WO2001086220A2 - Cuve refractaire sous pression - Google Patents

Cuve refractaire sous pression Download PDF

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Publication number
WO2001086220A2
WO2001086220A2 PCT/US2001/014595 US0114595W WO0186220A2 WO 2001086220 A2 WO2001086220 A2 WO 2001086220A2 US 0114595 W US0114595 W US 0114595W WO 0186220 A2 WO0186220 A2 WO 0186220A2
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WO
WIPO (PCT)
Prior art keywords
pressure vessel
reactor
refractory
lining
vessel
Prior art date
Application number
PCT/US2001/014595
Other languages
English (en)
Other versions
WO2001086220A3 (fr
Inventor
Dennis W. Jewell
Original Assignee
Dow Global Technologies Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Priority to MXPA02010887A priority Critical patent/MXPA02010887A/es
Priority to JP2001583119A priority patent/JP2003532789A/ja
Priority to EP01935096A priority patent/EP1285049A2/fr
Priority to BR0110397-0A priority patent/BR0110397A/pt
Priority to AU2001261220A priority patent/AU2001261220A1/en
Publication of WO2001086220A2 publication Critical patent/WO2001086220A2/fr
Publication of WO2001086220A3 publication Critical patent/WO2001086220A3/fr
Priority to NO20025248A priority patent/NO20025248D0/no

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/74—Construction of shells or jackets
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/78—High-pressure apparatus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/122—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1223—Heating the gasifier by burners
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water

Definitions

  • the invention relates to a refractory vessel for gasifying carbonaceous materials, and more particularly to a vessel wall construction and temperature control system.
  • Gasification is in this regard a well-known technology for consuming by-product and waste carbonaceous materials and producing useful, more valuable products therefrom.
  • the related application of the preceding paragraph provides a new approach to the treatment of a particular class of carbonaceous materials and wastes now predominantly processed in liquid thermal oxidation facilities — namely, halogenated materials and especially by-product and waste chlorinated hydrocarbons.
  • the refractory pressure vessel of the present invention is considered to be especially useful in this particular context, but finds utility also in the gasification of other carbonaceous materials.
  • Gasification offers several potential advantages to liquid thermal oxidation, including lower economic costs, reduced emissions and capture of maximal chemical values of the feed stream constituents.
  • gasification is also more flexible than other competing halogenated material waste treatment technologies (that is, other than liquid thermal oxidation), in that gasification is suited to working with a significantly broader range of acceptable feedstock compositions.
  • gasification typically occurs at partial oxidation conditions, that is, at oxygen to fuel ratios that are substoichiometric, with an excess of hydrogen.
  • Reaction temperatures are typically greater than 1200°C and more typically greater than 1400°C, and reaction pressures are typically around 5 bars, gauge (barg).
  • reaction temperatures are typically greater than 1200°C and more typically greater than 1400°C
  • reaction pressures are typically around 5 bars, gauge (barg).
  • the halide content of halogenated organic material should be converted to its gas phase hydrogen halide form.
  • Halogen halides are very corrosive in both the gas phase as well as the condensed aqueous phase.
  • the dry gas phase corrosion rate of most materials of construction in contact with hydrogen halides increases exponentially with temperature.
  • Aqueous hydrogen halide corrosion rates for materials also increase with temperature, but are exacerbated by the presence of oxygen or oxidizing metal salt species.
  • the aggressive nature of the hydrogen halides thus, as an example, emphasizes the need for specific attention in the design of safe and reliable pressure vessels for gasification reactor service. In the field of the gasification of hydrocarbonaceous as opposed to halogenated feeds, two principal refractory vessel designs have been used.
  • a "hot wall” design employs one or more layers of refractory, for example, hot face 20, insulating refractory 22, ceramic fiber paper 24, and optionally castable or plastic refractory 26, which collectively simply limit heat transfer from a reactor chamber C to an outside vessel wall 28, which might be a carbon steel shell, teflon lined or lined with Hastelloy Alloy B-2(ID), and ultimately limit heat loss to the atmosphere A.
  • This design provides no positive means of controlling vessel wall temperatures themselves. The result is that vessel wall temperature can vary widely with operating conditions, refractory integrity and ambient conditions.
  • One aspect of the present invention is to improve upon such design, finding the design particularly not optimal for use in gasifying halogenated organic materials, primarily because it lacks positive wall temperature control and the degree of influence over hydrogen halides-related corrosion of the vessel wall afforded by such control.
  • FIG. 4 A second design used in refractory wall construction for the gasification of hydrocarbonaceous materials, the interior "membrane wall” design, is illustrated in Figure 4.
  • the interior "membrane wall” design again employs one or more layers of a refractory 20, 22, 24 and optionally 26 within a so-called membrane 34 located within the pressure vessel 28.
  • This membrane is constructed of any number of conduits or passages 38 (usually tubes) for circulating a fluid heat control substance 36.
  • the conduits together make up an interior "membrane” barrier.
  • the membrane and refractory materials are all contained within the pressure vessel (typically leaving a small space between the membrane and vessel wall).
  • the membrane may be made of any of various materials of construction.
  • a heat transfer fluid flows through the membrane conduits to absorb heat from the reactor chamber C, thereby limiting vessel wall temperatures.
  • Internal membrane systems which do provide a measure of control over vessel wall temperatures, have other disadvantages which include high costs of construction and maintenance in the harsh environment.
  • the interior membrane design can be further complicated if a "gas-tight" design is desired, to minimize process gas migration to the pressure vessel wall.
  • One aspect of the instant invention is to improve upon this interior membrane design for purposes of a reactor for the gasification of carbonaceous materials, in particular of halogenated materials whereby one or more hydrogen halides result.
  • the interior membrane design is unsuitably complex and expensive, both in construction and in maintenance, the latter aspect being particularly critical for service in a harsh hydrogen halide gasification environment.
  • Jacketing techniques are known. Such are described, for instance, in R.E. Markovitz, "Picking the Best Vessel Jacket” , Chem. Engr. pp 156-162, Nov. 15, 1971; R.E. Markovitz, Chapter: Heat Transfer: Jacketed Vessels in Heat Transfer Design Methods, ed. J.J. McKetta, Marcel Dekker, 1991; W.R. Penney, Section 3.14 (3.14.1, .2 and .3) in: Hemisphere Handbook of Heat Exchanger Design, G.F. Hewitt, ed. 1981; I.H. Lehrer, "Jacket-Side Nusselt Number", IEC Proc. Des. Dev., 9 No. 4, pp 553-558, 1970; J.A.
  • jacketed reactors for use with the gasification of carbonaceous materials and in particular halogenated materials.
  • the temperature-controlled jacketed gasification reactor of the instant invention is not structured or designed to control the bulk temperature of the contents of the reactor itself. Rather the function of the jacket design is to control and limit the temperature of the pressure vessel walls and cladding, if used, separately from and essentially independently of, and substantially below normal operational levels of the temperature in the reaction chamber and its contents, per se.
  • the new externally jacketed reactor is designed with heat transfer fluid circulation for wall temperature control, including cooling during operations and also preferably heating during down time.
  • This wall temperature control system can limit the maximum or high wall temperature, thus limiting hot dry gas corrosion. Because high levels of hydrogen halide are contemplated in a process according to the above-referenced, related PCT application, and because gas phase corrosion rates of materials such as HC1 rise exponentially with temperature, disciplined wall temperature control is very important.
  • High wall temperature can occur due to high ambient temperatures, high internal gasifier operating temperatures, or gas permeation or "by-passing" of the refractory such that gas contacts the vessel wall. These "hot-spots" are not uncommon in large, refractory lined vessels. For these reasons, simple hot wall designs, as discussed above, are believed inferior for long term gasifier service. Furthermore, wall temperature control can be extremely important during stand-by, start-up, heat-up, degradation, or shut-down run conditions for a gasifier, especially a gasifier for halogenated materials.
  • the wall temperature control of the instant invention is also preferably designed to prevent cold or wet aqueous acid, in particular hydrogen halide, condensation. Aqueous acids or hydrogen halides are very corrosive.
  • the new jacketed vessel construction of the instant invention can also eliminate problems with crevices and stress points inherent in membrane designs.
  • the membrane design is typically fabricated from bent and welded tubes or channels. This bending, fabrication and welding process inevitably results in residual material stresses, and will also have some crevices. These higher stressed areas and crevices result in higher local corrosion rates in the membrane material.
  • a refractory pressure vessel externally jacketed for temperature control provides a simpler, cheaper construction and maintenance program compared to that for an internal membrane design and promises greater reliability.
  • An internal membrane wall requires that many panels or components be assembled inside of the pressure vessel. To allow for future repairs, these pieces are typically fabricated small enough to pass through vessel manways. These pieces must be assembled inside the vessel.
  • Interior membrane design thus, is quite complex, requires appropriate strength to support the weight of all refractory and is further complicated in that it must allow for thermal growth differences between refractory, the membrane wall, and the pressure vessel shell. With the possibility for achieving a more uniform wall temperature by an exterior temperature-controlled jacketed vessel, thermal growth differences can be minimized. Further, the number of pressure vessel penetrations is limited with an exterior temperature-controlled jacketed reactor design, as compared to the interior membrane wall design. The interior membrane wall requires numerous nozzles for coolant inlet and outlet. These vessel wall penetrations offer undesirable points of stress and crevice corrosion for the pressure vessel.
  • an exterior temperature-controlled jacketed pressure vessel may be clad, lined, or coated with a wide variety of materials, simply and economically.
  • an exterior temperature-controlled jacket design system tends to provide a more uniform temperature (and thus better corrosion control) across exposed surfaces
  • the external temperature controlled jacketed reactor design can reduce the necessity for inert gas purges, as per those that would be necessary for the gas spaces or chamber behind an interior membrane wall design. These purges are undesirable gas diluents.
  • the invention comprises a reactor for gasifying carbonaceous materials, and in particular halogenated materials.
  • the reactor includes an interior lining of one or more refractory materials defining a reactor chamber, a pressure vessel enclosing the refractory lining and reactor chamber and one or more channels defined about the pressure vessel and substantially surrounding or encompassing the enclosed reactor chamber, and through which a heat transfer fluid may be circulated.
  • the one or more channels are connected to a heat transfer fluid circulation system.
  • pressure vessel and also preferably lining wall temperatures can be controlled. Operationally, when the reactor chamber temperature is high, the circulation system will be operated to cool the vessel wall, or maintain the vessel wall temperature below certain desirable limits. When the reactor is not running, the circulation system can be operated to heat the reactor chamber lining above a minimal desired temperature.
  • a corrosion resistant cladding lining the pressure vessel is included.
  • the invention includes methods for gasifying a carbonaceous feed including halogenated materials in a reactor which comprises a first pressure vessel lined with a refractory material, comprising the steps of feeding the carbonaceous feed and oxygen to the reactor under reducing conditions so as to produce products therefrom including a synthesis gas, and circulating a heat transfer fluid in contact with outside first pressure vessel wall portions such that the fluid maintains an exterior reactor wall temperature over at least the outside first pressure vessel wall portions which is below a target level, the target level being substantially below operational reactor temperatures and preferably being within a range of approximately 150°C to 250°C.
  • Figure 1 is a block flow diagram of a preferred embodiment of a gasification process, to which the instant invention applies.
  • Figure 2A details more specifically features of a gasifier found in Figure 1.
  • Figure 2B illustrates a heat transfer fluid control system useable with a gasifier of Figure 2.
  • Figure 3 illustrates a prior art hot wall concept for a reactor vessel.
  • Figure 4 illustrates a prior art concept of an internal membrane wall reactor vessel for a gasifier.
  • Figures 5A-5F illustrate an integrally jacketed vessel of the instant invention, illustrating a vessel within a vessel concept, with one or more channels being defined by various means including by dimpling or baffling.
  • Figures 6A-6D illustrate an external membrane wall or a panel embodiment of the instant invention, with channels defined by coil type structure.
  • Figure 7 illustrates jacket zone arrangements.
  • An embodiment of a preferred, illustrative gasification process for halogenated materials of a type more particularly described in our related PCT application ("Method and Apparatus for the Production of One or More Useful Products from Lesser Value Halogenated Materials", PCT international application PCT/US/98/26298, published 1 July 1999, international publication number WO 99/32937) will be discussed briefly, offering a prime application for the instant invention.
  • Such gasification process can be viewed as comprised of a number of major processing areas, as illustrated in the block flow diagram of Figure 1. 1) Gasifier 200
  • the gasifier area 200 of a preferred embodiment consists of two reaction vessels, R-200 and R-210, and their ancillary equipment for the principal purpose of reforming the halogenated material, typically RCl's.
  • the halogenated feed (stream 144) is atomized into a primary reactor R- 200 with oxygen 291 and steam 298.
  • the RC1 or the like components are partially oxidized and converted to carbon monoxide, hydrogen chloride, hydrogen and lesser amounts of water vapor and carbon dioxide, with trace amounts of other substances including soot (being essentially carbon).
  • the products from R-200 preferably flow into a secondary reactor R-210, where all reactions proceed to completion, thus yielding high efficiencies for all halogenated species and tending to minimize undesirable side products such as soot.
  • the reactor vessel shells and connecting conduit are preferably "jacketed", as discussed more fully below in accordance with the instant invention.
  • the jacketing creates one or more channels connected to a closed heat transfer fluid system S- 280, illustrated in part in Figure 2B.
  • hot gases from the reactor R-210 are preferably cooled in a quench area 300 by direct contact with a circulating aqueous stream.
  • Reactor effluent or product gas and the aqueous stream can be intimately mixed in a quench vessel.
  • the mixture can then flow to a vapor- liquid separator drum from which a quenched gas can pass overhead and a bottoms liquid can be cooled and recycled to the quench.
  • Particulates in the product gas from a reactor system can be scrubbed from the gas stream in a scrubber in particle recovery stage 350.
  • the gas from the scrubber is preferably then introduced to a hydrogen halide or HCl absorption column 400.
  • Noncondensible components can pass through the absorber overheads and on to a syngas finishing area 700.
  • HCl in the gas from the scrubber can be absorbed to provide an aqueous acid bottoms stream.
  • This aqueous acid stream can be filtered and passed through an acid cleanup unit 450 to remove final traces of particulates and organics, yielding a product grade aqueous HCl product.
  • the product can be sold as is, or further processed to yield anhydrous HCl as desired (the suitable steps and apparatus for doing so being taught in the prior application).
  • a caustic scrubber and syngas flare system are included in a syngas finishing area 700.
  • Gasifier area 200 in the embodiment as discussed above, consists of two reaction vessels R-200 and R- 210 and their ancillary equipment for the principal purpose of halogenated feed material reformation.
  • the halogenated material will be assumed to comprise chlorinated organic materials (RCl's).
  • Primary gasifier R-200 functions as a down fired, jet stirred reactor, the principal purposes of which are to atomize the liquids fed to R- 200, evaporate the liquids, and thoroughly mix the vaporized feed with oxygen, moderator, and hot reaction products.
  • the gasifier preferably operates at approximately 1450°C and 5 bars gauge (75 psig). These harsh conditions tend to insure near complete conversion of all feed components in R-200.
  • the instant invention discloses providing a gasifier shell that is jacketed for pressure vessel wall temperature control.
  • System S-280 includes a cooler E-280, surge drum D-280, and pumps P-280 for circulating a heat transfer fluid, preferably Dowtherm GRP or Syltherm 800, but possibly being other fluids including water.
  • a heat transfer fluid preferably Dowtherm GRP or Syltherm 800, but possibly being other fluids including water.
  • Hot, refractory-lined gas vessels and piping up to and including a quench inlet are preferably completely jacketed.
  • a small heater E-281 is also preferably provided to heat a heat transfer fluid to operating conditions from a cold start as well as for maintaining lining temperature during down times.
  • the temperature of a vessel shell will preferably be controlled at approximately 200°C, or between approximately 250°C and 150°C.
  • the theoretical dewpoint of the hydrogen-halide containing gas mixture is approximately 130° -150°C.
  • the true dewpoint however can be altered by the presence of salts, metals, or other corrosion products.
  • the wall temperature is preferably maintained at a safe margin above the theoretical dew point.
  • the dry gaseous HCl corrosion rate increases exponentially with temperature. It is therefore undesirable to heat the vessel shell walls more than necessary to prevent aqueous condensation.
  • the jacketing system will attempt to control wall temperatures at all times, even downtime, except as necessary to perform system maintenance. Such control, even during down time, prevents atmospheric moisture from condensing as a corrosive liquid due to residual HCl or like substances in the system.
  • the temperature of the reactor walls preferably receives constant control.
  • the present invention discloses a refractory lined pressure vessel, preferably with careful selection of materials of construction to insure a reliably long life for the gasifier.
  • prior art "hot wall” concepts, illustrated in Figure 3 are not optimal and are possibly inadequate by themselves for controlling pressure vessel wall conditions for the gasification of carbonaceous materials, especially halogenated materials.
  • the wall temperature cannot be preferably maintained with sufficient discipline, including both above dewpoint and below desired maximum dry temperatures, at all times and across the range of ambient conditions necessary. For instance, gas by-passing behind refractory 20, 22, 24 and optionally 26 or a local refractory failure could overheat wall 28 resulting in excessive corrosion rates. Further, wall conditions during start-up, shutdown, idle periods and normal operation at cold ambient conditions cannot be controlled. Permitting such conditions and risks is not particularly desirable for a vessel operating at approximately 5 barg and especially if containing hot HCl -bearing syngas.
  • the prior art interior membrane design provides better wall temperature control than the "hot wall” concept of Figure 3, but is still not ideal.
  • the membrane 34 presents significant complexity and challenges for the design and fabrication of the numerous panels and sections required to cover an entire vessel wall 28 area.
  • the membrane 34 also poses substantial maintenance problems, requiring vessel entry, refractory removal, and possibly membrane panel removal for repair. Since the membrane must be of high alloy, this installation may be more expensive than the jacketed vessel design of the instant invention.
  • the vessel 28 will require lining or cladding 30, or a complex chamber pad system with inert gas installed. This pad, typically N 2 , is an undesired gas diluent. In some designs of the instant invention, such cladding may be foregone.
  • the jacketed shell of the instant invention including an exterior channel or channels as illustrated in Figures 5-11, combined with a heat transfer fluid control system, as illustrated in Figure 2B, is a preferred design for gasifier vessels, in particular for halogenated material gasifier vessels.
  • a vessel wall temperature can also be maintained above dewpoint for essentially all operating modes.
  • a jacketed heat transfer design provides an efficient, practical and disciplined cooling capability to limit wall temperatures.
  • Design alternatives for the jacketing as illustrated in Figures 5-11 include internal jacketing, external membrane wall or panels, welded "half-pipe,” dimple jacketing, coil jacketing of the vessel, and external panels.
  • a temperature control jacket could be a "vessel in a vessel” design, illustrated in Figure 5 as well as Figure 2 A.
  • a heat transfer fluid 36 could be circulated through a channel or channels 38 defined by such jacket 40, which channel 38 might comprise simply a space created between two vessel walls. In such a space, as illustrated in Figure 5B, the heat temperature control fluid could preferably be introduced with tangentially oriented nozzles to impart a swirling flow pattern throughout the jacket.
  • a plain jacket offers the simplest construction and thus potentially a lower initial cost. The plain jacket may be more suitable for condensing, heating media than for use with sensible fluids.
  • the plain jacket amounts to a double wall on the reactor vessel.
  • agitating nozzles are recommended, as illustrated in Figure 5B.
  • Agitating nozzles 50 may be used to direct inlet fluid 36 more or less tangentially into a jacket 40, increasing the effective velocity and turbulence level. Then used with condensing media, impingement protection is highly recommended.
  • Alternatives include the use of larger or multiple inlet nozzles.
  • a "jacket in jacket" design is used with internal baffling, illustrated in
  • FIGS 5C and 5D This consists of a "vessel in a vessel” where the heat transfer fluid is circulated through chambers defined by two pressure vessel walls, interior pressure vessel wall 28 and jacket pressure vessel wall 40 and baffles 52.
  • the fluid is circulated by a circulation control system to carefully control the velocity and heat transfer coefficient of the heat transfer fluid in order to maintain vessel walls and cladding within certain temperature ranges, substantially independently of the temperature within the reactor.
  • Preferred conduit designs could balance between heat transfer coefficients and pressure drop considerations.
  • Preferred baffles could be wound in a spinal or helix pattern around the reactor shell 28, for one preferred embodiment.
  • a spiral plate baffle consists of a spiral strip welded edgewise to the pressure vessel shell.
  • a dimpled jacket, Figure 5E and 5F offers a variation on the baffled jacket design.
  • an outer shell 40 is fitted with regular indentations 54 of the shell material. These dimples 54 are applied in regular pattern and are intended to induce turbulence. Dimples 52 are welded to vessel wall 28.
  • a plate coil of the weld-on variety as illustrated in Figure 6D is also possible, with embossing to create fairly well-defined flow channels.
  • a clamp on plate coil might be used as well, being attached by clamping rather than by spot welding to the vessel.
  • jackets may be divided into several sections, each having a separate inlet and outlet. These zones can be used to advantage in critical applications to improve temperature uniformity in the vessel to remove condensate more rapidly from all the areas of the jacket when a condensing medium is used, to decrease the temperature change in a sensible medium, to control weld temperature in any vapor spaced area and to keep the jacket pressure drop within allowable values.
  • cladding the pressure vessel wall may be desirable.
  • Non-metal claddings for the gasifier vessel are not a preferred design, as they may be insufficiently "tough" to provide long service life. Refractory thermal movement and local hotspots due to refractory failure or gas bypassing may breach the integrity of presently known non-metal linings. Therefore, a high alloy corrosion resistant metal cladding 30 will preferably be used in current preferred embodiments.
  • inside vessel wall portions are preferably maintained at or slightly above 200°C to remain above the gas dewpoint.
  • Bulk HCl gas dewpoint is estimated in the 130 - 150°C range, but local dewpoint elevation due to metal corrosion products dictates the higher operating temperature.
  • a high temperature, synthetic heat transfer fluid such as a Dowtherm A
  • High temperature stability of the fluid is important to minimize the effects of local hotspots on long term fluid stability and temperature control.
  • Fluid properties and shell failure scenarios should dictate operating pressures of the jacket system. Care should be exercised in the inclusion and design of nozzles and appurtenances on the gasifier pressure vessel. Shell penetrations should be minimized, and the necessary penetrations carefully jacketed and designed for temperature control.
  • the instant jacketed reactor design as illustrated in Figures 5-11 employs one or more interior layers of refractory 20, 22, 24 and optimally 26 suitable for exposure to hot raw gas, possibly hydrogen halide-containing gas, see Figure 5A.
  • the one or more layers of refractory will typically include a "hot-face" refractory layer 20 for chemical resistance and an insulating refractory layer 22 for heat transfer control.
  • High alumina refractory brick (more than 99 percent) with an insulating firebrick refractory is one option.
  • This refractory system would be installed directly in a pressure vessel 28. External insulation 32 may also be included.
  • any number of corrosion resistant materials could surround the refractory layer to serve as cladding, if desired, and protect the pressure vessel wall against corrosive media.
  • the vessel shell could be lined with plastic materials, ceramic, glass, or other coatings. Most preferably, however, the vessel wall would be clad with a metal in the form of a corrosion resistant alloy 30. The alloy provides the best combination of corrosion resistance and mechanical toughness.
  • Other known lining alternatives could be subject to damage and gas permeation due to thermal movement of the refractory, or differential expansion between the lining and the steel shell. Hastelloy Alloy B3 and Hastelloy Alloy C- 276 are two good cladding alternatives for the lining.
  • Hastelloy Alloy C-276 offers less resistance to pure aqueous hydrogen halide solutions but higher resistance to solutions with minor contaminants such as metal salts, dissolved oxygen or similar.
  • Use of a corrosion resistant alloy layer also allows the use of low alloy steel for the actual pressure vessel shell 28 construction.
  • Corrosion resistance and vessel integrity is further achieved in the instant invention by separately and independently (within limits, given the reactor temperature) controlling the temperature of the pressure vessel walls 28 and lining through the channel or channels 38 provided by an external jacketing system 40.
  • the pressure vessel wall and lining can be maintained above the condensation point of the vessel contents, plus a nominal margin of safety of typically 50°C. Securing such wall temperature control has the additional advantage that a cladding material can then be selected for maximum dry gas phase corrosion resistance.
  • vessel well temperature control is accomplished by "jacketing" the vessel with one or more conduits 38 and circulating through these a temperature control medium 36.
  • the conduit or conduits should be connected to a fluid circulation control system, as illustrated Figure 2B.
  • Preferred embodiments of the present invention could employ one or two phase heat transfer.
  • a two-phase system requires a more sophisticated design and complex piping, but provides a very high heat transfer coefficient.
  • the heat transfer fluid can be water or any number of commercially available fluids such as Dowtherm® products or Therminol® products or similar. Important parameters to consider in fluid selection concern the physical properties and behavior of the fluid and their interaction with the design of the jacket.
  • a heat transfer fluid circulation system S-280 of the instant invention consists of a surge drum or tank D-280 for holding fluid inventory, a pump P-280 suitable for pressuring the fluid through the network and jacket(s), and heat exchanger H-280 for (1) rejecting heat to the atmosphere or another media during normal operating conditions and for (2) heating the heat transfer fluid to bring the system to operating conditions prior to introduction of halogenated organic materials.
  • the system S- 280 can be furnished complete with appropriate instrumentation (not shown) to control the jacketed reactor surface temperature at the desired temperature given the status of the gasification reactor process in general.
  • Example 1 The following example is provided for appreciation of the instant inventive design. Example 1
  • Chlorinated Organic Material 9037 kg/hr
  • the resulting gasification reactions resulted in a synthesis gas stream rich in hydrogen chloride and chamber conditions of approximately 1450°C and 5 barg.
  • the reactor was lined with a 6" (15.24 cm) thick layer of hot-face high alumina refractory brick backed by 9" (22.86 cm) of insulating firebrick. This refractory installation limited heat loss to the vessel wall.
  • the pressure vessel was a low-alloy steel clad with 3 mm thick Hastelloy C-276.
  • the vessel included an integral jacket that covered essentially all vessel surface area.
  • the jacket included internal baffling to direct fluid flow and control velocity and heat transfer coefficients.
  • Typical limits were a minimum of 1 m sec to minimize fouling and maintain an acceptable heat transfer coefficient. A maximum velocity of approximately 4 m/sec limited pressure drop to within acceptable bounds.
  • the heat transfer fluid inventory was stored in a low-pressure tank. This tank may be padded with an inert gas to control pressure and exclude oxygen from the system. A typical flow of approximately 1200 gpm was pumped by a centrifugal pump through the jacket system. Fluid return from the jacket passed through a water-cooled heat exchanger for rejecting heat from the system. The heat exchanger exit was controlled at 200°C, which was approximately 50°C above the pure hypothetical condensation point of the vessel contents; 50°C was considered a safe margin to avoid the effects of contaminants that elevated the condensation temperature. The surface temperature was thus controlled near its target of 200°C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Apparatus For Radiation Diagnosis (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un réacteur de gazéification de matières carbonées pourvu d'un revêtement intérieur contenant au moins une matière réfractaire, d'une cuve sous pression renfermant ledit revêtement réfractaire, de préférence un placage résistant à la corrosion revêtant ladite cuve, et d'au moins un canal de circulation d'un fluide de transfert thermique enveloppant ladite cuve sous pression pour réguler la température des parois de la cuve et de préférence la température dudit revêtement, pendant le temps d'immobilisation.
PCT/US2001/014595 2000-05-05 2001-05-04 Cuve refractaire sous pression WO2001086220A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MXPA02010887A MXPA02010887A (es) 2000-05-05 2001-05-04 Recipiente refractario a presion.
JP2001583119A JP2003532789A (ja) 2000-05-05 2001-05-04 耐熱圧力容器
EP01935096A EP1285049A2 (fr) 2000-05-05 2001-05-04 Cuve refractaire sous pression
BR0110397-0A BR0110397A (pt) 2000-05-05 2001-05-04 Recipiente de pressão refratário
AU2001261220A AU2001261220A1 (en) 2000-05-05 2001-05-04 Refractory pressure vessel
NO20025248A NO20025248D0 (no) 2000-05-05 2002-11-01 Ildfast trykkbeholder

Applications Claiming Priority (2)

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US56582600A 2000-05-05 2000-05-05
US09/565,826 2000-05-05

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WO2001086220A2 true WO2001086220A2 (fr) 2001-11-15
WO2001086220A3 WO2001086220A3 (fr) 2002-06-13

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JP (1) JP2003532789A (fr)
CN (1) CN1427879A (fr)
AU (1) AU2001261220A1 (fr)
BR (1) BR0110397A (fr)
MX (1) MXPA02010887A (fr)
NO (1) NO20025248D0 (fr)
RU (1) RU2002132656A (fr)
WO (1) WO2001086220A2 (fr)

Cited By (20)

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WO2007054505A2 (fr) * 2005-11-08 2007-05-18 Solvay (Société Anonyme) Procede de fabrication de dichloropropanol par chloration de glycerol
EP2162510A1 (fr) * 2007-05-25 2010-03-17 Gasek OY Procédé pour gazéifier un combustible solide et gazéificateur à co-courant
CN101767387A (zh) * 2010-03-02 2010-07-07 烟台桑尼橡胶有限公司 一种硫化罐
CN101892084A (zh) * 2010-08-09 2010-11-24 华东理工大学 规模化固定床生物质气化炉及低含氧燃气的生产工艺
CN101987974A (zh) * 2010-08-09 2011-03-23 建设部沈阳煤气热力研究设计院 规模化生物质固定床气化炉
US8124814B2 (en) 2006-06-14 2012-02-28 Solvay (Societe Anonyme) Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol
EP2404984A3 (fr) * 2010-05-21 2012-05-30 General Electric Company Système de protection des surfaces de gazogène contre la corrosion
US8197665B2 (en) 2007-06-12 2012-06-12 Solvay (Societe Anonyme) Aqueous composition containing a salt, manufacturing process and use
US8258350B2 (en) 2007-03-07 2012-09-04 Solvay (Societe Anonyme) Process for the manufacture of dichloropropanol
US8273923B2 (en) 2007-06-01 2012-09-25 Solvay (Societe Anonyme) Process for manufacturing a chlorohydrin
US8314205B2 (en) 2007-12-17 2012-11-20 Solvay (Societe Anonyme) Glycerol-based product, process for obtaining same and use thereof in the manufacturing of dichloropropanol
US8378130B2 (en) 2007-06-12 2013-02-19 Solvay (Societe Anonyme) Product containing epichlorohydrin, its preparation and its use in various applications
US8471074B2 (en) 2007-03-14 2013-06-25 Solvay (Societe Anonyme) Process for the manufacture of dichloropropanol
US8507643B2 (en) 2008-04-03 2013-08-13 Solvay S.A. Composition comprising glycerol, process for obtaining same and use thereof in the manufacture of dichloropropanol
US8536381B2 (en) 2008-09-12 2013-09-17 Solvay Sa Process for purifying hydrogen chloride
US8715568B2 (en) 2007-10-02 2014-05-06 Solvay Sa Use of compositions containing silicon for improving the corrosion resistance of vessels
US8795536B2 (en) 2008-01-31 2014-08-05 Solvay (Societe Anonyme) Process for degrading organic substances in an aqueous composition
WO2015074741A1 (fr) * 2013-11-23 2015-05-28 Linde Aktiengesellschaft Récipient pour gazéificateur à basse température
US9309209B2 (en) 2010-09-30 2016-04-12 Solvay Sa Derivative of epichlorohydrin of natural origin
US9663427B2 (en) 2003-11-20 2017-05-30 Solvay (Société Anonyme) Process for producing epichlorohydrin

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US8673234B2 (en) 2008-03-04 2014-03-18 Aerojet Rocketdyne Of De, Inc. Reactor vessel and liner
US20100031570A1 (en) * 2008-08-07 2010-02-11 Wei Chen Method and system for an integrated gasifier and syngas cooler
CN102851080B (zh) * 2011-06-30 2015-08-26 通用电气公司 整体气化联合循环发电系统和气化反应器以及方法
CN104479755B (zh) * 2014-11-26 2017-02-22 新奥科技发展有限公司 流化床气化炉、煤催化气化系统及气化工艺

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US4343626A (en) * 1980-02-19 1982-08-10 Brennstoffinstitut Freiberg Reactor for producing a carbon monoxide and hydrogen containing gas
DE3009850A1 (de) * 1980-03-14 1981-09-24 Karrena GmbH, 4000 Düsseldorf Reaktorbehaelter
EP0079092A1 (fr) * 1981-11-09 1983-05-18 Shell Internationale Researchmaatschappij B.V. Appareil pour gazéifier des combustibles finement divisés
US4655793A (en) * 1984-08-25 1987-04-07 Krupp Koppers Gmbh Method for operating a coal gasifier
DE4017219A1 (de) * 1990-05-29 1991-12-05 Babcock Werke Ag Vorrichtung zur vergasung von kohlenstoffhaltigen materialien
WO1999032397A1 (fr) * 1997-12-22 1999-07-01 The Dow Chemical Company Production d'un ou plusieurs produits utiles, a partir de materiaux halogenes de valeur inferieure
DE19829385C1 (de) * 1998-07-01 1999-10-28 Krc Umwelttechnik Gmbh Vorrichtung zur Flugstromvergasung von kohlenstoffhaltigen Brenn-, Rest- und Abfallstoffen

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9663427B2 (en) 2003-11-20 2017-05-30 Solvay (Société Anonyme) Process for producing epichlorohydrin
WO2007054505A3 (fr) * 2005-11-08 2007-07-26 Solvay Procede de fabrication de dichloropropanol par chloration de glycerol
WO2007054505A2 (fr) * 2005-11-08 2007-05-18 Solvay (Société Anonyme) Procede de fabrication de dichloropropanol par chloration de glycerol
CN101068761B (zh) * 2005-11-08 2011-11-23 索尔维公司 通过甘油的氯化制备二氯丙醇的方法
US8124814B2 (en) 2006-06-14 2012-02-28 Solvay (Societe Anonyme) Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol
US8258350B2 (en) 2007-03-07 2012-09-04 Solvay (Societe Anonyme) Process for the manufacture of dichloropropanol
US8471074B2 (en) 2007-03-14 2013-06-25 Solvay (Societe Anonyme) Process for the manufacture of dichloropropanol
EP2162510A4 (fr) * 2007-05-25 2012-08-22 Gasek Oy Procédé pour gazéifier un combustible solide et gazéificateur à co-courant
EP2162510A1 (fr) * 2007-05-25 2010-03-17 Gasek OY Procédé pour gazéifier un combustible solide et gazéificateur à co-courant
US8273923B2 (en) 2007-06-01 2012-09-25 Solvay (Societe Anonyme) Process for manufacturing a chlorohydrin
US8378130B2 (en) 2007-06-12 2013-02-19 Solvay (Societe Anonyme) Product containing epichlorohydrin, its preparation and its use in various applications
US8399692B2 (en) 2007-06-12 2013-03-19 Solvay (Societe Anonyme) Epichlorohydrin, manufacturing process and use
US8197665B2 (en) 2007-06-12 2012-06-12 Solvay (Societe Anonyme) Aqueous composition containing a salt, manufacturing process and use
US8715568B2 (en) 2007-10-02 2014-05-06 Solvay Sa Use of compositions containing silicon for improving the corrosion resistance of vessels
US8314205B2 (en) 2007-12-17 2012-11-20 Solvay (Societe Anonyme) Glycerol-based product, process for obtaining same and use thereof in the manufacturing of dichloropropanol
US8795536B2 (en) 2008-01-31 2014-08-05 Solvay (Societe Anonyme) Process for degrading organic substances in an aqueous composition
US8507643B2 (en) 2008-04-03 2013-08-13 Solvay S.A. Composition comprising glycerol, process for obtaining same and use thereof in the manufacture of dichloropropanol
US8536381B2 (en) 2008-09-12 2013-09-17 Solvay Sa Process for purifying hydrogen chloride
CN101767387A (zh) * 2010-03-02 2010-07-07 烟台桑尼橡胶有限公司 一种硫化罐
US8372251B2 (en) 2010-05-21 2013-02-12 General Electric Company System for protecting gasifier surfaces from corrosion
EP2404984A3 (fr) * 2010-05-21 2012-05-30 General Electric Company Système de protection des surfaces de gazogène contre la corrosion
CN101987974A (zh) * 2010-08-09 2011-03-23 建设部沈阳煤气热力研究设计院 规模化生物质固定床气化炉
CN101892084A (zh) * 2010-08-09 2010-11-24 华东理工大学 规模化固定床生物质气化炉及低含氧燃气的生产工艺
US9309209B2 (en) 2010-09-30 2016-04-12 Solvay Sa Derivative of epichlorohydrin of natural origin
WO2015074741A1 (fr) * 2013-11-23 2015-05-28 Linde Aktiengesellschaft Récipient pour gazéificateur à basse température

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CN1427879A (zh) 2003-07-02
NO20025248L (no) 2002-11-01
BR0110397A (pt) 2003-02-25
WO2001086220A3 (fr) 2002-06-13
EP1285049A2 (fr) 2003-02-26
JP2003532789A (ja) 2003-11-05
MXPA02010887A (es) 2004-09-06
NO20025248D0 (no) 2002-11-01
RU2002132656A (ru) 2004-08-10
AU2001261220A1 (en) 2001-11-20

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