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Publication numberUS3552924 A
Publication typeGrant
Publication dateJan 5, 1971
Filing dateAug 15, 1966
Priority dateAug 15, 1966
Publication numberUS 3552924 A, US 3552924A, US-A-3552924, US3552924 A, US3552924A
InventorsHarold J Hepp
Original AssigneePhillips Petroleum Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydrogen manufacture
US 3552924 A
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Description  (OCR text may contain errors)

Jam 971 H. J. HEPP 3,552,924

HYDROGEN MANUFACTURE Filed Aug. 15, 1966 Nouvavdas im- WATER GAS SHIFT STEAM REFORMING HEAVY AROMATIC OILp NOliVHVdHS HYDRORACKING A 7' TOR/VEYS United States Patent O 3,552,924 HYDROGEN MANUFACTURE Harold J. Hepp, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware Filed Aug. 15, 1966, Ser. No. 572,316 Int. Cl. 'C01b N18 US. Cl. 23-212 8 Claims ABSTRACT OF THE DISCLOSURE A process for producing hydrogen from an excess refinery stream or mixture of refinery streams by hydrocracking, steam reforming a vaporous fraction from the hydrocracking step, contacting the effluent from the reforming step admixed with additional steam with a water gas shift catalyst, recycling a portion of the hydrogen separated from the shift reaction to the hydrocracking step, and recovering the remainder of the hydrogen as product.

This invention relates to a process for producing hydrogen from excess refinery streams ranging from C to heavy oils.

In most petroleum refineries a complete balance of operations is rarely achieved. Usually, there is an excess of materials such as naphtha, distillates, gas oils, residual oils, and the like, and there is almost always a deficiency of hydrogen for use in hydrotreating, hydrogenation, hydrocracking, and similar operations.

This invention is concerned with a process for converting excess liquid petroleum streams to hydrogen.

Accordingly, it is an object of the invention to provide a process for converting liquid hydrocarbons to hydrogen. Another object is to provide a simple and eflicient process for converting liquid hydrocarbons into H and CO with recovery of heavy aromatic oils from the process. Other objects of the invention will become apparent to one skilled in the art upon consideration of the accompanying disclosure.

In accordance with the invention, a liquid hydrocarbon feed comprising an excess refinery stream or a mixture of refinery streams ranging from C to heavy oils is hydrocracked in admixing with hydrogen under severe hydrocracking conditions; the hydrocracking efiluent is cooled so as to condense C and heavier hydrocarbons therein with separate recovery of the vaporous fraction and the liquid fraction; the vaporous fraction is admixed with steam and passed to a steam reforming step in contact with a reforming catalyst to produce principally H CO, and CO the efiiuent from the steam reforming step in admixed with additional steam as required for reaction and/or cooling, and passed to a Water gas shift step for conversion of the CO to CO in contact with a shift reaction catalyst to produce additional H and the gaseous efiiuent from the shift reaction is separated into an H stream and a C0 stream, a portion of the H being recycled to the hydrocracking step and the remaining portion being recovered as product H The effluent from the hydrocracking step is partially condensed in indirect heat exchange with water to convert the water to steam, which is then passed to the steam reforming step and to the water gas shift reaction. The C and heavier hydrocarbons comprising the condensate from the cooling step is passed to a separation zone for recovery of a heavy aromatic oil as a product of the process and a lighter fraction which is recycled to the hydrocracking step. When catalytic hydrocracking is used, essentially no heavy aromatic oil is made, and the total liquid product is recycled to the hydrocracking zone.

The liquid oil feed is hydrocracked under severe cracking conditions, either pyrolytically or catalytically, such that only about 5 to 12 percent of the feedstock is yielded as heavy aromatic hydrocarbons. Operating conditions in the hydrocracking zone or step include a ratio of hydrogen to feedstock in the range of 1,000 to 15,000 cu. ft./bbl., a pressure in the range of 250-1000 p.s.i.g, a temperature in the range of 750-1350 F., and a liquid hourly space velocity in the range of 0.1 to 1-0 (catalytic) or a contact time of 0.1 to 10 minutes (pyrolytic). It is preferred to utilize a catalyst but pyrolytic hydrocracking is feasible. Any hydrocracking catalysts having both a hydrogenation component and a cracking component may be utilized. Preferred catalysts include the metals, oxides and/or sulfides of nickel, moylbdenum, platinum, palladium, ruthenium, tungsten, and/or cobalt deposited on alumina, silica-alumina, silica-zirconia, or silica-magnesia support.

Conditions in the steam reforming zone include a steam to dry gas mol ratio in the range of 1:1 to 10:1, a pressure in the range of 250-1000 p.s.i.g, a temperature in the range of 1250-1600 F., and a dry gas hourly space velocity in the range of 500 to 10,000. The preferred catalyst is nickel on alundum (aluminum oxide) but any of the steam reforming catalysts known to the industry may be utilized.

In the water gas shift reaction, conditions include a steam to dry gas mol ratio in the range of 0.521 to 3:1, a pressure in the range of 300-500 p.s.i.g, a temperature in the range of 450-850 F., a dry gas hourly space velocity in the range of 500 to 5,000, and, preferably, an iron oxide-chromium oxide catalyst. Other water gas shift reaction catalysts known to the industry, such as zinccopper chromite, may be utilized.

Separation of H and CO from the efliuent from the water gas shift reaction is effected, for example, by absorption of the CO in ethanolamine in conventional manner. Any manner of effecting this separation is within the scope of the invention.

The C and heavier oil fraction downstream of the condensation step is either separated by fractional distillation or any other conventional means into a heavy aromatic oil and a lighter fraction which is recycled to the hydrocracking step (pyrolytic hydrocracking) or is recycled without such a separation step (catalytic hydrocracking). The heavy aromatic oil is a marketable product of the operation, for example, for carbon black manufacture.

A more complete understanding of the invention may be had by reference to the accompanying schematic drawing, which is a flow or arrangement of apparatus suitable for performing the invention.

'Referring to the drawing, a suitable liquid oil feed in line 10 is fed to hydrocracking unit 12 in admixture with hydrogen from line -14 and the liquid oil fraction from line 16' obtained as hereinafter disclosed. The hydrocracked efiiuent is passed via line 18 thru indirect heat exchanger 20 and cooled therein by heat exchange with water introduced thru line 22 which converts at least the major portion of the water to steam. The heat exchange in exchanger .20 is controlled so as to condense the C and heavier hydrocarbons and leave most of the C and lighter hydrocarbons in vapor form. The efiiuent from exchanger 20 passes thru line 24 into knock-out drum 26, the liquid oil being withdrawn from the bottom of the drum thru line 128 and the overhead vapor being passed thru line 30 to steam reforming zone 32 in admixture with steam from line 34 which connects with line 22.

The efiiuent from steam reforming zone 32 consisting essentially of H CO, and CO along with steam, is passed via line 36 to water shift reaction zone 38 in admixture with added steam 'from line 40. The water shift reaction converts CO to CO with the formation of additional hydrogen, the effluent from this reaction being passed via line 42 to separation or absorption zone 44 where it is contacted with ethanolamine from line 45 The ethanolamine, containing CO is Withdrawn from this zone thru line 46 and passed to CO recovery means (not shown) to condition the ethanolamine for reuse in the process. The CO is recovered as a product of the process. The hydrogen remaining in vapor form after contacting with the ethanolamine is recovered thru line 48, a minor portion being recycled thru line 14 to the hydrocracking operation in zone 12 and the major portion being recovered as hydrogen for use in refinery processes or for any other suitable use.

The liquid C to heavy aromatic oil fraction recovered from knock-out drum 26 thru line 28 is passed to separation zone 50 in which the oil stream is fractionated into a heavy aromatic oil fraction and a lighter oil fraction, the former being recovered as a product of the process thru line 52 and the latter being passed thru lines 16 and 10 to the hydrocracking step, or is recycled directly to the hydrocracking step via line 51.

The following example is illustrative of the process of the invention but is not to be construed as unnecessarily limiting the invention:

EXAMPLE Hydrogen 40 Methane 40 Ethane 17 C 3 These product gases are then reacted with steam at a mol ratio of steam to dry gas of 2:1 and a dry gas hourly space velocity of 1500 over a nickel-alundum catalyst at about 500 p.s.i.g. and 1500 F. to convert the hydrocarbons to hydrogen and the oxides of carbon. This mixture is further reacted with additional steam over an iron oxide-chromium oxide shift catalyst using a steam to dry gas ratio of 0.6: 1, a pressure of 400 p.s.i.g., a temperature of 800 F., and a dry gas hourly space rate of 1500 to convert the carbon monoxide to carbon dioxide with formation of additional H and the carbon dioxide in the resulting stream is absorbed in ethanolamine. This operation produces 31,000 cubic feet of hydrogen per barrel of kerosene of which 8000 cubic feet are recycled. Thus, the net hydrogen production is 23,000 cubic feet per barrel of kerosene.

The foregoing example clearly demonstrates the effectiveness of the process in producing large amounts of hydrogen per barrel of feed, the net hydrogen production being 23,000 cu. ft./bbl. of kerosene distillate. Other excess refinery streams of liquid oils, alone or in admixture, are amenable to hydrogen production in accordance with the invention.

Certain modifications of the invention will become apparent to those skilled in the art and the illustrative details disclosed are not to be construed as imposing unnecessary limitations on the invention.

I claim:

1. A process for producing H from a feed comprising available refinery oils ranging from C to heavy oils, which comprises the steps of:

(a) hydrocracking a stream of said oils in admixture with H under severe conditions to form principally C and lighter hydrocarbons;

(b) cooling the cracked eflluent from step (a) to condence C and heavier hydrocarbons including heavy aromatic oils and leave C and lighter hydrocarbons in vapor form;

(b) into a heavy aromatic oil fraction as a product and (c) catalytically reforming the vapor effluent from step (b) in the presence of steam to convert same principally to H CO, and CO (d) contacting the effluent from step (c) in admixture with steam with a Water gas shift reaction catalyst to increase the production of H (e) selectively removing CO from the eflluent from step (d) thereby leaving the H in the vapor form;

(f) recycling a portion of the H of step (e) to step (g) recovering the remaining portion of H from step (e) as product,

(h) separating the C and heavier fraction of step (b) into a heavy aromatic oil fraction as a product and a lighter fraction, and

(i) recycling the lighter fraction of step (h) to step (a).

2. The process of claim 1 wherein step (a) is effected pyrolytically and only about 5 to 12 weight percent of the feed is yielded as heavy aromatics.

3. The process of claim 1 wherein step (b) is effected by indirect heat exchange with water to form steam and resulting steam is used as steam in steps (c) and (d).

4. A process for producing hydrogen from a feed comprising essentially a kerosene distillate boiling in the range of about 350 to 520 R, which comprises the steps of:

(a) hydrocracking said feed in admixture with H under severe conditions of a ratio of H to feed in the range of 1000 to 15,000 cubic feet per barrel, a pressure in the range of 250 to 1000 p.s.i.g., a temperature in the range of 75 to 1350 F., and a contact time in the range of 0.1 to 10 minutes in the absence of a catalyst, to form principally C and lighter hydrocarbons;

(b) cooling the cracked eflluent from step (a) to condense C and heavier hydrocarbons including heavy aromatic oils and leave 0;, and lighter hydrocarbons in vapor form; (0) passing the vapor efiiuent from step (b) to a catalytic steam reforming step including a nickelalundum catalyst, a steam to dry gas mol ratio in,

the range of 1:1 to 10:1, a pressure in the range of 250 to 1000 p.s.i.g., a temperature in the range of 1250 to 1600 F., and a dry gas hourly space velocity in the range of 500 to 10,000, to convert said vapor efiiuent principally to H C0, and CO (d) passing the efiluent from step (c) in admixture with steam to a water gas shift step with a steam to total dry gas mol ratio in the range of 0.5: 1 to 3: 1, a pressure in the range of 300 to 500 p.s.i.g., a temperature in the range of 450 to 850 F., a dry gas hourly space velocity in the range of 500 to 5000, and an iron oxide-chromium oxide catalyst, to increase the production of hydrogen;

(e) passing the effluent from step (d) to a separation absorption step where it is contacted with ethanolamine to remove CO and to leave H in the vapor form;

(f) recycling a portion of the H of '(e) to step and (g) recovering a remaining portion of H from step (e) as product.

5. The process of claim 4 wherein step (a). is effected pyrolytically and only about 5 to 10 Weight percent of the feed is yielded as heavy aromatics.

6. The process of claim 4 including the step of: (h) recycling the condensate of step (b) to step (a). 7. The process of claim 4 including the steps of: '(h) separating the C and heavier fraction of step a lighter fraction; and (i) recycling the lighter fraction of step (h) to step (a). 8. A process for producing H from a feed comprising available refinery oils ranging from C to heavy oils, which comprises the steps of:

(a) hydrocracking a stream of said oils in admixture with H under severe conditions to form principally C and lighter hydrocarbons, said severe conditions including a ratio of H to feed in the range of 1000 to 15,000 cu. ft./bbl., a pressure in the range of 250 to 1,000 p.s.i.g., a temperature in the range of 750 to 1350 F., and a contact time in the range of 0.1 to min. in the absence of a catalyst;

(b) cooling the cracked efi'luent from step (a) to condensed C and heavier hydrocarbons including heavy aromatic oils and leave C and lighter hydrocarbons in vapor form;

(0) catalytically reforming the vapor efiluent from step (b) to convert sarne principally to H CO, and CO using a nickel-alundum catalyst, a steam to dry gas mol ratio in the range of 1:1 to 10:1, a pressure in the range of 250 to 1000 p.s.i.g., a temperature in the range of 1250 to 1600 F., and a dry gas hourly space velocity in the range of 500 to 10,000;

(d) contacting the efiluent from step (c) in admixture with steam in a steam to total dry gas mol ratio in the range of 0.521 to 3:1, at a pressure in the range of 300 to 500 p.s.i.g., a temperature in the range of 450 to 850 F., a dry gas hourly space velocity in the range of 500 to 5000, with a water gas shift reaction catalyst comprising an iron oxide-chromium oxide catalyst, to increase the production of H (e) selectively removing CO from the efiluent from step ((1) thereby leaving the H in the vapor form;

(f) recycling a portion of the H of step (e) to step (a); and

(g) recovering the remaining portion of H from step (e) as product.

References Cited UNITED STATES PATENTS 6/ 1961 DuBois Eastman et al.

208-107 8/1965 Brooks et a1 260290 12/ 1966 Carson 260672 1/ 1968 DuBois Eastman et al.

208143 7/ 1956 Kaulakis 23212X 4/1962 Tucker 23212X 9/1964 Jahnig 23-2l2 4/ 1966 Ramella 23212 8/1966 Pfcfferle 23-212X 1/1967 Marshall, Jr 23-212 5/ 1967 Paterson 23212-X 1/ 1968 Johnson et al. 23-212X 5/1968 Cromeans 23--212 6/1968 Habermehl et al. 23-212X FOREIGN PATENTS 1/ 1961 Great Britain 260672 EDWARD STERN, Primary Examiner US. Cl. X.R.

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US3988425 *Jul 30, 1974Oct 26, 1976Metallgesellschaft AktiengesellschaftProcess of producing carbon monoxide from light hydrocarbons
US4076612 *Dec 9, 1974Feb 28, 1978Rio Tinto (Rhodesia) LimitedProcess for obtaining liquid fuel-oil and/or gaseous hydrocarbons from solid carbonaceous feed stocks
US6783877Aug 17, 2001Aug 31, 2004Toyota Jidosha Kabushiki KaishaFuel reforming apparatus
US7479217Dec 14, 2005Jan 20, 2009Institut Francais Du PetroleIn a slurry or an ebullated bed, catalytic hydroconversion of a hydrocarbon phase and H2-containing vapor phase hydrocarbons heavier than methane; pre-reforming the product stream to produce H2 and methane; steam reforming the product to convert methane to hydrogen; recycling H2 to first upstream process
US7687048Sep 28, 2006Mar 30, 2010Uop LlcAmine treatment in light olefin processing
US7732499Jan 27, 2009Jun 8, 2010Acetex (Cyprus) LimitedMethanol is reacted with oxygen to produce a syngas stream; syngas stream is separated into a carbon dioxide rich stream and a mixed stream containing hydrogen/carbon monoxide; mixed stream is separated into a hydrogen-rich stream and a carbon monoxide-rich stream; vaporization
US7737317Sep 28, 2006Jun 15, 2010Uop Llc.Separation and recovery of such light olefins as ethylene and propylene from such fluid catalytic cracking of heavy petroleum feedstock; processing effluent using zeolite catalysts having large- and medium-sized pores; separating liquid/gas; gasoline, light/heavy cycle oil, clarified oil
US7973209Sep 28, 2006Jul 5, 2011Uop LlcFractionation recovery processing of light olefins free of carbon dioxide
US8043600Aug 11, 2009Oct 25, 2011Haldor Topsøe A/SHydrotreatment process
CN101517041BSep 27, 2007Dec 12, 2012环球油品公司Absorption recovery processing of fcc-produced light olefins
CN101676367BSep 4, 2009Nov 27, 2013赫多特普索化工设备公司Improved hydrotreatment process
EP1188712A2 *Aug 23, 2001Mar 20, 2002Toyota Jidosha Kabushiki KaishaFuel reforming apparatus
WO2002014215A2 *Aug 17, 2001Feb 21, 2002Aral Ag & Co KgMembrane reactor and method for the production of highly pure hydrogen gas
WO2003097523A2 *May 20, 2003Nov 27, 2003Acetex Cyprus LtdIntegrated process for making acetic acid and methanol
WO2006064100A1 *Nov 29, 2005Jun 22, 2006Inst Francais Du PetroleSequence of hydroconversion and vapour reforming processes to optimize hydrogen production on production fields
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Classifications
U.S. Classification423/654, 423/437.1, 423/229, 252/373
International ClassificationC10G47/00, C01B3/48, C01B3/16
Cooperative ClassificationC01B2203/0475, C01B3/16, C01B2203/1052, C01B2203/1247, C01B2203/0233, C01B3/48, C01B2203/1258, C01B2203/1041, C01B2203/0283, C01B2203/148, C01B2203/1082, C01B2203/1047, C01B2203/1076, C01B2203/0415, C10G2400/26
European ClassificationC01B3/48, C01B3/16