogen-containing gas in a substantially moisture-free atmosphere.
The process may be carried out in any suitable equipment but preferably in a fixed bed reaction system where the catalyst is disposed as discrete particles in a reaction zone and the hydrocarbon feed passed therethrough in upward, downward or radial flow.
Reaction conditions for the present invention depend upon the kerosene feed composition properties and the catalyst composition and degree of activation.
Suitable conditions are temperatures in the range of 500 to 800 F., pressure in the range of 500 to 1,500 p.s.i.g., liquid hourly space velocities of from 0.5 to 5 volumes of feed per volume of catalyst per hour and hydrogen to hydrocarbon mole ratios of about 5 to 20.
The moisture content of the kerosene feed is especially important and should be maintained below about p.p.m. by weight and preferably at about 2 p.p.m. by weight. The importance of low water content will be demonstrated in the examples.
The following examples serve to further elucidate the practice and advantages ofthe present invention.
EXAMPLE 1 Catalysts were prepared with platinum contents of0.1, 0.68 and 1.5 w/o and 0.6 w/o fluorine by uniformly dispersing platinum on porous alumina. The metal was incorporated by competitive ion exchange of chloroplatinate ions in dilute ammonium nitrate solution. Fluorine was incorporated by impregnation of the catalyst with ammonium bifluoride solution. The catalysts were washed free of unreacted ions, dried, calcined and reduced in dry hydrogen. These catalysts were tested with a hydrotreated naphthenic kerosene fraction (310 to 540 F. boiling range) at 665 F., 1.5 liquid hourly space velocity (LHSV) and 10 H jhydrocarbon mole ratio. The results are shown in table 1.
TABLE 1 Pt/AlzOa-F Catalyst Feed 0. 1% 0.68% 1. 5%
Catalyst age, hours 144 3241 99 Conditions:
Temperature, F 665 665 665 Pressure, p.s.i.g.. 1, 600 1, 500 1, 500 LHSV 1. 5 1. 5 1. 6 Hg/Oll, molar 10 10 10 Yields:
C -C5, percent w 0.8 1. 5 1. 6 113-310 F., percent v 0. 8 6.7 7. 8 310 F.+, percent v 100.1 95.0 94. 7 Kerosene properties:
Gravity, API at 60 F 37.0 38. 5 40.3 40. 8 Hydrocarbon type, percent v:
Paraffins 20. 3 21. 4 25.1 27. 3 Naphthenes- 68. 7 77. 3 73. 7 71. 9 Aromatics 12. 0 1. 3 1. 2 0. 8 N aphthenes, total product (moles/100 g. of feed):
One-ring 0. 1782 0. 1921 0. 2320 Two-ring 0. 1844 0. 1584 0. 1435 Three-ring 0. 0593 0. 0454 0. 0172 Net decrease in rings, percent In 9. 9 14. 3
These results show that ring opening is greatest with the highest platinum-content catalyst. The results with the 0.1 We platinum catalyst are substantially the same as would be obtained by hydrogenation alone without ring-opening. Note that the paraffin content of the product is not greatly increased over that of the feed, the net effect being conversion of aromatics to naphthenes. This product does not meet the 39 APl minimum gravity specification. In all cases diand triring naphthenes are ring opened selectively with a net increase in monoring naphthenes and paraffins.
EXAMPLE 2 A catalyst prepared by competitive ion exchange of platinum and impregnation with fluoride of a commercial catalytic reforming catalyst was used to study the effect of moisture in the process. Platinum and fluoride were added as described in example 1 to give a catalyst having 1.5 w/o' platinum and 1 w/o fluorine. Prior to use the catalyst was calcined in a reactor with dry air, purged with nitrogen and reduced with dry hydrogen for 1 hour at atmospheric pressure.
The catalyst was used for ring opening a kerosene fraction like that in example 1. Conditions were 850 p.s.i.g., 660 F., 2 LHSV and 10 H joil ratio (mole). The kerosene was dried to a water level of 10 p.p.m. by weight by passing it over molecular sieves. After hours of processing the product AP] gravity was about 39.7. After 200 hours of operation of feed water level was increased to 570 p.p.m. and the product APl gravity immediately fell to 38.8. On returning to 10 p.p.m. water the product API gravity increased to 39.5.
During the dry operation the aromatics content of the product was about 3 percent (compared to 13 percent in the feed).
Thus, the effect of water in the system is to severely reduce ring openinggiving results much like simple hydrogenation of aromatics.
EXAMPLE 3 A catalyst substantially the same as the 1.5 w/o platinum catalyst described in example 2 was used for ring opening the 310-540 F. kerosene fraction of example 1 at 850 p.s.i.g., 660 F., 2 LHSV and 10 H loil ratio (mole). The kerosene was dried to 2 p.p.m. by weight water with molecular sieves. During 1,000 hours of operation (after which the run was terminated without evidence of catalyst deactivation) the product API gravity was 40 or above. Yield of product during this time was about 96 percent volume of 310 F. plus kerosene.
This operation under very dry conditions results in sufficient ring opening to provide a balanced specification jet fuel and significantly increases the long term process stability.
We claim as our invention:
1. A process for hydrogenating/ring-opening a feed consisting essentially of kerosene boiling range hydrocarbons wherein the feed substantially free of heteroatomic impurities is contacted in the presence of hydrogen with a catalyst comprising at least about 1.0 w/o of a platinum group metal and at least 0.5 w/o by weight fluorine on an alumina support at temperature in the range of about 500 to 800 F., a pressure in the range of about 500 to 1,500 p.s.i.g. and a hydrogen to hydrocarbon mole ratio of from about 5 to 20 and wherein the water content of the contacted hydrocarbons is below about 10 p.p.m. by weight.
2. The process of claim 1 wherein the water content of the contacted hydrocarbons is about 2 p.p.m. by weight.
3. The process of claim 1 wherein the contacted hydrocarbons are substantially free of sulfur compounds.
4. The process of claim 1 wherein the contacted hydrocarbons have a total ring content, aromatic plus napthenes, of greater than about 50 percent.
5. The process of claim 4 wherein the contacted hydrocarbons have a water content of about 2 p.p.m. by weight.
6. The process of claim 5 wherein the heteroatomic impurities have been removed by hydrotreating the kerosene boiling range hydrocarbons.
7. The process of claim 5 wherein the catalyst comprises about 1.5 w/o platinum and about 1 W10 fluorine on the alumina support.
8. The process of claim 1 wherein the kerosene boiling range hydrocarbons have an APl gravity of below about 39.
9. The process of claim 1 wherein the platinum group metal is platinum.
Claims (8)
- 2. The process of claim 1 wherein the water content of the contacted hydrocarbons is about 2 p.p.m. by weight.
- 3. The process of claim 1 wherein the contacted hydrocarbons are substantially free of sulfur compounds.
- 4. The process of claim 1 wherein the contacted hydrocarbons have a total ring content, aromatic plus napthenes, of greater than about 50 percent.
- 5. The process of claim 4 wherein the contacted hydrocarbons have a water content of about 2 p.p.m. by weight.
- 6. The process of claim 5 wherein the heteroatomic impurities have been removed by hydrotreating the kerosene boiling range hydrocarbons.
- 7. The process of claim 5 wherein the catalyst comprises about 1.5 w/o platinum and about 1 w/o fluorine on the alumina support.
- 8. The process of claim 1 wherein the kerosene boiling range hydrocarbons have an API gravity of below about 39.
- 9. The process of claim 1 wherein the platinum group metal is platinum.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81452069A | 1969-04-07 | 1969-04-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3607729A true US3607729A (en) | 1971-09-21 |
Family
ID=25215291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US814520A Expired - Lifetime US3607729A (en) | 1969-04-07 | 1969-04-07 | Production of kerosene jet fuels |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3607729A (en) |
| JP (1) | JPS4918443B1 (en) |
| CA (1) | CA940856A (en) |
| DE (1) | DE2016358C3 (en) |
| FR (1) | FR2038298B1 (en) |
| GB (1) | GB1296772A (en) |
| NL (1) | NL165210C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4875992A (en) * | 1987-12-18 | 1989-10-24 | Exxon Research And Engineering Company | Process for the production of high density jet fuel from fused multi-ring aromatics and hydroaromatics |
| US5954941A (en) * | 1995-05-22 | 1999-09-21 | Total Raffinage Distribution S.A. | Jet engine fuel and process for making same |
| US6274029B1 (en) | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6309432B1 (en) | 1997-02-07 | 2001-10-30 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US6822131B1 (en) | 1995-10-17 | 2004-11-23 | Exxonmobil Reasearch And Engineering Company | Synthetic diesel fuel and process for its production |
| US20070021636A1 (en) * | 2003-05-22 | 2007-01-25 | Willem Bosch | Process to upgrade kerosenes and a gasoils from naphthenic and aromatic crude petroleum sources |
| US20090288982A1 (en) * | 2005-04-11 | 2009-11-26 | Hassan Agha | Process for producing low sulfur and high cetane number petroleum fuel |
| RU2657733C1 (en) * | 2017-12-20 | 2018-06-15 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method for producing high-density jet fuel for supersonic aviation |
| EP4527499A1 (en) | 2023-09-19 | 2025-03-26 | Indian Oil Corporation Limited | A catalyst for hydrogenation of unsaturated hydrocarbons and a method for preparation thereof |
-
1969
- 1969-04-07 US US814520A patent/US3607729A/en not_active Expired - Lifetime
-
1970
- 1970-01-19 CA CA072,486A patent/CA940856A/en not_active Expired
- 1970-04-06 JP JP45028976A patent/JPS4918443B1/ja active Pending
- 1970-04-06 NL NL7004885.A patent/NL165210C/en not_active IP Right Cessation
- 1970-04-06 DE DE2016358A patent/DE2016358C3/en not_active Expired
- 1970-04-06 FR FR7012352A patent/FR2038298B1/fr not_active Expired
- 1970-04-06 GB GB1296772D patent/GB1296772A/en not_active Expired
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4875992A (en) * | 1987-12-18 | 1989-10-24 | Exxon Research And Engineering Company | Process for the production of high density jet fuel from fused multi-ring aromatics and hydroaromatics |
| US5954941A (en) * | 1995-05-22 | 1999-09-21 | Total Raffinage Distribution S.A. | Jet engine fuel and process for making same |
| US6274029B1 (en) | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6296757B1 (en) | 1995-10-17 | 2001-10-02 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6822131B1 (en) | 1995-10-17 | 2004-11-23 | Exxonmobil Reasearch And Engineering Company | Synthetic diesel fuel and process for its production |
| US6607568B2 (en) | 1995-10-17 | 2003-08-19 | Exxonmobil Research And Engineering Company | Synthetic diesel fuel and process for its production (law3 1 1) |
| US6669743B2 (en) | 1997-02-07 | 2003-12-30 | Exxonmobil Research And Engineering Company | Synthetic jet fuel and process for its production (law724) |
| US6309432B1 (en) | 1997-02-07 | 2001-10-30 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US20070021636A1 (en) * | 2003-05-22 | 2007-01-25 | Willem Bosch | Process to upgrade kerosenes and a gasoils from naphthenic and aromatic crude petroleum sources |
| US20090288982A1 (en) * | 2005-04-11 | 2009-11-26 | Hassan Agha | Process for producing low sulfur and high cetane number petroleum fuel |
| US7892418B2 (en) | 2005-04-11 | 2011-02-22 | Oil Tech SARL | Process for producing low sulfur and high cetane number petroleum fuel |
| RU2657733C1 (en) * | 2017-12-20 | 2018-06-15 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Method for producing high-density jet fuel for supersonic aviation |
| EP4527499A1 (en) | 2023-09-19 | 2025-03-26 | Indian Oil Corporation Limited | A catalyst for hydrogenation of unsaturated hydrocarbons and a method for preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1296772A (en) | 1972-11-15 |
| JPS4918443B1 (en) | 1974-05-10 |
| NL165210B (en) | 1980-10-15 |
| FR2038298B1 (en) | 1977-01-21 |
| FR2038298A1 (en) | 1971-01-08 |
| DE2016358A1 (en) | 1970-12-17 |
| NL7004885A (en) | 1970-10-09 |
| NL165210C (en) | 1981-03-16 |
| DE2016358C3 (en) | 1978-09-28 |
| CA940856A (en) | 1974-01-29 |
| DE2016358B2 (en) | 1977-12-08 |
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