US3469946A - Apparatus for high-temperature conversions - Google Patents

Apparatus for high-temperature conversions Download PDF

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US3469946A
US3469946A US484414A US3469946DA US3469946A US 3469946 A US3469946 A US 3469946A US 484414 A US484414 A US 484414A US 3469946D A US3469946D A US 3469946DA US 3469946 A US3469946 A US 3469946A
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heat
furnace
air
combustion
temperature
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US484414A
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Peter Von Wiesenthal
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Linde GmbH
Alcorn Combustion Co
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Alcorn Combustion Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00Reforming naphtha
    • C10G35/04Catalytic reforming
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/062Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/384Production 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 the catalyst being continuously externally heated
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18Apparatus
    • C10G9/20Tube furnaces
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S165/00Heat exchange
    • Y10S165/905Materials of manufacture

Definitions

  • a number of commercially important endothermal conversions proceed at appreciable speeds only when elevated temperatures are reached.
  • the steam pyrolysis of vaporous hydrocarbons to produce olefins is normally conducted at temperatures of 1100 to 1600 F.
  • Catalytic reforming in the presence of hydrogen to improve octane normally proceeds at temperatures in the vicinity of 900 F.
  • temperatures in excess of 1000 F. are normally required. Since each of these processes are endothermal and occur at appreciable rates only with elevated temperatures, tubular furnaces can be used to add heat continuously to the reactants in the tubes thereby maintaining or increasing these temperatures while the reactions proceed.
  • tubular furnaces to carry out high-temperature conversions as practiced heretofore has occasioned some diflicultties as can be illustrated by consideration of typical conditions employed in a furnace in which catalytic steam reforming of methane to produce hydrogen and carbon monoxide is conducted.
  • a light hydrocarbon is preheated to a temperature of about 1000 F. and is introduced together with steam into catalyst-packed, vertical tubes disposed in the furnace chamber to be heated by burning a fuel.
  • tube wall temperatures above 1600" F. are maintained and the hot combustion products leave the furnace chamber at about 2100 F.
  • the efficiency of the furnace is only about 40% from the standpoint of utilization in the reaction of the heat released by the combustion of the fuel.
  • the hot combustion products from the furnace chamber are flowed through a convection section of the furnace to preheat the gas feed and to generate steam. Thereafter the combustion products are vented via a stack.
  • steam must generally be the principal source of power in the associated plant thereby precluding in some instances the use of electric motors for pumps, compressors, etc. Where large supplies of steam are not needed the operation of reformer furnaces for hydrogen 3,469,946 Patented Sept. 30, 1969 ice production has frequently been deemed commercially impractical.
  • the present invention uses a heat-transfer fluid in a combustion-air-preheating system to step up furnace efficiency.
  • the heat-transfer fluid receives heat in a convection section of the furnace.
  • the heat-transfer fluid is easily piped to the vicinity of the burners where it gives up its heat to incoming combustion air.
  • furnace chambers can be reduced in size by from ten to thirty percent and fuel requirements are reduced.
  • FIGURE I is an elevation view in section of a reformer furnace according to this invention.
  • FIGURE II is a schematic flow diagram depicting a heat-transfer system in accordance with this invention.
  • a heat-transfer fluid stored in drum 1 is circulated by pump 2 via line 3 to convection coil 4 for heating.
  • the heated fluid is circulated via line 6 through air-preheat coils 7 and is returned by means of pump 8 to drum 1.
  • Heat-transfer fluids for the service here contemplated may be selected from among readily available commercial products such as eutectic mixtures of potassium and sodium salts, eutectic mixtures of diphenyl and diphenyloxide, o-dichlorobenzene, aromatic heat transfer oils tetrachlorobiphenyl compounds and the like. Information on the selection and application of these heat transfer fluids is contained in such publications as Aromatic Heat Transfer Oils, a technical bulletin of Socony Mobil Oil Company, Dowtherm Handbook, Form -276-60 by Dow Chemical Company; Hitec Heat Transfer Salt, Bulletin A-15821 of E. I. Du Pont de Nemours & Co., Inc. and Therminol Fluid Heat Systems by Monsanto Company. Some of the design criteria which must be considered in the selection of a suitable fluid include cost, operating temperature ranges, freezing point, toxicity and stability.
  • a hydrocarbon such as methane or propane
  • a suitable oxidant such as H 0 and/ or CO
  • inlet manifolds 9 a hydrocarbon (such as methane or propane) along with a suitable oxidant such as H 0 and/ or CO is coursed downward from inlet manifolds 9 through furnace tubes 11' which are filled with a granular catalyst such as nickel oxide to outlet manifolds 12 all in a manner well known to those familiar with the art.
  • elongated settings 14 are provided with side walls 16 which are relatively close to tubes 11.
  • Linear burners 17 are arranged in elongated troughs made of tile and disposed along side walls 16 so that the combustion gases from these burners wash side walls 16 to heat them to uniform incandescence so that substantially the entire surfaces of these side walls act as heating elements,
  • a furnace suitable for a high-tempreature endothermal reaction comprising an elongated box-like setting having parallel side walls and enclosing a furnace chamber therein,
  • the setting defining a plurality of air-inlet passages communicating in flow series with the source of air to receive combustion air therefrom,
  • a plurality of linear burners each operatively connected with the source of fuel and positioned in one of the air-inlet passages and arranged along both of the side walls in at least two tiers thereof for heating said side walls to incandescence and for supplying hot combustion gases to the furnace chamber,
  • the setting defining a convection section arranged to receive the combustion gases from the furnace chamber
  • At least one air-preheat coil mounted in the air-inlet passage

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Description

P 1969 P. VON WIESENTHAL 3,469,946
APPARATUS FOR HIGH-TEMPERATURE CONVERSIONS Filed Sept. 1, 1965 INVENT'OR.
PETER VMWIESENTHAL ATTORNEY United States Patent 3,469,946 APPARATUS FOR HIGH-TEMPERATURE CONVERSIONS Peter von Wiesenthal, New York, N .Y., assignor to Alcorn Combustion Company, New York, N.Y., a corporation of Delaware Filed Sept. 1, 1965, Ser. No. 484,414 Int. Cl. Blj 9/04; F23l 9/00 US. Cl. 23-277 1 Claim ABSTRACT OF THE DISCLOSURE This disclosure contemplates high-temperature endothermal conversions. The invention resides in a tube furnace and related process by which high efficiency for such reactions is attained.
A number of commercially important endothermal conversions proceed at appreciable speeds only when elevated temperatures are reached. For example, the steam pyrolysis of vaporous hydrocarbons to produce olefins is normally conducted at temperatures of 1100 to 1600 F. Catalytic reforming in the presence of hydrogen to improve octane normally proceeds at temperatures in the vicinity of 900 F. In the case of catalytic steam reforming of hydrocarbons to produce hydrogen and carbon monoxide, temperatures in excess of 1000 F. are normally required. Since each of these processes are endothermal and occur at appreciable rates only with elevated temperatures, tubular furnaces can be used to add heat continuously to the reactants in the tubes thereby maintaining or increasing these temperatures while the reactions proceed.
Unfortunately, however, the use of tubular furnaces to carry out high-temperature conversions as practiced heretofore has occasioned some diflicultties as can be illustrated by consideration of typical conditions employed in a furnace in which catalytic steam reforming of methane to produce hydrogen and carbon monoxide is conducted. Typically, a light hydrocarbon is preheated to a temperature of about 1000 F. and is introduced together with steam into catalyst-packed, vertical tubes disposed in the furnace chamber to be heated by burning a fuel. In order to supply the heat of reaction and to attain an outlet temperature in excess of 1500 F., tube wall temperatures above 1600" F. are maintained and the hot combustion products leave the furnace chamber at about 2100 F. Under these conditions the efficiency of the furnace is only about 40% from the standpoint of utilization in the reaction of the heat released by the combustion of the fuel. To obtain reasonable efficiency, the hot combustion products from the furnace chamber are flowed through a convection section of the furnace to preheat the gas feed and to generate steam. Thereafter the combustion products are vented via a stack. To make use of the steam thus generated, steam must generally be the principal source of power in the associated plant thereby precluding in some instances the use of electric motors for pumps, compressors, etc. Where large supplies of steam are not needed the operation of reformer furnaces for hydrogen 3,469,946 Patented Sept. 30, 1969 ice production has frequently been deemed commercially impractical.
Another approach toward improving thermal efficiency was to recycle combustion gases in order to preheat combustion air. This approach was frustrated by cumbersome and expensive ductwork. Even when a regenerativetype air preheater was considered, the ductwork still was elaborate.
The present invention uses a heat-transfer fluid in a combustion-air-preheating system to step up furnace efficiency. The heat-transfer fluid receives heat in a convection section of the furnace. The heat-transfer fluid is easily piped to the vicinity of the burners where it gives up its heat to incoming combustion air. By this expedient ductwork is practically avoided, furnace chambers can be reduced in size by from ten to thirty percent and fuel requirements are reduced.
These and other features will appear more fully from the accompanying drawings wherein:
FIGURE I is an elevation view in section of a reformer furnace according to this invention.
FIGURE II is a schematic flow diagram depicting a heat-transfer system in accordance with this invention.
As best seen in FIGURE II, a heat-transfer fluid stored in drum 1 is circulated by pump 2 via line 3 to convection coil 4 for heating. The heated fluid is circulated via line 6 through air-preheat coils 7 and is returned by means of pump 8 to drum 1.
Heat-transfer fluids for the service here contemplated may be selected from among readily available commercial products such as eutectic mixtures of potassium and sodium salts, eutectic mixtures of diphenyl and diphenyloxide, o-dichlorobenzene, aromatic heat transfer oils tetrachlorobiphenyl compounds and the like. Information on the selection and application of these heat transfer fluids is contained in such publications as Aromatic Heat Transfer Oils, a technical bulletin of Socony Mobil Oil Company, Dowtherm Handbook, Form -276-60 by Dow Chemical Company; Hitec Heat Transfer Salt, Bulletin A-15821 of E. I. Du Pont de Nemours & Co., Inc. and Therminol Fluid Heat Systems by Monsanto Company. Some of the design criteria which must be considered in the selection of a suitable fluid include cost, operating temperature ranges, freezing point, toxicity and stability.
To produce a mixture of H and CO in the furnace shown in FIGURE I, a hydrocarbon (such as methane or propane) along with a suitable oxidant such as H 0 and/ or CO is coursed downward from inlet manifolds 9 through furnace tubes 11' which are filled with a granular catalyst such as nickel oxide to outlet manifolds 12 all in a manner well known to those familiar with the art.
Temperatures in excess of 2000" F. are desirable in furnace chamber 13. Toward this objective elongated settings 14 are provided with side walls 16 which are relatively close to tubes 11. Linear burners 17 are arranged in elongated troughs made of tile and disposed along side walls 16 so that the combustion gases from these burners wash side walls 16 to heat them to uniform incandescence so that substantially the entire surfaces of these side walls act as heating elements,
It is important that impingement of flames onto catalyst filled tubes 11 be avoided, so combustion of the gaseous fuel is contained from burner tips 19 to the upper extents 21 of troughs 18.
At the heart of this invention is the recovery of heat from combustion gases for use in air preheating. Combustion gases are drawn from furnace chamber 13 through convection section 22 and are subsequently vented through stack 23 all by means of induced draft fan 24. Convection coil 4 serves to raise the temperature of the heat- It will be understood by those skilled in furnace design that wide deviations may be made from the shown embodiment without departing from the main spirit of invention as set forth in the claims.
What is claimed is: 1. A furnace suitable for a high-tempreature endothermal reaction and comprising an elongated box-like setting having parallel side walls and enclosing a furnace chamber therein,
a source of fuel and a source of air,
the setting defining a plurality of air-inlet passages communicating in flow series with the source of air to receive combustion air therefrom,
a plurality of linear burners each operatively connected with the source of fuel and positioned in one of the air-inlet passages and arranged along both of the side walls in at least two tiers thereof for heating said side walls to incandescence and for supplying hot combustion gases to the furnace chamber,
at least one row of furnace tubes mounted in the furnace chamber approximately midway between the side walls,
means for coursing a hydrocarbon stream through at least one of the furnace tubes for noncontact heating by the combustion gases,
the setting defining a convection section arranged to receive the combustion gases from the furnace chamber,
at least one convection coil mounted in the convectionsection,
at least one air-preheat coil mounted in the air-inlet passage,
means for circulating a heat-transfer liquid in turn through the convection coil and then through the airpreheat coil.
References Cited UNITED STATES PATENTS 1,833,130 11/1931 Roe. 3,119,671 1/1964 Koniewiez 23277 3,129,065 4/1964 Koniewiez 23-277 3,240,204 3/ 1966 Wiesenthal 122-356 FOREIGN PATENTS 299,436 1930 Great Britain.
JAMES H. TAYMAN, J R., Primary Examiner US. Cl. X.R.
US484414A 1965-09-01 1965-09-01 Apparatus for high-temperature conversions Expired - Lifetime US3469946A (en)

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US48441465A 1965-09-01 1965-09-01
DEA0056240 1967-07-11
FR48951A FR1538588A (en) 1965-09-01 1967-07-21 Process and plant for high temperature chemical reactions

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3667429A (en) * 1971-01-25 1972-06-06 Lummus Co Fired heater
US3677234A (en) * 1970-01-19 1972-07-18 Stone & Webster Eng Corp Heating apparatus and process
US4238403A (en) * 1975-03-03 1980-12-09 Imperial Chemical Industries Limited Methanol synthesis process
US4321130A (en) * 1979-12-05 1982-03-23 Exxon Research & Engineering Co. Thermal conversion of hydrocarbons with low energy air preheater
WO1991002195A1 (en) * 1989-07-31 1991-02-21 Exxon Chemical Patents Inc. Natural draft air preheater
US4999089A (en) * 1988-09-30 1991-03-12 Mitsui Engineering & Shipbuilidng Co., Ltd. Cracking furnace
EP0935094A3 (en) * 1998-02-05 2002-01-02 The M. W. Kellogg Company Process furnace

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325916A (en) * 1979-12-31 1982-04-20 Exxon Research & Engineering Co. Reformer furnace seal
US4617109A (en) * 1985-12-23 1986-10-14 The M. W. Kellogg Company Combustion air preheating

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB299436A (en) * 1927-10-26 1929-07-04 Emile Prat Improvements in or relating to apparatus for heating air
US1833130A (en) * 1929-12-09 1931-11-24 Stephen W Borden Air preheater
US3119671A (en) * 1960-09-28 1964-01-28 Chemical Coustruction Corp Upright fluid heating furnace with heat recovery system
US3129065A (en) * 1960-09-14 1964-04-14 Chemical Construction Corp Upright fluid heating furnace with integral heat recovery means
US3240204A (en) * 1964-02-19 1966-03-15 Alcorn Comb Co Pyrolysis heater

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB299436A (en) * 1927-10-26 1929-07-04 Emile Prat Improvements in or relating to apparatus for heating air
US1833130A (en) * 1929-12-09 1931-11-24 Stephen W Borden Air preheater
US3129065A (en) * 1960-09-14 1964-04-14 Chemical Construction Corp Upright fluid heating furnace with integral heat recovery means
US3119671A (en) * 1960-09-28 1964-01-28 Chemical Coustruction Corp Upright fluid heating furnace with heat recovery system
US3240204A (en) * 1964-02-19 1966-03-15 Alcorn Comb Co Pyrolysis heater

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3677234A (en) * 1970-01-19 1972-07-18 Stone & Webster Eng Corp Heating apparatus and process
US3667429A (en) * 1971-01-25 1972-06-06 Lummus Co Fired heater
US4238403A (en) * 1975-03-03 1980-12-09 Imperial Chemical Industries Limited Methanol synthesis process
US4321130A (en) * 1979-12-05 1982-03-23 Exxon Research & Engineering Co. Thermal conversion of hydrocarbons with low energy air preheater
US4999089A (en) * 1988-09-30 1991-03-12 Mitsui Engineering & Shipbuilidng Co., Ltd. Cracking furnace
WO1991002195A1 (en) * 1989-07-31 1991-02-21 Exxon Chemical Patents Inc. Natural draft air preheater
EP0935094A3 (en) * 1998-02-05 2002-01-02 The M. W. Kellogg Company Process furnace

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DE1601152A1 (en) 1970-06-04
FR1538588A (en) 1968-09-06

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