WO2015155256A1 - A process for heating an atr - Google Patents

A process for heating an atr Download PDF

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Publication number
WO2015155256A1
WO2015155256A1 PCT/EP2015/057641 EP2015057641W WO2015155256A1 WO 2015155256 A1 WO2015155256 A1 WO 2015155256A1 EP 2015057641 W EP2015057641 W EP 2015057641W WO 2015155256 A1 WO2015155256 A1 WO 2015155256A1
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WO
WIPO (PCT)
Prior art keywords
atr
process according
process stream
stream
pox
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2015/057641
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French (fr)
Inventor
Per Juul Dahl
Thomas Sandahl Christensen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Priority to BR112016021426-9A priority Critical patent/BR112016021426B1/en
Priority to AU2015243290A priority patent/AU2015243290B2/en
Priority to US15/117,002 priority patent/US10106405B2/en
Priority to EA201691984A priority patent/EA034285B1/en
Priority to CA2941909A priority patent/CA2941909C/en
Priority to MX2016013127A priority patent/MX2016013127A/en
Priority to CN201580017886.3A priority patent/CN106132870A/en
Publication of WO2015155256A1 publication Critical patent/WO2015155256A1/en
Priority to ZA201605309A priority patent/ZA201605309B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using oxygen; using mixtures containing oxygen as gasifying agents
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts with external heating of the catalyst
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D99/00—Subject matter not provided for in other groups of this subclass
    • F27D99/0001—Heating elements or systems
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1604—Starting up the process

Definitions

  • the present invention relates to a process for heating and igniting an ATR or similar reactor.
  • a dedicated start-up (SU) burner has been used to heat-up the ATR reactor to high temperature (i.e. 800-1000°C), which is above the autoigni ⁇ tion temperature at atmospheric pressure before introduc ⁇ tion of the hydrocarbon containing feed stream and the oxygen containing feed stream.
  • the dedicated SU burner must be removed and replaced by a main process burner before the feedstream is introduced.
  • a process for heating an ATR or POX comprising the steps of
  • the process stream is heated prior to being admitted to the ATR/POX reformer and is used to heat the ATR/POX reformer to a desired temperature.
  • the external heating of the process stream can comprise equipment such as tube-and-shell heat-exchanger, fired heater or similar.
  • the SU burner is removed when a desired temperature is achieved. After the SU burner is removed a main burner had to be installed and the system leak tested to make sure that the main burner is properly installed and the system leak tight. Due to the burner change over in known systems the temperature control at the time of ignition is also likely to be less than optimal as the temperature decrease as function of time from the time the SU burner is removed and the temperature may decrease below auto ignition tem ⁇ perature .
  • the process stream contain combustible components and may e.g. be a hydrocarbon feed, hydrocarbon (such as natural gas) and steam mixture, hydrocarbon and steam mixture which has been partial converted in a low temperature reformer, which could be adiabatic, a mixture of hydrocarbons and hy ⁇ drogen, a hydrogen containing stream or a methanol contain- ing stream. Any of the above process streams could contain a mixture of the combustible components and steam and/or C0 2 .
  • the fact that the burner and/or other parts does not need to be changed when proceeding from heating to ignition means that the system can be leak tested under safe and less demanding conditions as it can be done before the heating of the system is initiated. Also the ignition by the present process can be performed at highly controlled parameters e.g. at a specific tempera- ture as there is no change over of burner and/or of the gas used for heating the reactor.
  • no oxygen is flowing as well as the process stream may be flowing isothermally through the combustion chamber as no reaction is taking place as no oxygen is admitted.
  • no premixing of combustibles and oxidant is taking place before introduction into the ATR through the main burner.
  • POX refers to systems where a hydrocarbon feed is combusted together with O 2 via a burner in a reactor at fuel-rich conditions leading to partial combustion of the hydrocar ⁇ bons.
  • ATR refers to systems where combustion e.g. as de ⁇ scribed for the POX is combined with a catalytically re ⁇ forming i.e. where partial oxidation is followed by a cata ⁇ lytic steam reforming over a steam reforming catalyst.
  • the autoignition temperatures may be dependent on a number of parameters, which include but are not limited to the steam/carbon ratio (mole 3 ⁇ 40 /mole C atoms), the content of higher hydrocarbon in the feed gas, the CO 2 and 3 ⁇ 4 content in the feed gas, the content of methanol or other oxygen ⁇ ates in the feed gas, the residence time and/or the operat ⁇ ing pressure in the reactor.
  • autoignition temperature can be dependent on the ratio between oxygen and the hydrocarbon containing feedstream (process stream) when an oxygen feed is admitted to the reactor for mixing with the hydrocarbon containing stream to establish the flame.
  • the process stream is heated in a fired heater and/or heat exchanger and the higher hydrocarbons are converted by means of prereformer
  • the effluent gas from the prereformer can be further heated to high temperature before the ATR reformer.
  • higher hydrocarbons can be removed which changes the limitations on e.g. the temperature range the process stream i.e. the prereformer effluent can be heated to.
  • the prereformer it is possible to heat the process stream to higher temperatures without formation of coke or carbon caused by higher hydrocarbons .
  • the process stream may preferably comprise less than 20% 3 ⁇ 4, such as less than 15% 3 ⁇ 4 or less than 10% 3 ⁇ 4 .
  • a process stream which has been prereformed may comprise less than 20% 3 ⁇ 4, but usually more than 5% 3 ⁇ 4, such as 5 - 15% 3 ⁇ 4.
  • %3 ⁇ 4 is dry mole%, i.e. excl steam partial pressure.
  • the applicant surprisingly has shown that, depending on various factors, more 3 ⁇ 4 is not necessarily preferred in order to achieve optimized ignition.
  • NG natural gas
  • a process without a direct recy ⁇ cle from ATR effluent to the process stream may also result in a relatively low 3 ⁇ 4 concentration in the process stream, such as a 3 ⁇ 4 concentration below 20% e.g. below 10% or be- low 5% H 2 .
  • the process stream is heated to a temperature of 300 to 650°C, preferably over 400°C, for ex ⁇ ample 450 - 600°C or 530 - 580°C.
  • the ATR or POX reactor is heated to a temperature above 300°C such as above 450°C where some preferred embodiments can be achieved.
  • ATR/POX may thus be heated to temperatures in the range 300 to 650°C, for example in the range of 450-600°C, 530 - 580°C or e.g. 470 - 550°C in order to obtain conditions for opti ⁇ mal ignition.
  • the pressure in the ATR or POX reactor can advantageously be increased to 1 - 80 bar, such as at least 10 bar, 12 - 30 bar or 15 - 25 bar at the time of ignition. After ignition the pressure may be elevated to operational pressure. If ignition is carried out at 15 - 25 bar the operational pressure may e.g. be in the range of 25 - 50 bar.
  • the present method can advantageously be carried out in a plant comprising a prereformer and means for heating the process stream to the desired temperatures.
  • the plant fur ⁇ thermore may comprise the ATR/POX reformer with burner and means for admitting the process stream and oxygen prefera ⁇ bly through the main burner.
  • the POX/ATR reformer can be heated to 575°C where after ignition is carried out at a pressure of 20bar. When the ignition is ensured the pressure is raised and the temperature will rise to operation temperature.
  • the tempera ⁇ ture/pressure is outside the curve of soot formation when ignition occurs which means that the system is not taken through a stage with heavy soot formation as the tempera ⁇ ture/pressure is risen to reach operation conditions.
  • parameters within the disclosed temperature ranges preferably of 450 - 600°C and at the elevated pressure ranges may be chosen in order to avoid soot formation during ignition and transition to operation conditions.
  • the process stream admitted through the main burner can be ignited by admitting O 2 via the main burner. This way the process stream and O 2 can be fed to the reformer under controlled conditions. I.e. the ratio between process stream and O 2 can be controlled as well as the flow pattern and mixing of the streams admitted through the burner can be controlled.
  • hydrocarbon feed is preferably pro ⁇
  • the Oxygen/hydrocarbon ratio in the ATR or POX reactor is advantageously 0.05-0.30 Nm 3 /Nm 3 such as 0.1 - 0.25 at ignition and 0.50-0.70 such as approxi ⁇ mately 0.60 during operation.
  • the feed ratio between oxygen and hydrocarbon feed stream flows is calculated before ad ⁇ dition of steam streams. So Oxygen feed flow (Nm3/hr) is before additional burner steam is added and hydrocarbon feed flow is the flow of the hydrocarbon feed flow (Nm3/hr) before feed steam is mixed with the hydrocarbon feed to form the process stream.
  • the hydrocarbon feed can typical be a natural gas after a desulphurization step.
  • the temperature increase (heat of reaction) will be several hundred degree C and the temperature in the ATR reactor combustion chamber will rise from 600°C to 1300-1400°C in short time (within minutes) . This will give a rapid temperature gradient on the refractory lining. If ignition is carried out at Ox/hydrocarbon of 0.05-0.30 the temperature increase will be limited and the stress on re ⁇ actor walls and other hard ware can be reduced compared to ignition at operation ratio (0.50-0.70).
  • the ignition temperature may depend on the Ox/hydrocarbon ratio. As Ox/hydrocarbon ratio is increased ignition temperature is decreased. This means that ignition at e.g. 0.1 Ox/ hydrocarbon ratio is more difficult to obtain than ig ⁇ nition at 0.2. However, the applicant has shown that the advantages of igniting at a lower Ox/ hydrocarbon ratio than traditionally used outweigh the disadvantages.
  • the ATR or POX reactor can also be partly preheated by an inert gas if desired in special setups.
  • Used process streams may for example comprise desulfurized Natural gas and/or prereformed natural gas.
  • composition of the natural gas may vary depending on its origin, but exemplary compositions (mole %) are giv ⁇ en below for a standard NG and a heavy NG. Similarly light NG having a reduced heavy hydrocarbon content compared to the standard NG exists. Standard NG Heavy NG
  • the normal process equipment which preferably include an adiabatic prereformer and a heater e.g. a fired heater (it could also be other type of preheaters for example shell and tube heat exchangers) to heat the process hydro ⁇ carbon feed stream to high temperatures and admit this stream to the ATR reformer through the main process burner with the purpose of heating the ATR reactor to above the autoignition temperature.
  • a heater e.g. a fired heater (it could also be other type of preheaters for example shell and tube heat exchangers) to heat the process hydro ⁇ carbon feed stream to high temperatures and admit this stream to the ATR reformer through the main process burner with the purpose of heating the ATR reactor to above the autoignition temperature.
  • the autoignition temperature of the process streams e.g. hydrocarbon feed streams, like mixtures of natural gas and steam
  • the autoignition temperature of the process streams e.g. hydrocarbon feed streams, like mixtures of natural gas and steam
  • the autoignition temperature is reduced when the pressure in the reformer is elevated dur ⁇ ing ignition.
  • the ignition of the flame in the ATR/POX at pressurized conditions and the fuel rich condi ⁇ tions applied during ignition at preferably 450-600°C or more preferably 530-580°C.
  • the described process enables that the ATR/POX process safely can be started up without a dedicated SU burner or other heating device by using the in-line process heater (s) to heat-up a feed gas containing combustible com ⁇ ponents directly in the heater.
  • the heated process stream is used to heat the downstream ATR/POX reactor to above the autoignition temperature.
  • the present invention provides a meth ⁇ od in which the start-up can be carried out with the actual hydrocarbon process stream without additives such as chemicals with low ignition point.
  • an ATR unit consists of a system for providing feeds to the ATR reactor, a fired heater, a pre- reformer, the ATR reactor itself, and equipment for post- treatment of the product gas.
  • the streams consist of natural gas, steam oxygen and hydro ⁇ gen. All gasses are compressed to the operating pressure and heated to the operating temperature. The natural gas is desulphurized before entering the ATR reactor.
  • a first feed stream contained natural gas, hydrogen and steam. This was heated to a variable tempera- ture in the range 300 to 650°C: A second feed stream con ⁇ tained oxygen and steam. The second stream was heated to approx. 200 °C .
  • the substoichiometric combustion and subsequent catalytic steam reforming and shift reactions are carried out.
  • the inlet and exit gas compositions are measured by gas chromatograph .
  • the tests were successfully carried out to demonstrate that flame ignition can be obtained at low temperature with fuel rich conditions with the configuration described above.
  • the feed stream composition or the operating conditions have been changed and it has been detected if ignition is obtained or not.
  • the first stream I.e. the hy ⁇ drocarbon containing stream is passing the ATR reactor con- tinuously.
  • the hydrocarbon containing stream Before entering the ATR the hydrocarbon containing stream is mixed with steam and heated in a fired heater and then led to an adiabatic prereformer. Prereformer is optional and can be bypassed.
  • the effluent stream from the prere ⁇ former is sent to a separate fired heater section and heat ⁇ ed to a temperature in the range of 300-650°C.
  • the preheated mixture is sent to the ATR reformer and its burner.
  • the hydrocarbon feed mixture may be mixed with a small steam flow which is used to cool the burner .
  • the feed mixture is passing a catalyst bed in which adia- batic steam reforming is taking place and the temperature is decreasing as the steam reforming reactions are endo- thermic .
  • an oxidant stream (mixture of pure 99% oxygen and saturated steam) is introduced to the burner periodi ⁇ cally for short periods. Flame ignition is detected by tem ⁇ perature increase monitored by thermocouples. The feed mix- ture is in the present tests allowed to equilibrate for min 120 seconds. Flame ignition should be detected within this time period.
  • test data is for a case with adiabatic prereformer and the test result show that at 15 bar g the autoignition is obtained for temperatures > 475°C.
  • the applicant has furthermore shown that the ignition tem ⁇ perature decrease with increasing pressure and that the ig ⁇ nition temperature decrease with increased Oxygen/NG ratio.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)

Abstract

The present invention relates to a process for heating an ATR or POX comprising the steps of heating a process stream by at least one heating means, admitting the heated process stream to an ATR or POX reactor through a main burner, and heating the ATR or POX reactor to or above autoignition temperature of the process stream via the heated process stream.

Description

A process for heating an ATR
The present invention relates to a process for heating and igniting an ATR or similar reactor.
Background of the invention
In known ATR or POX systems the reformer must be heated up to a sufficiently high temperature before the hydrocarbon and the oxygen containing feed can safely be admitted to allow autoignition of the combustible feedstream and allow flame propagation.
In traditional ATR reformers a dedicated start-up (SU) burner has been used to heat-up the ATR reactor to high temperature (i.e. 800-1000°C), which is above the autoigni¬ tion temperature at atmospheric pressure before introduc¬ tion of the hydrocarbon containing feed stream and the oxygen containing feed stream. The dedicated SU burner must be removed and replaced by a main process burner before the feedstream is introduced. These known labour intensive work steps are demanding and time consuming as heavy equipment needs to be handled at very high temperatures. Furthermore in the known processes the connecting flanges must be en- sured to be leak tight after the mounting which means that leak test must be carried out also in hot conditions after the main process burner has been mounted.
Thus there is a need for a new process enabling faster and more efficient start-up of ATR/POXs and similar reforming systems . Summary of the invention
In a first aspect of the present invention is provided a process enabling a system and process wherein the dedicated start-up burner can be omitted
In a second aspect of the present is provided a process which minimizes or even eliminates the change of equipment between the heating and ignition of the ATR
In a third aspect of the present invention is provided a process which allows the ATR system to be leak tested in a safe manner in cold condition, These and other advantages are achieved by a process for heating an ATR or POX comprising the steps of
- heating a process stream by at least one heating means,
- admitting the heated process stream to an ATR or POX re¬ actor through a main burner,
- heating the ATR or POX reactor to or above autoignition temperature via the heated process stream. I.e. according to the present process the process stream is heated prior to being admitted to the ATR/POX reformer and is used to heat the ATR/POX reformer to a desired temperature.
The external heating of the process stream can comprise equipment such as tube-and-shell heat-exchanger, fired heater or similar. In known systems where the ATR is heated by a start-up (SU) burner, the SU burner is removed when a desired temperature is achieved. After the SU burner is removed a main burner had to be installed and the system leak tested to make sure that the main burner is properly installed and the system leak tight. Due to the burner change over in known systems the temperature control at the time of ignition is also likely to be less than optimal as the temperature decrease as function of time from the time the SU burner is removed and the temperature may decrease below auto ignition tem¬ perature . As the reactor according to the present process is heated by the process stream entering the reactor through the main burner no parts needs to be removed or changed between the step of heating the ATR and the step of igniting the flame. The process stream contain combustible components and may e.g. be a hydrocarbon feed, hydrocarbon (such as natural gas) and steam mixture, hydrocarbon and steam mixture which has been partial converted in a low temperature reformer, which could be adiabatic, a mixture of hydrocarbons and hy¬ drogen, a hydrogen containing stream or a methanol contain- ing stream. Any of the above process streams could contain a mixture of the combustible components and steam and/or C02.
The fact that the burner and/or other parts does not need to be changed when proceeding from heating to ignition means that the system can be leak tested under safe and less demanding conditions as it can be done before the heating of the system is initiated. Also the ignition by the present process can be performed at highly controlled parameters e.g. at a specific tempera- ture as there is no change over of burner and/or of the gas used for heating the reactor.
Before ignition preferably no oxygen is flowing as well as the process stream may be flowing isothermally through the combustion chamber as no reaction is taking place as no oxygen is admitted.
According to desired embodiments of the present invention no premixing of combustibles and oxidant is taking place before introduction into the ATR through the main burner.
POX refers to systems where a hydrocarbon feed is combusted together with O2 via a burner in a reactor at fuel-rich conditions leading to partial combustion of the hydrocar¬ bons. ATR refers to systems where combustion e.g. as de¬ scribed for the POX is combined with a catalytically re¬ forming i.e. where partial oxidation is followed by a cata¬ lytic steam reforming over a steam reforming catalyst.
The autoignition temperatures may be dependent on a number of parameters, which include but are not limited to the steam/carbon ratio (mole ¾0 /mole C atoms), the content of higher hydrocarbon in the feed gas, the CO2 and ¾ content in the feed gas, the content of methanol or other oxygen¬ ates in the feed gas, the residence time and/or the operat¬ ing pressure in the reactor.
Further the autoignition temperature can be dependent on the ratio between oxygen and the hydrocarbon containing feedstream (process stream) when an oxygen feed is admitted to the reactor for mixing with the hydrocarbon containing stream to establish the flame.
If the process stream is heated in a fired heater and/or heat exchanger and the higher hydrocarbons are converted by means of prereformer several advantages is achieved as the effluent gas from the prereformer can be further heated to high temperature before the ATR reformer. In the prereformer higher hydrocarbons can be removed which changes the limitations on e.g. the temperature range the process stream i.e. the prereformer effluent can be heated to. Thus with the prereformer it is possible to heat the process stream to higher temperatures without formation of coke or carbon caused by higher hydrocarbons .
In the present context higher hydrocarbons are CnHm where n>2, m>4.
The process stream may preferably comprise less than 20% ¾, such as less than 15% ¾ or less than 10% ¾ . For example a process stream which has been prereformed may comprise less than 20% ¾, but usually more than 5% ¾, such as 5 - 15% ¾. %¾ is dry mole%, i.e. excl steam partial pressure. The applicant surprisingly has shown that, depending on various factors, more ¾ is not necessarily preferred in order to achieve optimized ignition. For example it may be preferred to use a process stream comprising less than 10% ¾ such as less than 5% ¾ when the process stream further comprises a natural gas (NG) with higher hydrocarbons. It has for example been shown that it is possible to achieve autoignition of a natural gas which has been desul- furized and thus comprises 2 - 3 % ¾ (added for the desul- furization step) and CI - C5 hydrocarbons which for example is the case if the process stream is not prereformed before admission into the ATR/POX.
In preferred embodiments according to the present applica¬ tion no direct recycle from the ATR effluent to the process stream is used before or during ignition whereby a simple process setup is achieved. A process without a direct recy¬ cle from ATR effluent to the process stream may also result in a relatively low ¾ concentration in the process stream, such as a ¾ concentration below 20% e.g. below 10% or be- low 5% H2.
In various embodiments the process stream is heated to a temperature of 300 to 650°C, preferably over 400°C, for ex¬ ample 450 - 600°C or 530 - 580°C.
By the heated process stream the ATR or POX reactor is heated to a temperature above 300°C such as above 450°C where some preferred embodiments can be achieved. The
ATR/POX may thus be heated to temperatures in the range 300 to 650°C, for example in the range of 450-600°C, 530 - 580°C or e.g. 470 - 550°C in order to obtain conditions for opti¬ mal ignition.
The applicant has shown that ignition of the POX/ATR burner at elevated pressure preferably in the above mentioned tern- perature ranges results in a significantly reduced soot formation .
The pressure in the ATR or POX reactor can advantageously be increased to 1 - 80 bar, such as at least 10 bar, 12 - 30 bar or 15 - 25 bar at the time of ignition. After ignition the pressure may be elevated to operational pressure. If ignition is carried out at 15 - 25 bar the operational pressure may e.g. be in the range of 25 - 50 bar.
The present method can advantageously be carried out in a plant comprising a prereformer and means for heating the process stream to the desired temperatures. The plant fur¬ thermore may comprise the ATR/POX reformer with burner and means for admitting the process stream and oxygen prefera¬ bly through the main burner.
In some embodiments the POX/ATR reformer can be heated to 575°C where after ignition is carried out at a pressure of 20bar. When the ignition is ensured the pressure is raised and the temperature will rise to operation temperature. By these ignition parameters (575°C, 20 bar) the tempera¬ ture/pressure is outside the curve of soot formation when ignition occurs which means that the system is not taken through a stage with heavy soot formation as the tempera¬ ture/pressure is risen to reach operation conditions.
Thus according to the present invention parameters within the disclosed temperature ranges preferably of 450 - 600°C and at the elevated pressure ranges may be chosen in order to avoid soot formation during ignition and transition to operation conditions. According to the present method the process stream admitted through the main burner can be ignited by admitting O2 via the main burner. This way the process stream and O2 can be fed to the reformer under controlled conditions. I.e. the ratio between process stream and O2 can be controlled as well as the flow pattern and mixing of the streams admitted through the burner can be controlled. In the ATR/POX reformer hydrocarbon feed is preferably pro¬ cessed by under-stoichiometric homogeneous combustion (or fuel rich combustion) to syngas in a combustion chamber. Further conversion to syngas takes place by catalytic steam reforming reactions in a fixed bed catalyst bed.
In the present process the Oxygen/hydrocarbon ratio in the ATR or POX reactor is advantageously 0.05-0.30 Nm3/Nm3 such as 0.1 - 0.25 at ignition and 0.50-0.70 such as approxi¬ mately 0.60 during operation. The feed ratio between oxygen and hydrocarbon feed stream flows is calculated before ad¬ dition of steam streams. So Oxygen feed flow (Nm3/hr) is before additional burner steam is added and hydrocarbon feed flow is the flow of the hydrocarbon feed flow (Nm3/hr) before feed steam is mixed with the hydrocarbon feed to form the process stream. The hydrocarbon feed can typical be a natural gas after a desulphurization step.
If the ATR is ignited at an Ox/hydrocarbon ratio of 0.5 - 0.7 Nm3/Nm3 the temperature increase (heat of reaction) will be several hundred degree C and the temperature in the ATR reactor combustion chamber will rise from 600°C to 1300-1400°C in short time (within minutes) . This will give a rapid temperature gradient on the refractory lining. If ignition is carried out at Ox/hydrocarbon of 0.05-0.30 the temperature increase will be limited and the stress on re¬ actor walls and other hard ware can be reduced compared to ignition at operation ratio (0.50-0.70).
The ignition temperature may depend on the Ox/hydrocarbon ratio. As Ox/hydrocarbon ratio is increased ignition temperature is decreased. This means that ignition at e.g. 0.1 Ox/ hydrocarbon ratio is more difficult to obtain than ig¬ nition at 0.2. However, the applicant has shown that the advantages of igniting at a lower Ox/ hydrocarbon ratio than traditionally used outweigh the disadvantages. The ATR or POX reactor can also be partly preheated by an inert gas if desired in special setups.
Used process streams may for example comprise desulfurized Natural gas and/or prereformed natural gas.
The composition of the natural gas (NG) may vary depending on its origin, but exemplary compositions (mole %) are giv¬ en below for a standard NG and a heavy NG. Similarly light NG having a reduced heavy hydrocarbon content compared to the standard NG exists. Standard NG Heavy NG
N2 0.45 0.79
C02 1.20 1.50
CH4 96.36 84.82
C2H6 2.22 6.64
C3H8 0.45 3.55
C4H10 0.23 2.31
C5 and C5+ 0.08 0.91
Table 1
Thus according to the present invention it is possible to use the normal process equipment which preferably include an adiabatic prereformer and a heater e.g. a fired heater (it could also be other type of preheaters for example shell and tube heat exchangers) to heat the process hydro¬ carbon feed stream to high temperatures and admit this stream to the ATR reformer through the main process burner with the purpose of heating the ATR reactor to above the autoignition temperature.
The applicant has shown that the autoignition temperature of the process streams e.g. hydrocarbon feed streams, like mixtures of natural gas and steam, under the right condi¬ tions has autoignition temperatures in substoichiometric or fuel rich conditions that are much lower than the ranges of 800-1000°C which previously has been used. Also it has been shown that the autoignition temperature is reduced when the pressure in the reformer is elevated dur¬ ing ignition. Furthermore the ignition of the flame in the ATR/POX at pressurized conditions and the fuel rich condi¬ tions applied during ignition at preferably 450-600°C or more preferably 530-580°C. It has further been shown that mixtures auto ignited by this process at elevated pressure and temperature in range 300-600°C and with a partial addi¬ tion of oxygen will minimize the soot formation and other formation of organic hydrocarbons during the flame ignition and during the subsequent heat-up to normal operating tem¬ peratures at 1000-1300°C.
In summary the described process enables that the ATR/POX process safely can be started up without a dedicated SU burner or other heating device by using the in-line process heater (s) to heat-up a feed gas containing combustible com¬ ponents directly in the heater. The heated process stream is used to heat the downstream ATR/POX reactor to above the autoignition temperature.
Also according to the invention we can apply the normal feed stream with combustible and avoid using special chemi¬ cals with low ignition point to initiate the flame propaga- tion reactions. I.e. the present invention provides a meth¬ od in which the start-up can be carried out with the actual hydrocarbon process stream without additives such as chemicals with low ignition point.
Example - Start Up (SU) without dedicated SU burner:
In the present example an ATR unit consists of a system for providing feeds to the ATR reactor, a fired heater, a pre- reformer, the ATR reactor itself, and equipment for post- treatment of the product gas.
The streams consist of natural gas, steam oxygen and hydro¬ gen. All gasses are compressed to the operating pressure and heated to the operating temperature. The natural gas is desulphurized before entering the ATR reactor.
In the tests the feeds were combined into two streams and were send to the burner of the ATR. The burner used in the example is described in US patents No. 5,496,170, which by reference is included herein.
A first feed stream (process stream) contained natural gas, hydrogen and steam. This was heated to a variable tempera- ture in the range 300 to 650°C: A second feed stream con¬ tained oxygen and steam. The second stream was heated to approx. 200 °C .
In the ATR reactor, the substoichiometric combustion and subsequent catalytic steam reforming and shift reactions are carried out. The inlet and exit gas compositions are measured by gas chromatograph .
The tests were successfully carried out to demonstrate that flame ignition can be obtained at low temperature with fuel rich conditions with the configuration described above. In each test the feed stream composition or the operating conditions have been changed and it has been detected if ignition is obtained or not. The first stream I.e. the hy¬ drocarbon containing stream is passing the ATR reactor con- tinuously.
Before entering the ATR the hydrocarbon containing stream is mixed with steam and heated in a fired heater and then led to an adiabatic prereformer. Prereformer is optional and can be bypassed. The effluent stream from the prere¬ former is sent to a separate fired heater section and heat¬ ed to a temperature in the range of 300-650°C.
The preheated mixture is sent to the ATR reformer and its burner. At the burner the hydrocarbon feed mixture may be mixed with a small steam flow which is used to cool the burner .
Before ignition no oxygen is flowing and the first stream i.e. the feed mixture (process stream) is flowing isother- mally through the combustion chamber as no reaction is taking place as no oxygen is admitted.
The feed mixture is passing a catalyst bed in which adia- batic steam reforming is taking place and the temperature is decreasing as the steam reforming reactions are endo- thermic .
In the test an oxidant stream (mixture of pure 99% oxygen and saturated steam) is introduced to the burner periodi¬ cally for short periods. Flame ignition is detected by tem¬ perature increase monitored by thermocouples. The feed mix- ture is in the present tests allowed to equilibrate for min 120 seconds. Flame ignition should be detected within this time period.
The test data is for a case with adiabatic prereformer and the test result show that at 15 bar g the autoignition is obtained for temperatures > 475°C.
The applicant has furthermore shown that the ignition tem¬ perature decrease with increasing pressure and that the ig¬ nition temperature decrease with increased Oxygen/NG ratio.
Figure imgf000015_0001
Table 2

Claims

Claims
1. A process for heating an ATR or POX, said process com- prising the steps of
- heating a process stream by at least one heating means ,
- admitting the heated process stream to an ATR or POX reactor through a main burner, and
- heating the ATR or POX reactor to or above autoigni- tion temperature of the process stream via the heated process stream.
. A process according to any of the preceding claims wherein the process stream is heated to a temperature 300 to 650°C, such as 450 - 600°C or 530 - 580°C.
A Process according to any of the preceding claims wherein ignition is established below 650°C.
A process according to any of the preceding claims wherein the ATR or POX reactor is heated to a tempera ture 300 to 650°C, such as 450 - 600°C or 530 - 580°C by means of the heated process stream.
A process according to any of the preceding claims wherein the pressure in the ATR or POX reactor is 1 - 80 bar, 12 - 30 bar or 15 - 25 bar during ignition.
6. A process according to any of the preceding claims comprising the step of admitting O2 via the main burn¬ er to ignite the process stream in the reformer.
A process according to any of the preceding claims wherein the Oxygen is admitted to the ATR or POX vi the main burner when the ATR or POX reactor tempera ture has reached at least autoignition temperature.
A process according to any of the preceding claims wherein the Oxygen/hydrocarbon ratio in the process stream and oxygen feed stream to the ATR or POX reactor is 0.05-0.30 Nm3/Nm3 at ignition and/or 0.50-0.70 Nm3/Nm3 during operation.
9. A process according to any of the preceding claims wherein the ATR or POX reactor is preheated by an in- ert gas.
10. A process according to any of the preceding
claims wherein the process stream comprises a Natural gas comprising C1-C5 hydrocarbons.
A process according to any of the preceding claims wherein the process stream comprises less 20% H2.
A process according to any of the preceding claims wherein the process stream comprises less 10% ¾, preferably less than 5% ¾ .
13. A process according to any of the preceding
claims wherein the process stream comprises steam, 2 - 3% ¾ and Natural Gas comprising CI - C5 hydrocarbons. A process according to any of the preceding claims wherein the process stream e.g. natural gas has been desulfurized, preferably before steam addition. 15. A plant arranged to carry out the process accord¬ ing to any of claims 1 - 14.
An ATR or POX reformer arranged to be preheated and ignited by the process according to claim 1 - 14
PCT/EP2015/057641 2014-04-08 2015-04-08 A process for heating an atr Ceased WO2015155256A1 (en)

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US15/117,002 US10106405B2 (en) 2014-04-08 2015-04-08 Process for heating an ATR
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MX2016013127A MX2016013127A (en) 2014-04-08 2015-04-08 A process for heating an atr.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4174151A1 (en) 2021-10-27 2023-05-03 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Partial oxidation reactor with heating burner for producing synthesis gas

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EP3838841B1 (en) 2019-12-19 2023-11-01 L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude Process for start-up of an autothermal reformer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0936182A2 (en) * 1998-02-13 1999-08-18 Haldor Topsoe A/S Method of soot-free start-up of autothermal reformers
EP1400489A1 (en) * 2002-09-23 2004-03-24 Kellogg Brown & Root, Inc. Process and apparatus for autothermal reforming with recycle of a portion of the produced syngas
US20040081593A1 (en) * 2002-08-17 2004-04-29 Daimlerchrysler Ag Reactor system for hydrogen production
WO2012123100A1 (en) * 2011-03-17 2012-09-20 Thyssenkrupp Uhde Gmbh Method of starting up autothermal reforming reactors
WO2014037201A1 (en) * 2012-09-05 2014-03-13 Haldor Topsøe A/S Method for starting-up a gas to liquid process

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69808521T2 (en) * 1998-07-21 2003-01-30 Haldor Topsoee A/S, Lyngby SYNTHESIS GAS PRODUCTION BY STEAM REFORMING
CN1323937A (en) * 2000-02-21 2001-11-28 七环机械电子工程公司 Production process of molded paper pulp porduct
US20070264186A1 (en) * 2004-09-09 2007-11-15 Dybkjaer Ib Process for Production of Hydrogen and/or Carbon Monoxide
JP4781652B2 (en) * 2004-10-13 2011-09-28 日揮株式会社 Syngas production method and production equipment
EP1944268A1 (en) * 2006-12-18 2008-07-16 BP Alternative Energy Holdings Limited Process
DK2419375T3 (en) * 2009-04-15 2016-07-25 Air Prod & Chem A process for producing a hydrogen-containing product gas
US20110085967A1 (en) * 2009-10-14 2011-04-14 Troy Michael Raybold Hydrogen product method and apparatus
PL2526044T3 (en) * 2010-01-19 2019-05-31 Topsoe Haldor As Process for reforming hydrocarbons
RU2570659C2 (en) * 2010-05-26 2015-12-10 ДжиТиЭлПЕТРОЛ ЭлЭлСи Producing ammonia using ultrapure, high-pressure hydrogen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0936182A2 (en) * 1998-02-13 1999-08-18 Haldor Topsoe A/S Method of soot-free start-up of autothermal reformers
US20040081593A1 (en) * 2002-08-17 2004-04-29 Daimlerchrysler Ag Reactor system for hydrogen production
EP1400489A1 (en) * 2002-09-23 2004-03-24 Kellogg Brown & Root, Inc. Process and apparatus for autothermal reforming with recycle of a portion of the produced syngas
WO2012123100A1 (en) * 2011-03-17 2012-09-20 Thyssenkrupp Uhde Gmbh Method of starting up autothermal reforming reactors
WO2014037201A1 (en) * 2012-09-05 2014-03-13 Haldor Topsøe A/S Method for starting-up a gas to liquid process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4174151A1 (en) 2021-10-27 2023-05-03 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Partial oxidation reactor with heating burner for producing synthesis gas
US12459812B2 (en) 2021-10-27 2025-11-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Partial oxidation reactor with warm-up burner for production of synthesis gas

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