GB1563357A - Hydrogenation process - Google Patents
Hydrogenation process Download PDFInfo
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- GB1563357A GB1563357A GB5207476A GB5207476A GB1563357A GB 1563357 A GB1563357 A GB 1563357A GB 5207476 A GB5207476 A GB 5207476A GB 5207476 A GB5207476 A GB 5207476A GB 1563357 A GB1563357 A GB 1563357A
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- hydrogenation
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 15
- 239000003054 catalyst Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000000852 hydrogen donor Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- -1 hydrogenated polycyclic aromatic compound Chemical class 0.000 claims description 7
- 239000000386 donor Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 33
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 150000002790 naphthalenes Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910003294 NiMo Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZIDCYKOQDVAKMQ-UHFFFAOYSA-N 1-butyl-1,2-dihydronaphthalene Chemical compound C1=CC=C2C(CCCC)CC=CC2=C1 ZIDCYKOQDVAKMQ-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical class CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- NNBZCPXTIHJBJL-AOOOYVTPSA-N cis-decalin Chemical compound C1CCC[C@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-AOOOYVTPSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 201000010549 croup Diseases 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- GKROKAVBUIADBS-UHFFFAOYSA-N phenanthrene-2-carbaldehyde Chemical compound C1=CC=C2C3=CC=C(C=O)C=C3C=CC2=C1 GKROKAVBUIADBS-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
- C10G47/34—Organic compounds, e.g. hydrogenated hydrocarbons
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
Landscapes
- 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)
Description
(54) HYDROGENATION PROCESS
(71) We, THE BRITISH PETROLEUM COMPANY LIMITED, of
Britannic House, Moor Lane, London EC2Y 9BU, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to a process for the hydrogenation of unsaturated hydrocarbons and optionally cracking the hydrogenated derivatives.
The process is particularly suitable for treating polynuclear aromatic hydrocarbons contained in heavy petroleum fractions such as atmospheric residue, waxy distillate and vacuum residue.
In the operation of a typical oil refinery, crude oil is initially fed to a distillation unit in which it is separated at atmospheric pressure into benzine, naphtha, kerosine and gas oil. The residue from the atmospheric distillation unit, known as atmospheric residue, is composed of fractions boiling under atmospheric pressure at a temperature greater than 3500 C. This residue may either be used directly as a fuel oil or as a feedstock to a distillation unit operating under reduced pressure.
The distillate from the vacuum distillation unit, known as waxy distillate, vacuum distillate or vacuum gas oil may be used as a catalytic cracker feedstock or used in lubricating oil manufacture, whilst the residue, known as vacuum residue, may be used as a fuel oil component.
The naphtha fraction is particularly important since, amongst other reasons, directly or indirectly it is the source of benzene, toluene and xylene, known collectively as BTX, and indirectly the source of olefins via steam cracking. BTX is a valuable motor spirit component because of its high octane number and it is also in demand as chemical feedstock.
With increasing crude oil prices, it is becoming more necessary to increase the conversion of crude petroleum to high value products, particularly the conversion of heavier fractions and to minimise the production of relatively low value residues.
Our British Patent 1361671 claims a process for the production of olefins which process comprises hydrogenating a petroleum distillate feedstock containing aromatic hydrocarbons in the presence of a hydrogenation catalyst and hydrogen to at least partially saturate the aromatic hydrocarbons in the feedstock and thermally cracking directly the resulting hydrogenated product in the presence of steam.
We have now discovered a process for the hydrogenation of heavy petroleum fractions using a hydrogen donor instead of or as a partial replacement for hydrogen, which may be combined with a cracking process.
Thus according to the present invention there is provided a process for the hydrogenation of a petroleum fraction containing at least 25% by wt of materialboiling above 350"C, preferably at least 25% by wt of material boiling above 5500 C, which process comprises contacting the fraction at elevated temperature and pressure with a hydrogen donor and a catalyst comprising from 525% of a metal of Group VIA of the Periodic Table, i.e., Mo, W, or Cr, on a refractory support, the percentage being by weight of total catalyst.
The catalyst may be promoted by the addition of 1--10% by wt of an Iron
Group metal, i.e., Fe, Co or Ni.
Suitable hydrogen donors include partially hydrogenated polycyclic aromatic compounds, such as tetralin, the preferred donor, and naphthenes, such as decalin.
The hydrogen donor is suitably present in amount 20:1 to 1:1 by wt of the feedstock, preferably in amount 4:1.
Particularly preferred feedstocks are atmospheric residues boiling above 350"C. Depending on the original crude oil source the feedstocks may contain 1 -8% by wt sulphur, 01% by wt nitrogen, 1W10,000 ppm by wt metals and 1-20% by wt asphaltenes.
The catalyst may be used in the sulphided or unsulphided form and under an inert atmosphere, e.g., nitrogen, or hydrogen.
The feedstock may, if desired, be given a preliminary treatment, to remove asphaltenes and/or metal compounds.
The hydrogenation process conditions may be chosen from the following ranges:
Broad Range Preferred Range
Temperature OC 100 - 400 250 - 350
Pressure bars(ga) 1 - 100 1 - 20
Space velocity v/v/hr 0.1 - 10 0.5 - 2
The catalyst percentages above are expressed as element per cent by wt of
total catalyst, but the metals will normally be present as compounds, particularly
the oxides or sulphides. Preferred combinations are cobalt and molybdenum,
nickel and molybdenum, nickel and tungsten or nickel, cobalt and molybdenum. If
two or more iron group metals are used the total iron group metal content should
remain in the range 1--10% wt.
The refractory support may be one or more oxides of elements of Groups III
or IV of the Periodic Table, particularly alumina, silica, or silica-alumina. A single
oxide, particularly alumina, is preferred to limit side reactions. The alumina may
contain up to 5% wt of silica or phosphate to stabilise it and/or give the required
pore characteristics.
The method of preparation of the catalyst as regards the Iron Group metal, the croup VIA metal and the support may follow standard practice. Thus the metals
may be added by simultaneous or sequential impregnation with suitable salt
solutions, followed by drying, calcination, and, if necessary, pre-sulphiding.
Attention must be paid to both physical and chemical characteristics of the
catalysts used. Microporous catalysts, with most of the surface area in pores with
diameters less than 300A combine good activity with reasonable life. These
catalysts show less tendency to pick up metals and asphaltenes present in the feed.
The hydrogenated material is more suitable for cracking to high value products than the unhydrogenated feedstock.
If an acidic catalyst support is employed then hydrogenation and cracking can occur in a one stage process over a single catalyst.
Thus according to a modification of the invention there is provided a process for the hydrogenation and cracking of a petroleum fraction containing at least 25% by wt of material boiling above 3500 C, preferably at least 25% by wt of material boiling above 5500 C, which process comprises contacting the fraction at elevated temperature and pressure with a hydrogen donor and a catalyst comprising from 1-1 0% by wt of an Iron Group metal, i.e., Fe,Co or Ni, and from 525% by wt of a metal of Group VIA, i.e., Mo, W or Cr, on a refractory acidic support, all percentages being in weight of total catalyst.
Suitable acidic catalysts include silica-alumina, zeolites and alumina or silicaalumina treated with a halide such as fluorine.
The cracked products include useful chemicals such as benzene, toluene and xylene, naphthalene and substituted naphthalenes. The naphthalenes and substituted naphthalenes are potential hydrogen donors and can be hydrogenated to donors in a separate step and recycled to the hydrogenation/cracking stage together with unconverted donor.
Thus according to a further feature of the present invention there is provided a process for the production of BTX from a petroleum fraction containing at least
25% by wt of material boiling above 3500C, preferably at least 25% of material
boiling above 5500 C, which process comprises (a) contacting the fraction at
elevated temperature and pressure with a hydrogen donor and a catalyst
comprising from 1--10% by wt of an Iron Group metal as hereinbefore defined and
from 525% by weight of a metal of Group VIA as hereinbefore defined on a
refractory acidic support, all percentages being by weight of total catalyst, (b)
fractionating the reaction product into a top fraction containing BTX, a middle
fraction containing unconverted donor and potential donor and a bottom residual
fraction, (c) removing the BTX and residue fractions as products, (d) selectively
hydrogenating the middle fraction and (e) recycling the selectively hydrogenated
fraction as hydrogen donor to Stage (a).
Suitable selective hydrogenation catalysts include Groups VIA and/or VIII
metal catalysts such as Cr2OJAI203, CoMo/Al2O3, NiMo/Al2O3 and Group IB
metal catalysts such as Cu/Al2O3.
If the feedstock has not been demetallised, by careful choice of the support for
the catalyst in Stage (a) it is possible to influence the properties of the residue from
this stage. It is possible to use a demetallising catalyst support, e.g., wide pore SiOAl2O3 which will give a demetallised residue of low metal content, but an
unregenerably catalyst. On the other hand if a regenerable catalyst is desired this
can be achieved by using a support which does not remove metallic contaminants
from the residue, e.g., a microporous basic alumina.
Demetallised residue can be further treated, e.g., by coking to produce coke
and a range of lighter products.
The invention is illustrated with reference to the following Examples.
Example 1.
The first table shows that of the Group VIA and Group VIII promoted
catalysts, WOJAI203 has the highest activity in'the oxide form. The catalysts are
charged in the ratio 1 to 2 parts of tetralin containing about 9% phenanthrene and
heated to 3000C for 15 hours in a stirred autoclave. The products are analysed by
GLC and include hydrogenated phenanthrenes, substituted naphthalenes,
naphthalene itself, decalin, a variety of light aromatics as well as unconverted
reactants.
TABLE 1
Activities and Selectivities of
Group VIA Catalysts at 3000C Cr2O3Y MoO3/ W03 / Catalyst Alp03 Al203 Awl 202 CoMo NiMo Atmosphere N2 N2 N2 N2 N2 % Phenanthrene conversion 17.0 12.2 89.6 30.7 32.7
Naphthalene % wt 3.7 8.2 8.5 22.8 13.6
Tetralin loss % wt 3.6 8.0 9.3 22.7 13.5
Example 2.
Hydrogen donation can be catalysed also by sulphided catalysts under
hydrogen. Table 2 summarises the results and shows good conversion of
phenanthrene over the unpromoted Group VIA catalysts.
TABLE 2
Activity and Selectivity of
Sulphided Group VIA Catalysts at 3000C
Catalyst Mo/A 1203 W/AI203 NiMo CoMo Atmosphere H2 H2 H2 H2 % Phenanthrene conversion 72.9 85.9 51.0 61.3
Naphthalene 6Xc wt 10.9 4.1 13.8 15.3
Tetralin loss % wt 10.1 7.1 10.0 10.6
Example 3.
Table 3 gives details of the results when an oxidic NiW catalyst is supported on
bases of increasing acidity.
TABLE 3
Activity and Selectivity of
Oxidic NiW Catalysts on Acidic Supports
Catalyst SiO2 /Al293 F-SiO2 /Al2O3 Y-Zeolite Atmosphere N2 N2 N2 % Phenanthene conversion 62.4 87.1 84.8
Naphthalene 7E wt 11.0 12.8 12.4
Tetralin loss % wt 16.1 20.9 41.1 The conversion of phenanthrene is high and hydrogen donation is the main
reaction. However it can be seen that more tetralin is lost than naphthalene
formed. This occurs because tetralin is cracked to BTX over these acidic supports.
The products of reaction for one support F-SiO2Al2O3 are shown in detail in
Table 4.
TABLE 4
Products from Phenanthrene
Conversion on F-SiO2/Al2O3 Catalysts
Catalyst NiW/F-SiO2/Al2O3 W/F-SiO2/Al2Oa Feed Phenanthrene % wt 8.5 8.5 Products Benzene 5.9 3.5 Toluene 1.6 0.8 Xylenes 0.6 0.9 Butyl benzenes - 1.6 Methyl naphthalene-s 0.4 0.3 Subset naphthalenes 1.9 1.9 Trmsdecalin 5.9 3.6 Cis-decalin 1.6 1.8 Tetralin 63.1 70.7 Naphthalene 12.8 9.5 Butyl-di-hydro-naphthalene 1.6 1.0 9 ::10-di-hydro-phenanthrene 1.0 1.3 Teflahydro-phenanthrene 1.7 1.8 Octhydrophenanthrene 0.8 1.2 Phenanthrene 1.1 1.0 In both cases about 7.5% phenanthrene has been converted partly to various hydrogenated derivatives (3.5 to 4.5% wt) and partly to naphthalene derivatives formed by cracking the hydrogenated products (3.0 to 3.5% wt). Large amounts of tetralin have been removed, 30 to 35%, part to decalin (5 to 7%) part to naphthalene by hydrogen transfer (10 to 13% and part to light aromatics (7 to 8%).
The potential hydrogen donor capacity of the system is made up of tetralin, decalin and naphthalenes which in principle can be rehydrogenated to donors in a separate step. The sum of these components is 87% and 89%, very close to the original amount of tetralin present allowing for dilution by light products. Thus the net reaction in this example is the conversion of phenanthrene partly to hydrogenated derivatives and partly to BTX. The yield of aromatics is about 50% on phenanthrene consumed.
Claims (12)
1. A process for the hydrogenation of a petroleum fraction containing at least 25% by wt of material boiling above 350"C which process comprises contacting the fraction at elevated temperature and pressure with a hydrogen donor and a catalyst comprising from 525% by wt of a metal of Group VIA of the Periodic Table.
2. A process according to Claim 1 wherein the petroleum fraction contains at least 25% by wt of material boiling above 5500C.
3. A process according to either of the preceding claims wherein the catalyst is promoted by the addition of 1--10% by wt of an Iron Group metal.
4. A process according to any of the preceding claims wherein the hydrogen donor is a partially hydrogenated polycyclic aromatic compound or a naphthene.
5. A process according to any of the preceding claims wherein the hydrogen donor is present in amount 20:1 to 1:1 by wt of the feedstock.
6. A process according to Claim I wherein hydrogenation is effected under a temperature in the range 1000--4000C, a pressure in the range 1--100 bars (ga) and a space velocity in the range 0.1-10 v/v/hr.
7. A process according to Claim 6 wherein hydrogenation is effected under a temperature in the range 2500--350"C, a pressure in the range 1-20 bars (ga) and a space velocity in the range 0.5-2 v/v/hr.
8. A process according to any of the preceding claims wherein the catalyst is supported on a refractory acidic material and cracking is effected in addition to hydrogenation.
9. A process according to Claim 8 wherein the refractory acidic support is silica-alumina, a zeolite or halogenated alumina.
10. A process for the production of benzene, toluene and xylene from a petroleum fraction containing at least 25% by wt of material boiling above 350"C which process comprises (a) hydrogenating and cracking the feedstock by a process according to either Claims 8 or 9, (b) fractionating the reaction product into a top fraction containing BTX, a middle fraction containing unconverted donor and potential donor and a bottom residual fraction, (c) removing the BTX and residue fractions as products, (d) selectively hydrogenating the middle fraction, and (e) recycling the selectively hydrogenated fraction as hydrogen donor to Stage (a).
11. A process according to Claim 1 as hereinbefore described with reference to the Examples.
12. Products whenever prepared by a process according to any of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5207476A GB1563357A (en) | 1977-12-13 | 1977-12-13 | Hydrogenation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5207476A GB1563357A (en) | 1977-12-13 | 1977-12-13 | Hydrogenation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1563357A true GB1563357A (en) | 1980-03-26 |
Family
ID=10462533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB5207476A Expired GB1563357A (en) | 1977-12-13 | 1977-12-13 | Hydrogenation process |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1563357A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7157401B2 (en) | 2002-10-17 | 2007-01-02 | Carnegie Mellon University | Catalyst for the treatment of organic compounds |
| US7387712B2 (en) | 2002-10-17 | 2008-06-17 | Carnegie Mellon University | Catalytic process for the treatment of organic compounds |
| US8039652B2 (en) | 2004-06-15 | 2011-10-18 | Carnegie Mellon University | Methods for producing biodiesel |
-
1977
- 1977-12-13 GB GB5207476A patent/GB1563357A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7157401B2 (en) | 2002-10-17 | 2007-01-02 | Carnegie Mellon University | Catalyst for the treatment of organic compounds |
| US7387712B2 (en) | 2002-10-17 | 2008-06-17 | Carnegie Mellon University | Catalytic process for the treatment of organic compounds |
| US7625832B2 (en) | 2002-10-17 | 2009-12-01 | Carnegie Mellon University | Catalyst for the treatment of organic compounds |
| US8039652B2 (en) | 2004-06-15 | 2011-10-18 | Carnegie Mellon University | Methods for producing biodiesel |
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