Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical 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
  • B01J8/06—Chemical 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
  • B01J8/062—Chemical 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
• • 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
  • 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
  • C01B3/384—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 the catalyst being continuously externally heated
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F28—HEAT EXCHANGE IN GENERAL
  • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
  • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F28—HEAT EXCHANGE IN GENERAL
  • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
  • F28F1/00—Tubular elements; Assemblies of tubular elements
  • F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
  • F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
  • F28F1/14—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending longitudinally
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00106—Controlling the temperature by indirect heat exchange
  • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
  • B01J2208/00212—Plates; Jackets; Cylinders
  • B01J2208/00221—Plates; Jackets; Cylinders comprising baffles for guiding the flow of the heat exchange medium
• • 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
  • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming 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
  • C01B2203/0205—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
  • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming 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
  • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
• • 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

Definitions

• the invention relates to a steam reforming furnace for the production of hydrogen comprising a plurality of reforming tubes.
• the objective is to increase the total heat transfer absorbed by the radiation and convection heated reforming tubes, and in particular in the upper part of the steam reforming furnace.
• the methane reforming is carried out by steam at high temperatures (900-980 ° C.) and pressures of between 10 and 40 bar in reforming tubes filled with supported nickel catalyst. on alumina.
• the decomposition reaction of methane is endothermic and needs an external heat source to be initiated. For this reason the reaction usually takes place inside a combustion chamber equipped with burners as heating systems.
• These operating conditions impose requirements on the tube; in fact, the refractory alloy tubes must be resistant to high temperature oxidation and creep. The operating conditions induce a thermal profile with a large gradient between high (650/700 ° C) and low (900/950 ° C) due to the endothermic reaction.
• the reformers are designed with a wide variety of tube and burner arrangements.
• the heat is transferred to the catalyst through the design of the tubes (section, length, thickness).
• a limiting step for the reforming reaction is the amount of heat supplied to the upper part of the reactor by the configuration of the existing tubes.
• An improvement of the current commercial tubes is proposed to improve this disadvantage.
• US 8529849 proposes a partially filled tube of at least one shape memory alloy element to increase the heat transfer coefficient.
• the alloy to shape memory can be deployed to stay in contact with the tube and close the gap between the tube and the catalytic bed;
• This set of patents proposes an improvement of heat transfer inside the tubes. This represents the following disadvantages for SMR furnaces: difficulty filling and emptying catalysts in the tubes, increasing the pressure drop inside the tubes due to the presence of additional structures, risk of heterogeneity of distribution of flow in the tube, less efficiency gain compared to an external structure.
• a solution of the present invention is a steam reforming furnace for the production of hydrogen, comprising a plurality of reforming tubes allowing flow of hydrocarbons and at least one fluid inside the tubes from top to bottom and having on their outer surfaces, one or more fins, the majority of which are located on at least a portion of the upper half, with the fins thickness between 1 and 30 mm, width between 3 mm and 100 mm and a length between 1 m and a length equivalent to the height of said oven (often 12 m).
• the chemical composition of the fin will be identical or very similar to that of the tube (refractory alloy).
• the thickness is between 3 and 10 mm, the width between 10 and 30 mm, the length between 1 and 10 m.
• the steam reforming oven according to the invention may have one or more of the following characteristics:
• the number of fins per tube is between 1 and 50, preferably between 2 and 26;
• the fin may have the shape of a plate in the shape of a rectangle, a trapezium, a triangular plate, a corrugated plate or a beveled plate;
• the fins are installed vertically;
• the reforming tubes are installed in a combustion chamber
• the fluid flowing with the hydrocarbons inside the tubes is water vapor.
• the fins are preferably welded to the coldest areas of the tube.
• the fluid flowing in the reforming tubes is preferably a mixture of methane and water vapor.
• the methane may contain a minimal amount of H 2 (1 to 10%, preferably 2 to 4%). This methane may also contain some impurities such as CO2 OR nitrogen.
• Figure 1 gives an example of a section of a tube having 4 parallelepiped fins.
• the fins are generally used to increase the heat exchange area in the heat exchangers. To obtain maximum heat gain with fins, it must be installed on the side of the heat exchanger where the thermal resistance is highest.
• the heat resistance R ext at the outer side of the tube is the highest (0.0064 mK / W) with respect to the conduction resistance R t of the tube wall (0.0012 mK / W) and the thermal resistance R int between the inner surface of the tube and the synthesis gas (0.0029 mK / W) ( Figure 2).
• D ext and D int are respectively the outer and inner diameter of the tube
• ⁇ is the thermal conductivity of the tube wall
• ext and h mt are respectively the heat transfer coefficients on the outer and inner side of the tube.
• the total thermal resistance between the combustion gases and the synthesis gas is the sum of the three resistances:
• the external thermal resistance R ex t represents approximately 61% of the total thermal resistance Rtot and is twice as large as the internal heat resistance R int .
• the heat transfer coefficient h ext is doubled, the external heat resistance R ext will be reduced by half and the total resistance R to t by 31%.
• R int is reduced by half and the R to t is only reduced by 14% and not by 31% as in the first case.
• the fins must be installed on the outer surface of the flue gas. tube as shown in Figure 1, which gives an example for the installation of four parallelepiped fins.
• h f is the total heat coefficient (radiation and convection) between the fin and the ambient temperature around the fin and X f is the thermal conductivity of the fins. It is assumed that the heat transfer coefficient around the fin is quite the same as that around the tube and the fin.
• P is the perimeter of the cross-section of the fin and A c is the area of the cross section of the fin.
• Figure 3 shows an example of a total heat transfer coefficient ext on the outer surface of the tube and the equivalent ambient temperature also known as Tinc incident temperature around the tube at the top of the oven as a function of the distance from the top of the oven.
• the incident temperature is calculated is calculated using the following relationship and knowing the total heat flow and the outside temperature of the tube inside the oven:
• cpi, cp r and ⁇ ⁇ are respectively the total heat flux, the radiation heat flux and the convective heat flux on the tube, ⁇ is the external emissivity of the tube, ⁇ is the Stefan constant.
• Bolztmann (5.67 10 "8 SI) and T is the external temperature of the tube in Kelvin.
• the parameter m of the fin is rati ously independent of its length.
• the width of the fin should therefore be below a certain limit determined by the following relation:
• im of the fin corresponds to 99% of the maximum heat acquired by a
• the maximum efficiency of the fin is obtained when the width of the fin is infinite (w ⁇ ⁇ or m w> 3). In this case, the efficiency of the fin becomes:
• n f is the number of fins on the perimeter of the tube.
• the efficiency of the tube with fins can be determined by a numerical calculation of 2-D conduction with boundary conditions inside the tube. This implies that the temperature at the base of the fin is not fixed.
• Figures 6 and 7 show the number of fins as a function of the flux increase for three thicknesses of fin 1mm, 3mm and 7 mm with a fin width meeting the criterion
• Figure 6 compares the two calculation approaches 1-D and 2-D.
• the 1-D approach considers that the temperature at the base of the fin is constant, the increase of the flux, for the same number of fins, is overestimated compared to the 2-D approach. Subsequently we will be based on the 2-D approach that is closer to reality.
• Figure 7 compares the efficiency of the tube for two different external pipe flow conditions 101 kW / m 2 , characteristic value for the tube region near the top of the furnace and 67kW / m2, characteristic value for the middle of the tube in the sense of height.
• the efficiency of the tube with fins varies slightly with the flow. We notice that the more the external flow is important, the more one gains efficiency.
• the efficiency of the finned tube varies significantly with the characteristics of the fin. For the same number of fins, the thicker the fin, the more the efficiency of the tube increases but the weight of the tube will be higher.
• FIG. 8 shows the increase in the weight of the tube due to the fins (assumed over the entire length of the tube) in% which is equal to the ratio:
• the increase of the weight of the tube is displayed according to the increase of the heat flux in% (equal to ⁇ 00 * (r ⁇ tf - 1)) for three thicknesses of fin 1mm, 3mm and 7 mm with a width
• the minimum distance between two fins is the minimum distance between two fins. This distance must be at least equal to the width of a fin so as to leave sufficient space for the radiation (radiation is the largest part of the heat transferred to the tubes) from the walls of the furnace and the combustion gases to heat the tube and fins.
• the maximum number of fins that can be put on a tube is:
• the number of fins on a tube must always be less than or equal to this limit (n f ⁇ n fmsx ).
• Figure 10 shows the increase of the tube temperature as a function of the number of fins with 3 mm thickness and 13.5 mm width and for two different external flux values 101 kW / m 2 and 67 kW / m 2 . It is observed that the flow has a significant impact on this increase in temperature.
• the thermal efficiency of the furnace can be increased up to 3.5%. This was obtained with a variable number of fins per tube depending on the height of the tube. The goal is to maximize the total heat flux absorbed by each tube while maintaining the maximum tube temperature below the MOT and avoiding the formation of carbon in the upper part of the tubes.
• Increasing the efficiency of the oven can be used to either increase tube feed and hydrogen production up to 3.9% with the same burner power or to reduce burner power up to 4.2 % with the same hydrogen production. This while keeping the exit temperature of the synthesis gas furnace constant.
• Each tube of this oven will be provided with 3 fins on a height between 0 and 1.5 m, 26 fins between 1.5 m and 3.3 m, 17 fins between 5.5 m and 7 m and 26 fins between 10 m and 12 m.
• the connection areas will have a constant number of fins in steps of 0.3 m.
• the circumferential position of the fins on the tube can also be optimized to homogenize the profile of the temperature at a given height.
• Another way to take advantage of the increased efficiency of the oven due to tube fins is to change the design of the oven for a given production by reducing the height of the oven or the number of tubes to 3.5%. inside this same oven. It may also be interesting to combine the last two possibilities, but with the lower reduction percentage for each.
• the optimal dimensions of the fins of the tubes of the reforming furnaces are defined in the range:
• the reforming furnace according to the invention is preferably used for the production of hydrogen.
• fins can be attached to a reforming tube by welding or casting or additive manufacturing.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• Hydrogen, Water And Hydrids (AREA)

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• 2014
  • 2014-10-21 FR FR1460107A patent/FR3027381A1/fr not_active Withdrawn
• 2015
  • 2015-09-18 US US15/520,556 patent/US20170312721A1/en not_active Abandoned
  • 2015-09-18 EP EP15780917.9A patent/EP3209602A1/de not_active Withdrawn
  • 2015-09-18 CN CN201580057203.7A patent/CN107073426A/zh active Pending
  • 2015-09-18 CA CA2964576A patent/CA2964576A1/en not_active Abandoned
  • 2015-09-18 WO PCT/FR2015/052503 patent/WO2016062932A1/fr active Application Filing

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