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Norges teknisk-naturvitenskapelige universitet

Chemical Reactors and their Applications
Chemical Reactors and their Applications

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Chemical Reactors and their Applications

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Outline
– Reactor concepts

– Natural gas reforming concepts

– Downstream processes

Chemical Reactors and their Applications

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Outline
– Reactor concepts

– Natural gas reforming concepts

– Downstream processes

Chemical Reactors and their Applications

5 Reactor Concepts – Fixed bed reactors – Fluidized bed reactors – Stirred tank reactors – Slurry loop reactors – Bubble columns Chemical Reactors and their Applications .

6 Reactor Concepts – Fixed bed reactors – Fluidized bed reactors – Stirred tank reactors – Slurry loop reactors – Bubble columns Chemical Reactors and their Applications .

7 Fixed Bed Reactors Concept – Collection of fixed solid particles. – The particles may serve as a catalyst or an adsorbent. – Continuous gas flow – (Trickling liquid) Applications – – – – – Synthesis gas production Methanol synthesis Ammonia synthesis Fischer-Tropsch synthesis Gas cleaning (adsorption) Chemical Reactors and their Applications .

8 Fixed Bed Reactors Challenges/Limitations – Temperature control – Pressure drop – Catalyst deactivation Chemical Reactors and their Applications .

9 Fixed Bed Reactors Challenges/Limitations – Temperature control – Pressure drop – Catalyst deactivation Chemical Reactors and their Applications .

10 Fixed Bed Reactors Temperature control – Endothermic reactions may die out – Exothermic reactions may damage the reactor – Selectivity control Chemical Reactors and their Applications .

11 Fixed Bed Reactors Single-Bed Reactor – All the particles are located in a single vessel Advantages/Disadvantages – Easy to construct – Inexpensive – Applicable when the reactions are not very exo-/endothermic Chemical Reactors and their Applications .

12 Fixed Bed Reactors Multi-Bed Reactor – Several serial beds with intermediate cooling/heating stages Advantages/Disadvantages – Applicable for exo-/endothermic reactions Chemical Reactors and their Applications .

13 Fixed Bed Reactors NH3 reactor SO3 reactor Chemical Reactors and their Applications .

14 Fixed Bed Reactors Multi-Tube Reactor – Several tubes of small diameter filled with particles. Advantages/Disadvantages – Expensive – High surface area for heat exchange  Very good very temperature control – Applicable for very exo/endothermic reactions Chemical Reactors and their Applications .

15 Fixed Bed Reactors Steam reformer Reactor height: Number of tubes: Tube length: 30 m 40-10000 6-12 m Tube diameter: 70-160 mm Chemical Reactors and their Applications .

16 Fixed Bed Reactors Challenges/Limitations – Temperature control – Pressure drop – Catalyst deactivation Chemical Reactors and their Applications .

Chemical Reactors and their Applications . – The pressure drop is mainly dependent on reactor length.17 Fixed Bed Reactors Pressure drop – Friction between the gas and particle phase results in a pressure drop. – High pressure drop  high compression costs – Some systems have low tolerance for pressure drop. particle diameter. void fraction and gas velocity.

Chemical Reactors and their Applications .18 Fixed Bed Reactors Large particles has to be used (dp>1mm).

19 Fixed Bed Reactors Porous catalyst particle – The particles are porous to increase the surface area of the catalyst. – Reactants are transported inside the pores by means of molecular diffusion and adsorb to the active sites where the reaction occurs. Intra-particle diffusion/conduction may be rate determining for large particles ( egg-shell particles). Chemical Reactors and their Applications . – Heat is transported by conduction. – Products desorb and diffuse back to the bulk.

20 Fixed Bed Reactors Challenges/Limitations – Temperature control – Pressure drop – Catalyst deactivation Chemical Reactors and their Applications .

causing hot-spots that damage the reactor. – Large carbon deposits may clog the tubes. – Formation of carbon deposits deactivate the catalysts. – Catalyst regeneration is necessary. Chemical Reactors and their Applications . – Sulfur compounds deactivate Ni-catalysts – Desulfurization is often necessary prior to reforming.21 Fixed Bed Reactors Catalyst deactivation – The catalyst gets deactivated if the active sites get contaminated.

or non-deactivating processes Chemical Reactors and their Applications .22 Fixed Bed Reactors Summary Advantages/Disadvantages – High conversion is possible – Large temperature gradients may occur – Inefficient heat-exchange – Suitable for slow.

23 Reactor Concepts – Fixed bed reactors – Fluidized bed reactors – Stirred tank reactors – Slurry loop reactors – Bubble columns Chemical Reactors and their Applications .

24 Fluidized Bed Reactors Concept – Collection of solid particles dispersed in a continuous phase. – Continuous flow of gas or liquid Applications – – – – – Catalytic cracking processes Fischer-Tropsch synthesis Polymerization Waste combustion Drying Chemical Reactors and their Applications . adsorbent or a heat carrier. – The particles may serve as a catalyst.

25 Fluidized Bed Reactors Chemical Reactors and their Applications .

26 Fluidized Bed Reactors A fluidized bed exhibits liquidlike behavior Chemical Reactors and their Applications .

27 Fluidized Bed Reactors Continuous regeneration Chemical Reactors and their Applications .

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Fluidized Bed Reactors
Summary Advantages/Disadvantages
– Conversion may be poor if gas is bypassing. – Erosion of vessel and pipe lines. – Uniform temperature – Efficient heat-exchange – Can handle rapid deactivating processes.
Chemical Reactors and their Applications

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Reactor Concepts
– Fixed bed reactors – Fluidized bed reactors – Stirred tank reactors – Slurry loop reactors – Bubble columns

Chemical Reactors and their Applications

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Stirred tank Reactors
Concept – Forced mixing by use of impeller. – Applied in reactive systems when mixing is the rate determining step. – Single phase: liquid mixing. – Two phases: liquid/gas, liquid/particle – Three phases: liquid/particle/gas Typical applications
– Chemical component and phase mixing – Fermentation reactor – Food and paper industry – Natural gas conversion/polymerization
Chemical Reactors and their Applications

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Stirred tank Reactors
The mixing is influenced by:
– stirring rate and pumping capacity – liquid height

– baffle design
– (baffles reduces solid body rotation)

– size and geometry of the tank

– size and geometry of heat equipment
– size and type of impeller
Chemical Reactors and their Applications

Chemical Reactors and their Applications . – Axial flow impellers are suitable to blend liquids and suspend solids in liquids.32 Stirred tank Reactors Impellers – Radial flow impellers are suitable for dispersion of gas in liquid.

Chemical Reactors and their Applications .33 Stirred tank Reactors Summary Advantages/Disadvantages – Uniform temperature – Efficient heat-exchange – Exception: slurries with high concentrations of large particles (difficult mixing).

34 Reactor Concepts – Fixed bed reactors – Fluidized bed reactors – Stirred tank reactors – Slurry loop reactors – Bubble columns Chemical Reactors and their Applications .

Typical application – Polymerization Chemical Reactors and their Applications . – The mixing pattern is very intensive and well defined. – The slurry is circulating at a high velocity impelled by an axial pump.35 Slurry loop Reactors Concept – Collection of solid catalyst particles dispersed in a liquid phase (slurry).

36 Slurry loop Reactors Summary Advantages/Disadvantages – Uniform temperature – Very efficient heat-exchange – Can operate at high polymer concentrations Chemical Reactors and their Applications .

37 Reactor Concepts – Fixed bed reactors – Fluidized bed reactors – Stirred tank reactors – Slurry loop reactors – Bubble columns Chemical Reactors and their Applications .

– Two phases: liquid/gas. – Three phases: slurry/gas Typical applications – Natural gas conversion – Waste water treatment – Bio-processes Chemical Reactors and their Applications .38 Bubble Columns Concept – Gas dispersed in a continuous liquid phase.

39 Bubble Columns Chemical Reactors and their Applications .

40 Bubble Columns Chemical Reactors and their Applications .

41 Bubble Columns Chemical Reactors and their Applications .

42 Bubble Columns Summary Advantages/Disadvantages – Non-uniform product if bubble size distribution is heterogeneous – Uniform temperature – Efficient heat-exchange Chemical Reactors and their Applications .

43 Outline – Reactor concepts – Natural gas reforming concepts – Downstream processes Chemical Reactors and their Applications .

ammonia) Typical composition CH4 CO2 N2 H 2S 70-90% 0-8% 0-5% 0-5% C2H6-C4H10 0-20% Chemical Reactors and their Applications . – Fuel – Most common feedstock for hydrogen production or synthesis gas production. 20%). – Production of base chemicals (methanol.44 Natural gas – Vital component of the world's supply of energy (approx.

45 Natural gas reforming concepts – Steam reforming (SR) – Partial oxidation (POX) – Autothermal reforming (ATR) – New reforming concepts Chemical Reactors and their Applications .

46 Natural gas reforming concepts – Steam reforming (SR) – Partial oxidation (POX) – Autothermal reforming (ATR) – New reforming concepts Chemical Reactors and their Applications .

47 Steam reforming Chemical Reactors and their Applications .

48 Steam reforming Primary reformer CH4 + H2O  CO + 3H2 ΔHr=206 kJ/mol CO + H2O  CO2 + H2 ΔHr= -41 kJ/mol (Water gas shift) – Overall heat of reaction is endothermic  multi-tube reformer – Reactions are catalyzed over Ni-catalyst. Temperature Pressure H2/CO 1100-1200K 15-30 bar >3 Chemical Reactors and their Applications .

49 Steam reforming Burner configurations Chemical Reactors and their Applications .

50 Steam reforming Catalyst deactivates  Retaining productivity by increasing temperature Better temperature control with side fired burners Chemical Reactors and their Applications .

5–4. Actions to reduce carbon formation – High steam/carbon (S/C) ratio reduces carbon formation.51 Steam reforming Carbon formation 2CO  C + CO2 ΔHr= -173 kJ/mol (The Boudouard reaction) CH4  C + 2H2 ΔHr= 75 kJ/mol (Decomposition of methane) CO + H2  C + H2O ΔHr= -132 kJ/mol (Heterogeneous water gas reaction) – Carbon deposits deactivates the catalyst. – Expensive to produce steam.5 Chemical Reactors and their Applications . – Addition of CO2 reduces carbon formation – Pre-reformer if higher hydrocarbons are present – Common S/C-ratio is 2.

52 Steam reforming Chemical Reactors and their Applications .

Chemical Reactors and their Applications .53 Steam reforming Adiabatic Pre-reformer CnHm + nH2O → nCO + (n+m/2)H2 CO + 3H2  CH4 + H2O ΔHr>0 ΔHr= -206 kJ/mol – Overall heat of reaction is exothermic or thermoneutral. – Reactions are catalyzed over Ni-catalyst.

54 Steam reforming Chemical Reactors and their Applications .

55 Steam reforming Hydro-desulfurizer (HDS) – Sulfur compounds are present in practically all gas feedstocks. – Ni-catalysts are poisoned by sulfur compounds  desulfurization – Cyclic organic sulfur compounds are hydrogenated to H2S over CoMo or Ni-Mo catalysts. – H2S and other sulfur species are adsorbed over a bed of zinc-oxide. Chemical Reactors and their Applications .

not for methanol.56 Steam reforming Advantages/Disadvantages – No need for expensive oxygen plant. – Material limitations on temperature  limited conversion.or FT-synthesis. – Costs in handling excess H2O. – High H2/CO ratio. Chemical Reactors and their Applications . suitable for hydrogen production with CO2 capture. – Carbon formation – Steam corrosion problems.

57 Natural gas reforming concepts – Steam reforming (SR) – Partial oxidation (POX) – Autothermal reforming (ATR) – New reforming concepts Chemical Reactors and their Applications .

58 Partial oxidation CH4 + ½O2 → CO + 2H2 CH4 + 2O2 → CO2 + 2H2O CO + ½O2 → CO2 H2 + ½O2 → H2O ΔHr= -36 kJ/mol ΔHr= -803 kJ/mol ΔHr= -284 kJ/mol ΔHr= -242 kJ/mol Temperature 1600-1900K →150 bar <2 Pressure H2/CO – Overall heat of reaction is slightly exothermic. – No catalyst (burners) Chemical Reactors and their Applications .

Chemical Reactors and their Applications .59 Catalytic partial oxidation Reactions are catalyzed to: – improve selectivities – eliminate the need for burners – eliminate soot formation – lower reaction temperatures Drawbacks – CH4/O2 mixtures can be explosive. – Problems with selectivities at high pressures (above 20 bars).

60 Partial oxidation Advantages/Disadvantages – Less expensive than SR-plants. – (dependent on downstream process) Chemical Reactors and their Applications . – H2/CO ratio suitable for methanol.or FT-synthesis – Soot problems (POX) – Needs expensive oxygen plant.

61 Natural gas reforming concepts – Steam reforming (SR) – Partial oxidation (POX) – Autothermal reforming (ATR) – New reforming concepts Chemical Reactors and their Applications .

62 Autothermal reforming Catalytic/non-catalytic partial oxidation provides heat for steam reforming  More energy efficient Temperature Pressure H2/CO 1200-1400K 20-100 bar 2-3 Chemical Reactors and their Applications .

– Higher conversion than SR (higher operating temperature). Chemical Reactors and their Applications . – No soot problems – Needs expensive oxygen plant.63 Autothermal reforming Advantages/Disadvantages – Less expensive than SR-plants. – (dependent on downstream process) – Often used as a secondary reformer downstream an SR.

64 Natural gas reforming concepts – Steam reforming (SR) – Partial oxidation (POX) – Autothermal reforming (ATR) – New reforming concepts Chemical Reactors and their Applications .

– Remove H2 in the reactor by using membranes and thereby avoid equilibrium limitations – Lower reaction temperatures can be used. – Simple separation of oxygen.65 Multifunctional reactors Membrane reactors – Combine air separation and partial oxidation in one unit by introduce oxygen permeable membranes. Chemical Reactors and their Applications . – No explosive mixtures. Chemical looping reforming – Continuous circulation of metal particles which serve as oxygenand heat carrier (metal oxide) for partial oxidation of methane. Two reactors are required: Air reactor and fuel reactor.

or pressure swing).66 Multifunctional reactors Sorption enhanced reaction process (SERP) – Remove CO2 in the SR-process by using adsorbents mixed with the catalyst particles and thereby avoid equilibrium limitations. Chemical Reactors and their Applications . The adsorbent is regenerated by either increasing the temperature or reducing the pressure (temperature.

67 Outline – Reactor concepts – Natural gas reforming concepts – Downstream processes Chemical Reactors and their Applications .

68 Downstream processes – Ammonia synthesis – Methanol synthesis – Fischer-Tropsch synthesis Chemical Reactors and their Applications .

KNO3) – Explosive industry Production history – 1905.69 Ammonia synthesis Ammonia – Base chemical for: – Nitrogen fertilizers (CaNO3. – 1913. The Haber/Bosch-process was developed. Chemical Reactors and their Applications . Birkeland/Eyde succeeded in producing CaNO3 from air.

70 Ammonia synthesis N2 + 3H2  2NH3 ΔHr = -91. – Low single-pass conversion  Recycling necessary.4 kJ/mol – Ideal H2/N2-ratio is 3. – CO and CO2 has to be removed prior to the ammonia synthesis  several extra process units. – Steam reforming is suitable reforming process due to high H2/COratio. It is combined with an air-blown ATR that introduces N2. – Equilibrium limited  High pressure (100-250 bar) and low temperature (675-770K). Chemical Reactors and their Applications .

71 Ammonia synthesis Chemical Reactors and their Applications .

72 Ammonia synthesis ICI quench reactor Chemical Reactors and their Applications .

73 Ammonia synthesis Haldor Topsøe radial flow reactor Kellogg vertical reactor Kellogg horizontal reactor Chemical Reactors and their Applications .

74 Ammonia synthesis Chemical Reactors and their Applications .

Chemical Reactors and their Applications . BASF was the first to synthesize methanol from syngas. – 1960s.75 Methanol synthesis Methanol – Base chemical for: – Formaldehyde – Acetic acid – Automobile fuel and fuel additive (MTBE) Production history – 1923. New catalysts were developed for low-pressure production.

– T < 570K due to catalyst sintering.e. – The catalyst has to be very selective since methanol is thermodynamically less stabile than i. – Low single-pass conversion  Recycling necessary.  Cu/ZnO/Al2O3 Chemical Reactors and their Applications . CH4. – Equilibrium limited  High pressure (50-100 bar) and low temperature (500-550K).8 kJ/mol ΔHr = -49.76 Methanol synthesis CO + 2H2  CH3OH CO2 + 3H2  CH3OH + H2O CO + H2O  CO2 + H2 ΔHr = -90.6 kJ/mol ΔHr = -41 kJ/mol – Ideal H2/CO-ratio is 2.

Chemical Reactors and their Applications . Separator – Gas and liquid are separated after several cooling steps.77 Methanol synthesis Reactor (ICI) – – 40% of the feed enters the reactor 60% of the feed is used as quench. Column 2: Methanol is separated from heavy alcohols and water. Distillation – – Column 1: Gases and light impurities are removed.

78 Methanol synthesis Lurgi reactor Haldor Topsøe reactor concept Chemical Reactors and their Applications .

) – Solid catalyst. uniform temp. Chemical Reactors and their Applications .79 Methanol synthesis Slurry reactor (fluidized bed) – Inert hydrocarbon liquid (absorbs heat. – Higher single-pass conversion less compression costs.

– Low yields. Chemical Reactors and their Applications . – No CO2 production.80 Methanol synthesis Direct conversion of methane CH4+ ½O2 CH3OH ΔHr = -126 kJ/mol – Significant efficiency increase.

Chemical Reactors and their Applications . Fischer/Tropsch converted synthesis gas into a wide range of hydrocarbons and/or alcohols. Germany applied FT-synthesis to make fuels. – WW II.81 Fischer-Tropsch synthesis Applicability – Fuels – Waxes History – 1923. – 1950s→. South Africa started to make fuels and base chemicals in FT-plants to reduce the dependence on imported oil.

+ H2O – Chain growth.82 Fischer-Tropsch synthesis CO + 2H2  -CH2. – Selective productivity is not possible  product ranges. – Effective heat removal is a major consideration in reactor design. – High exothermicity. ΔHr = -165 kJ/mol – Converted over Fe. Chemical Reactors and their Applications .or Co-based catalysts.

83 Fischer-Tropsch synthesis T<530 K due to carbon deposition T>570 K to avoid heavy wax formation T<570 K due to hydrocracking Chemical Reactors and their Applications .

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