US3744981A - Steam reforming of hydrocarbons - Google Patents

Steam reforming of hydrocarbons Download PDF

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Publication number
US3744981A
US3744981A US00137495A US3744981DA US3744981A US 3744981 A US3744981 A US 3744981A US 00137495 A US00137495 A US 00137495A US 3744981D A US3744981D A US 3744981DA US 3744981 A US3744981 A US 3744981A
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United States
Prior art keywords
reaction zone
steam
steam reforming
product
methane
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Expired - Lifetime
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US00137495A
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English (en)
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D Ward
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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Assigned to UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP reassignment UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KATALISTIKS INTERNATIONAL, INC., A CORP. OF MD
Assigned to UOP, A GENERAL PARTNERSHIP OF NY reassignment UOP, A GENERAL PARTNERSHIP OF NY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UOP INC.
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • 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
    • C10G2400/26—Fuel gas

Definitions

  • the present invention involves the reforming of hydrocarbonaceous material, in the presence of steam, to produce lower-boiling products. More specically, the present invention is directed toward hydrocarbon steam reforming to produce a methane-rich gaseous product particularly well suited for utilization as a synthetic natural gas (SNG), often referred to as Town Gas.
  • SNG synthetic natural gas
  • the process is effected catalytically, preferably utilizing a fixed-bed reaction zone through which the various reactants are passed.
  • a principal object of the present invention is to improve the efficiency of a process for effecting the steam reforming of hydrocarbons.
  • a corollary objective resides in extending the period of time during which the process functions acceptably and economically.
  • Another object of my invention is to provide a processing technique which decreases the extent to which carbon becomes deposited on the catalyst employed in a hydrocarbon steam reforming process.
  • the present invention involves a steam reforming process which comprises reacting a hydrocarbon and steam, in a first reaction zone, at steam reforming conditions; further reacting a portion of the resulting first zone etiluent, in a second reaction at hydrogen-producing conditions; and, recycling the resulting second zone effluent to said rst reaction zone.
  • a more limited embodiment of my invention is directed toward a steam reforming process which comprises reacting steam and a normally liquid naphtha charge stock, in a first reaction zone, at conditions seletced to convert said charge stock into methane, including a temperature in the range of about 800 F. to about 1100 F.; further reacting a portion of the resulting first zone eiiluent in a second reaction zone, at hydrogen-producing conditions including a temperature from l F. to about 1500 F.; recycling the resulting second zone eliluent to said first reaction zone; and, recovering a methane-rich product from the remaining portion of said first zone eiiluent.
  • steam is introduced into said second reaction zone in admixture with the portion of the first zone eiiluent.
  • the present invention encompasses a process for the catalytic conversion of hydrocarbons through the reforming thereof in the presence of steam.
  • the principal function of the present process is the production of normally gaseous material, and particularly a methane-rich end product.
  • Suitable charge stocks, from which high yields of methane will be obtained include normally gaseous components such as ethane, propane and butane; a normally liquid light naphtha having an end boiling point in the range of about 250 to about 300 F.; and a normally liquid heavy naphtha having an initial lboiling point of about 250 to about 300 F. and an end -boiling point of about 400 F. to about 450 F.
  • Another suitable charge stock would be a mixture of both normally gaseous and normally liquid componentseg a light straight-run naphtha containing, ethane, propane and butane.
  • suitable steam reforming catalytic composites are sensitive to the presence of sulfurous compounds in the charge stock, and are knovvn to deactivate rapidly as a result.
  • charge stock to the present process hasl previously been subjected to some form of hydrotreating, or hydrorefining in order to convert the sulfurous compounds into hydrogen sulfide and hydrocarbons, and that the resulting hydrogen sulfide has been removed prior to being charged to the present process.
  • suitable charge stocks for the present process should contain less than about 25 ppm. by weight of sulfurous compounds, and preferably less than about 10.0 ppm., calculated as elemental sulfur.
  • One particular suitable hydrorening pretreatment involves the use of a cobalt-molybdenum catalyst at a maximum catalyst bed temperature in the range of 600 F. to about 850 F.
  • Other operating conditions include a pressure of from 250 p.s.i.g. to about 1500 p.s.i.g., a liquid hourly space velocity of 0.1 to about 10.0 and a hydrogen concentration of about 100 to about 1500 s.c.f./ bbl.
  • the resulting hydrogen sulfide may be removed in any suitable manner including stripping, adsorption over a zinc oxide adsorbent, etc.
  • the hydrorefining pretreatment forms no essential part of my invention, and any suitable technique for reducing the sulfur content to less than about 25.0 ppm. by Weight will suffice.
  • the substantially sulfur-free charge stock is admixed with steam in an amount to result in a steam/carbon ratio in the range of about 1.1 to about 6.0, and preferably from about 1.3 to about 4.0.
  • the mixture is passed into a steam reforming reaction zone at a temperature such that the maximum catalyst bed temperature is in the range of about 800 F. to about 1100 F., and preferably from about 825 F. to about 1000"' F.
  • the steam reforming reactions will be effected at an imposed pressure in the range of about 250 p.s.i.g. to about 1500 p.s.i.g., and preferably from about 400 p.s.i.g. to about 1000 p.s.i.g.
  • Suitable refractory inorganic oxides material includes kieselguhr, kaolin, attapulgus clay, alumina, silica, zirconia, hafnia, boria, etc., and mixtures thereof.
  • One particularly suitable and preferred steam reforming catalyst is that described n U.S. Pat. No. 3,429,680 (Cl. 48-214), which catalyst utilizes a carrier material of kieselguhr and a catalytically active nickel component promoted through the use of a copper-chromium, or copper-chromium-man- Iganese complex, and may, or may not be further promoted by the addition of an alkaline-earth metal ⁇ oxide.
  • reaction zone product eiuent principally comprising methane, carbon monoxide, carbon dioxide, hydrogen and steam is cooled to a temperature in the range of about 400 F. to about 800 F., preferably with an upper limit of about 650 F.
  • a portion of the cooled product effluent generally from about 3.0 mol percent to about 50.0 mol percent, and preferably up to about 20.0 mol percent, is diverted to a second reaction zone functioning at substantially the same pressure, but at an elevated temperature in the range of about 1100 F. to about 1500 F.
  • up to about 50.0% of steam is admixed with the portion of the eiuent being diverted to the second reaction zone.
  • the catalytic composite in the second zone may be the same as that disposed in the first reaction zone, and is generally selected from those catalysts hereinbefore described.
  • the catalyst used in the hydrogen-producing reaction zone is an iron-group metal component combined with a refractory inorganic oxide such as a composite of alumina and silica.
  • hydrogen-producing reactions are effected with the result that the hydrogen concentration is increased from a level of about 20.0 mol percent to a level in the range of from about 40.0 mol percent to about 60.0 mol percent, on an essentially dry basis.
  • the hydrogen-enriched gaseous phase is then recycled to combine with the charge to the initial reaction zone.
  • a methane-rich gas is separated and recovered from the remaining portion of the lirst reaction zone eluent.
  • a particularly preferred system for recovering the desired end product is that shown in the accompanying drawing.
  • the drawing will be described in conjunction with a commercially-scaled unit designed to process approximately 6,273 bbls./day of the light straight-run naphtha.
  • the charge stock contains 221 barrels per day of propane, 607 barrels per day of butanes, 1,280 barrels per day of pentanes and 4,165 barrels per day of hexanes and heavier normally liquid hydrocarbons.
  • the charge stock enters the process through line 1, and is admixed therein with 6,910 mols/hr. of steam, from line 2, resulting in a steam to carbon ratio of 1.6.
  • the mixture continues through line 1 into heater 3, wherein the temperature is raised to a level such that the temperature at the inlet to the reactor is about 930 F.
  • Reactor 6 contains about 1,010 cubic feet of a catalytic composite having an apparent bulk density of about 0.98 gram per cc.
  • the catalyst comprises a carrier material of kieselguhr, about 38.0% by weight of a nickel component (calculated as elemental nickel), about 9.0% by weight of magnesium oxide and about 7.5% by weight of a copper-chromium-manganese component in which the mol ratio of copper to chromium to manganese is 1.0: 1,010.1.
  • the pressure imposed upon reactor 6 is about 590 p.s.i.g., as measured at the inlet thereto.
  • the product efiiuent from reaction zone 6 is Withdrawn by way of line 7 and introduced into condenser 8, wherein the temperature is reduced to a level of about 520 F., the cooled eiuent being withdrawn by way of line 9.
  • the total product etiluent from reaction zone 6 has the approximate composition indicated in the following Table I:
  • reactor 27 has disposed therein a catalytic composite of 15.0% iron, calculated as the element, combined with a composite of 63.0% alumina and 37.0% by Weight of silica.
  • the effluent from reactor 27 is withdrawn by way of line 5 and recycled to combine with the heated charge stock and steam in line 4.
  • the cooled eiiiuent is introduced via line 17 into a suitable separator 1.0, from which condensed Water is removed from the process by way of line 19.
  • the eiiiuent from shift converter i4 now substantially free from water, is introduced by Way of line Z0 into carbon dioxide removal system 2l. Carbon dioxide is removed via line 22, while a methane-rich product gas is recovered in line 23.
  • steam is diverted from line 2 through line 23, to combine with the iirst zone eflluent in line 24.
  • about 20.0% of steam, based upon the fresh feed in line 1, is so diverted.
  • the removal of carbon dioxide in system 21 may be effected in any manner Well-known to the prior art.
  • One such conventional manner involves mono-ethanolamine adsorption.
  • Another adsorption scheme utilizes hot potassium carbonate, while another suitable technique employs a catalytic reaction system utilizing vanadium pentoxide as the catalyst.
  • the final methane-rich gaseous product in line 23 has the composition indicated in the following Table
  • the principal advantage to be obtained through the utilization of the present invention stems from the increase in molecular hydrogen concentration in the total charge to gasification reactor 6.
  • the effective catalyst life expressed as barrels of normally liquid charge stock per pound of catalyst disposed in the reaction zone, will be increased from 25.0% to about 45.0%.
  • Other advantages include a smaller charge heater 3, signjiicantly more ethcient overall heat utilization and a more isothermal gasification reactor.
  • a method for producing a methane-rich gaseous product which comprises reacting a normally vaporous or normally liquid hydrocarbon charge stock and steam, in a rst catalytic reaction zone, at conditions selected to convert the charge stock ⁇ into methane; further reacting a portion of the resulting iirst zone etliuent, in a second catalytic reaction zone, at hydrogen-producing conditions; and, recycling the resulting second zone eiiiuent to said first reaction zone; and, recovering a methanerich product from the remaining portion of said first zone eiiiuent.
  • said steam reforming conditions include a temperature in the range of about 800 F. to about 1,025 F., a pressure from 250 p.s.i.g. to about 1,500 p.s.i.g ⁇ and a steam/ carbon ratio from about 1.1 to about 6.0.
  • a method for producing a methane-rich gaseous product which comprises reacting steam and a normally liquid naphtha charge stock, in a first catalytic reaction zone, at conditions selected to convert said charge stock into methane, including a temperature in the range of 800 F. to about ll00 F.; further reacting a portion of the resulting first zone effluent, in a second catalytic reaction zone, at hydrogen-producing conditions including a temperature from '1,100 F. to about 1,500" F.; recycling the resulting second zone eiiiuent to said first reaction zone; and, recovering a methane-rich product from the remaining portion of said tirst zone etiiuent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US00137495A 1971-04-26 1971-04-26 Steam reforming of hydrocarbons Expired - Lifetime US3744981A (en)

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US13749571A 1971-04-26 1971-04-26

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US (1) US3744981A (ja)
AT (1) AT357256B (ja)
AU (1) AU459133B2 (ja)
BE (1) BE782300A (ja)
BG (1) BG25652A3 (ja)
BR (1) BR7202552D0 (ja)
CA (1) CA960460A (ja)
CS (1) CS167980B2 (ja)
DD (1) DD98533A5 (ja)
DE (1) DE2219949B2 (ja)
EG (1) EG10931A (ja)
ES (1) ES401940A1 (ja)
FI (1) FI55046C (ja)
FR (1) FR2134471B1 (ja)
GB (1) GB1379498A (ja)
HU (1) HU167538B (ja)
IL (1) IL39255A (ja)
IT (1) IT952766B (ja)
NL (1) NL7205538A (ja)
NO (1) NO136463C (ja)
PH (1) PH9982A (ja)
PL (1) PL84598B1 (ja)
RO (1) RO64680A (ja)
SE (1) SE387100B (ja)
SU (1) SU434660A3 (ja)
YU (1) YU35374B (ja)
ZA (1) ZA722626B (ja)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882636A (en) * 1971-10-07 1975-05-13 Japan Gasoline Two-stage steam reforming process of hydrocarbons
US3904744A (en) * 1973-10-01 1975-09-09 Exxon Research Engineering Co Process for the production of hydrogen-containing gases
US3917467A (en) * 1972-01-14 1975-11-04 Japan Gasoline Process for manufacturing high purity methane gas
US3928002A (en) * 1972-11-28 1975-12-23 Japan Gasoline Low-temperature steam reforming process for hydrocarbons
US3992166A (en) * 1972-12-28 1976-11-16 Japan Gasoline Co., Ltd. Low temperature steam reforming process for hydrocarbons
US4000987A (en) * 1973-02-03 1977-01-04 Japan Gasoline Co., Ltd. Low-temperature steam reforming process for hydrocarbons
US4000988A (en) * 1973-06-20 1977-01-04 Japan Gasoline Co., Ltd. Low-temperature steam reforming process for hydrocarbons
US4160649A (en) * 1978-08-25 1979-07-10 Uop Inc. Substituted natural gas via steam reforming of kerosene
US20060207166A1 (en) * 2005-03-21 2006-09-21 Ben-Gurion University Of The Negev Research & Development Authority Production of diesel fuel from vegetable and animal oils
CN102762701A (zh) * 2010-01-05 2012-10-31 约翰森·马瑟公开有限公司 处理天然气的装置和方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1392474A (fr) * 1963-08-02 1965-03-19 Gas Council Procédé de préparation de mélanges gazeux à partir d'un distillat de pétrole
NL6804705A (ja) * 1967-04-03 1968-10-04

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882636A (en) * 1971-10-07 1975-05-13 Japan Gasoline Two-stage steam reforming process of hydrocarbons
US3917467A (en) * 1972-01-14 1975-11-04 Japan Gasoline Process for manufacturing high purity methane gas
US3928002A (en) * 1972-11-28 1975-12-23 Japan Gasoline Low-temperature steam reforming process for hydrocarbons
US3992166A (en) * 1972-12-28 1976-11-16 Japan Gasoline Co., Ltd. Low temperature steam reforming process for hydrocarbons
US4000987A (en) * 1973-02-03 1977-01-04 Japan Gasoline Co., Ltd. Low-temperature steam reforming process for hydrocarbons
US4000988A (en) * 1973-06-20 1977-01-04 Japan Gasoline Co., Ltd. Low-temperature steam reforming process for hydrocarbons
US3904744A (en) * 1973-10-01 1975-09-09 Exxon Research Engineering Co Process for the production of hydrogen-containing gases
US4160649A (en) * 1978-08-25 1979-07-10 Uop Inc. Substituted natural gas via steam reforming of kerosene
US20060207166A1 (en) * 2005-03-21 2006-09-21 Ben-Gurion University Of The Negev Research & Development Authority Production of diesel fuel from vegetable and animal oils
US8142527B2 (en) * 2005-03-21 2012-03-27 Ben-Gurion University Of The Negev Research And Development Authority Production of diesel fuel from vegetable and animal oils
CN102762701A (zh) * 2010-01-05 2012-10-31 约翰森·马瑟公开有限公司 处理天然气的装置和方法
US9284236B2 (en) 2010-01-05 2016-03-15 Johnson Matthey Plc Apparatus and process for treating natural gas
US10010858B2 (en) 2010-01-05 2018-07-03 Johnson Matthey Plc Apparatus and process for treating natural gas

Also Published As

Publication number Publication date
DE2219949B2 (de) 1979-07-12
YU108372A (en) 1980-06-30
SE387100B (sv) 1976-08-30
FR2134471A1 (ja) 1972-12-08
DD98533A5 (ja) 1973-06-20
CA960460A (en) 1975-01-07
FI55046B (fi) 1979-01-31
GB1379498A (en) 1975-01-02
NO136463B (ja) 1977-05-31
PL84598B1 (ja) 1976-04-30
CS167980B2 (ja) 1976-05-28
IT952766B (it) 1973-07-30
HU167538B (ja) 1975-10-28
BE782300A (fr) 1972-08-16
NO136463C (no) 1977-09-07
ZA722626B (en) 1973-01-31
BR7202552D0 (pt) 1973-05-24
PH9982A (en) 1976-07-13
AU459133B2 (en) 1975-03-20
IL39255A0 (en) 1972-06-28
IL39255A (en) 1975-05-22
AT357256B (de) 1980-06-25
ES401940A1 (es) 1975-03-01
SU434660A3 (ru) 1974-06-30
NL7205538A (ja) 1972-10-30
BG25652A3 (bg) 1978-11-10
ATA360472A (de) 1979-11-15
AU4153772A (en) 1973-11-01
RO64680A (ro) 1980-01-15
FR2134471B1 (ja) 1974-07-26
EG10931A (en) 1976-10-31
YU35374B (en) 1980-12-31
FI55046C (fi) 1979-05-10
DE2219949A1 (de) 1972-11-16

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