EP0581546A1 - Verfahren und Vorrichtung zur Vernichtung von Natrium enthaltenden Abfällen - Google Patents

Verfahren und Vorrichtung zur Vernichtung von Natrium enthaltenden Abfällen Download PDF

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Publication number
EP0581546A1
EP0581546A1 EP93305848A EP93305848A EP0581546A1 EP 0581546 A1 EP0581546 A1 EP 0581546A1 EP 93305848 A EP93305848 A EP 93305848A EP 93305848 A EP93305848 A EP 93305848A EP 0581546 A1 EP0581546 A1 EP 0581546A1
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EP
European Patent Office
Prior art keywords
refractory
combined
fuel
sodium
binder
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.)
Granted
Application number
EP93305848A
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English (en)
French (fr)
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EP0581546B1 (de
Inventor
Clifford Lawrence Spiro
Herbert Clark Peters
Thomas Link Guggenheim
Timothy Mark Allen
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.)
SABIC Global Technologies BV
Original Assignee
General Electric Co
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Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0581546A1 publication Critical patent/EP0581546A1/de
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Publication of EP0581546B1 publication Critical patent/EP0581546B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/44—Details; Accessories
    • F23G5/48—Preventing corrosion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/008—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for liquid waste
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
    • F23M5/00—Casings; Linings; Walls

Definitions

  • This invention relates to the destruction of waste materials, and more particularly to the combustion of waste streams which contain organic compounds and which are high in sodium.
  • a major cost element in chemical processes carried out on a commercial scale is the disposal of non-recyclable by-products and wastes. These may include organic and inorganic compounds, many of which are toxic or otherwise hazardous. Increased attention to environmental hazards has made it imperative to develop improved methods for disposing of such waste products. In particular, many of such products must be destroyed so that they do not pass into the environment and cause harm.
  • a single example of a plastics production process which produces wastes is the process of making polyimides, and particularly polyetherimides. Many steps are involved, only a few of which need be described here to indicate the complexity of the waste materials which must be dealt with.
  • an early step is the nitration of a phthalimide with nitric acid, which produces as wastes excess nitric acid and various nitro-substituted phthalic acid derivatives.
  • the nitrophthalimide is slurried with waterand the slurry is contacted with an organic solvent, whereupon the nitrophthalimide dissolves in the organic phase and leaves behind an aqueous waste containing traces of various compounds, organic and inorganic.
  • the nitrophthalimide in the organic solution undergoes a displacement reaction with the disodium salt of a dihydroxyaromatic compound such as 2,2-bis(4-hydroxyphenyl)propane, commonly designated bisphenol A, with the formation of a bisimide and sodium nitrite as a by-product.
  • This displacement reaction ordinarily takes place in the presence of a phase transfer catalyst, traces of which may also be found in the waste stream. Numerous other by-products, as well as further quantities of those already mentioned, are removed by further extraction of the organic reactant solutions with aqueous sodium hydroxide.
  • the bisimide subsequently undergoes further reactions to form the polyetherimide.
  • the complexity of the combined aqueous waste stream formed in this production process will be apparent from the above description. It contains large quantities of water, typically 60-80% and usually on the order of 70% by weight. About 15-30%, usually about 20%, is ordinarily nitrite ion (in the form of sodium nitrite) and about 5-10%, usually about 7-8%, various organic compounds, and the remainder includes sodium hydroxide. The sodium ion content of the aqueous waste stream is substantial, often on the order of 5-15% and usually about 7-8% by weight. pH values may be in the range of about 2-12 but are usually on the alkaline side, typically about 10-12.
  • a typical waste disposal method for such by-products involves feeding the aqueous waste stream into a multi-stage destruction apparatus including oxidation/combustion and reduction stages.
  • organic compounds are combusted and nitrogen compounds converted to nitrogen oxides in one or more stages conducted in an oxygen-rich atmosphere.
  • At least one other stage may be conducted in a reducing atmosphere created by the injection of natural gas, the effect of which is to convert nitrogen compounds to elemental nitrogen. All of these stages are carried out at very high temperature, typically on the order of 1000-1300°C.
  • refractories have been evaluated for use in a process such as that described above. They are typically in the form of brick containing various proportions of combined aluminum, generally in combination with combined silicon and other combined metals and nonmetals. For the most part, however, such brick has been found to have a very short life when exposed to a waste stream high in sodium.
  • the present invention is based on the discovery of certain types of refractory materials high in aluminum which are particularly resistant to the corrosive effects of sodium compounds. Combustion chambers lined with these refractory materials are capable of undergoing hundreds of hours of contact at high temperatures without failing. Moreover, the slag produced when such refractories are used is small in volume and relatively easy to remove and dispose of.
  • the invention in one of its aspects is a method for destroying waste materials which comprises feeding a stream comprising waste products, including at least about 0.1% by weight combined sodium, to a treatment vessel, combusting said organic waste products at temperatures in the range of about 1000-1300°C and removing by-products including sodium compounds from said vessel,
  • a refractory material which comprises at least about 85% by weight combined aluminum calculated as aluminum oxide, and which, if of sintered construction, comprises alumina grains and an aluminosilicate binder and contains at least about 6.5% combined silicon calculated as silicon dioxide.
  • the drawing illustrates a typical combustion apparatus for wastes which may be employed in accordance with the invention.
  • the present invention is capable of employment to destroy a wide variety of organic and inorganic waste products. For the most part, it is advantageous in connection with waste streams containing organic chemicals and a relatively high concentration of sodium compounds, the latter being at least about 0.1% by weight and frequently at least about 5% by weight.
  • the vessel into which the waste stream is fed may be made of any non-porous material which is capable of withstanding the combustion temperatures of about 1000-1300°C attained during the process. Metals such as steel are typically used. It is necessary, however, that the interior surface which contacts the waste products be a suitable refractory material in order to prevent the rapid corrosion of metal which occurs upon contact with sodium compounds at the prevailing combustion temperatures.
  • the nature of the refractory lining of the vessel is a key feature of the invention. It should comprise at least about 85% and preferably at least about 90% combined aluminum by weight, calculated as aluminum oxide (alumina).
  • a binder material In sintered refractories, the presence and nature of a binder material are also critical. Said binder should comprise a major proportion of aluminosilicate, and should be present in sufficient amount to provide at least about 6.5% combined silicon, calculated as silicon dioxide (silica), in the refractory. Mullite is a particularly effective form of aluminosilicate for use as a binder.
  • the alumina therein essentially serves as its own binder. In that case, the presence of a silicon-containing binder is not required, although it may be present in small proportions.
  • the refractory be free from heavy metals, which may be environmentally harmful if present in the slag.
  • some refractories contain chromium which remains in the slag in the hexavalent state, known to be an environmental hazard. Such materials are unsatisfactory for the purposes of the invention.
  • the bulk density of the refractory used according to the present invention is generally at least about 2.9 g./cm. 3 . It is most often above 3.0 g./cm. 3 .
  • the silicon proportion is substantially higher in sintered than in fused-cast brick.
  • the reason for this is essentially the one described hereinabove; no binder, which is the aluminosilicate-containing and therefore the predominant silicon-containing constituent, is necessary in the fused-cast brick, but one is necessary in the sintered brick.
  • GreenAl-90 differs from the other bricks in containing 1.5% phosphorus as phosphorus pentoxide.
  • “GreenAl-90” has been found slightly superior to "Korundal XD" in wear characteristics. Accordingly, in a preferred embodiment of the invention the refractory also contains at least about 1% combined phosphorus as P 2 0 5 .
  • the slag produced in the method of this invention may vary in nature from a uniformly granular material to one which is thick and flowable near the refractory surface and more granular at a distance from said surface.
  • the formation of a thick, flowable slag is frequently advantageous in that less shearing of the pebbles from the refractory surface may occur than with a granular slag.
  • the organic constituents of the waste stream are combusted in the aforementioned vessel, at temperatures above about 700°C and most often in the range of about 1000-1300°C.
  • the precise nature of the combustion step is not critical for the purposes of this invention. Most often, however, it comprises at least one oxidizing and at least one reducing step, conducted under fuel-lean and fuel-rich conditions, respectively.
  • the fuel is normally natural gas and is employed in admixture with an oxygen-containing gas, typically air.
  • Atypical combustion operation according to the invention utilizes the apparatus shown in the drawing.
  • the waste stream is charged at 2 to the top zone 4 of a three-zone combustion stack 1, where it is contacted with air and natural gas entering at 6 and 8, respectively.
  • the stream then passes downward via passage 10 into second zone 12, and finally through passage 16 into third zone 18.
  • Additional natural gas and air are introduced via nozzles 14 and 20, producing fuel-rich or fuel-lean zones as desired to result in reduction of the nitrogen oxides to elemental nitrogen or oxidation of nitrogen compounds to nitrogen oxides, respectively.
  • the vapors of the waste stream are passed through downcomer 22 where they are quenched and removed by contact with water introduced through water jet 24.
  • Volatile components are removed via at least one gas conduit, with two being shown at 26 and 28, and may be passed to scrubbers for further treatment.
  • Liquid components, predominantly water, are removed from quench tank 30 through liquid conduit 32.
  • combustion stack 1 includes an external metal shell 34, typically of steel, and an inner refractory lining 36, typically of brick as previously described.
  • the thickness of lining 36 will vary with the conditions but is generally on the order of 15-30 cm., with about 20-25 cm. often being preferred.
  • attack by sodium compounds on lining 36 often causes spalling of said lining in the form of pieces of various sizes, ranging from small particles to large chunks. Most of the larger pieces are caught by grate 38, with smaller particles passing through said grate and being caught in funnel 40.
  • Said apparatus comprises a plurality of intercommunicating vertically disposed combustion stacks, means for feeding waste and fuel materials to the uppermost of said stacks, and a downcomer from the lowermost of said stacks.
  • Each of said stacks, and each passage connecting them, has its inner surface lined with the above-described refractory.
  • Said apparatus optionally further comprises fuel-lean and fuel-rich zones and means for supplying oxygen-containing gas and fuel, respectively, to said zones, as described hereinabove.
  • the treatment system can be operated for substantially longer periods without deterioration of the interior of the treatment vessel.
  • the essential elimination of spalled refractory causes a substantial decrease or even elimination of the operational and cost burdens of conveying such material to a landfill.
  • a waste destruction unit according to the invention can operate without down time for periods of at least 128 days.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Processing Of Solid Wastes (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Gasification And Melting Of Waste (AREA)
EP93305848A 1992-07-31 1993-07-23 Verwendung eines Behandlungsgefässes zur Vernichtung von Natrium enthaltenden Abfällen Expired - Lifetime EP0581546B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US92272492A 1992-07-31 1992-07-31
US922724 1992-07-31
CA002108421A CA2108421A1 (en) 1992-07-31 1993-10-14 Method and apparatus for destroying sodium-containing waste products

Publications (2)

Publication Number Publication Date
EP0581546A1 true EP0581546A1 (de) 1994-02-02
EP0581546B1 EP0581546B1 (de) 1999-02-03

Family

ID=25676744

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93305848A Expired - Lifetime EP0581546B1 (de) 1992-07-31 1993-07-23 Verwendung eines Behandlungsgefässes zur Vernichtung von Natrium enthaltenden Abfällen

Country Status (5)

Country Link
EP (1) EP0581546B1 (de)
JP (1) JP3124871B2 (de)
CA (1) CA2108421A1 (de)
DE (1) DE69323359T2 (de)
ES (1) ES2127251T3 (de)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3712796A (en) * 1971-02-25 1973-01-23 Du Pont Heat shield for chemical waste incinerator
FR2219910A1 (de) * 1973-03-02 1974-09-27 Speichim Equip Ind Chimiq
GB2020403A (en) * 1978-04-19 1979-11-14 Heenan Environmental Systems Combustion furnace and method of operating same
DE3004186A1 (de) * 1979-02-08 1980-08-21 Nittetsu Kakoki Kk Verfahren zur verbrennungsbehandlung von ablassfluiden, die stickstoffverbindungen enthalten
US4237103A (en) * 1978-06-29 1980-12-02 Combustion Engineering, Inc. Method for disposal of sodium waste material
DE4128963A1 (de) * 1991-08-29 1993-03-04 Otto Feuerfest Gmbh Feuerfester, gegen fluorhaltige medien bestaendiger werkstoff und dessen anwendung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS622207A (ja) * 1985-06-28 1987-01-08 Hitachi Ltd 回折格子およびその製法
JPH03294780A (ja) * 1990-04-10 1991-12-25 Tokai Konetsu Kogyo Co Ltd 焼成炉

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3712796A (en) * 1971-02-25 1973-01-23 Du Pont Heat shield for chemical waste incinerator
FR2219910A1 (de) * 1973-03-02 1974-09-27 Speichim Equip Ind Chimiq
GB2020403A (en) * 1978-04-19 1979-11-14 Heenan Environmental Systems Combustion furnace and method of operating same
US4237103A (en) * 1978-06-29 1980-12-02 Combustion Engineering, Inc. Method for disposal of sodium waste material
DE3004186A1 (de) * 1979-02-08 1980-08-21 Nittetsu Kakoki Kk Verfahren zur verbrennungsbehandlung von ablassfluiden, die stickstoffverbindungen enthalten
DE4128963A1 (de) * 1991-08-29 1993-03-04 Otto Feuerfest Gmbh Feuerfester, gegen fluorhaltige medien bestaendiger werkstoff und dessen anwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CROWLEY: "Know causes of, solutions to CFB-boiler refractory problems", POWER, vol. 136, no. 1, January 1992 (1992-01-01), NEW YORK US, pages 54 - 57, XP000243659 *

Also Published As

Publication number Publication date
DE69323359D1 (de) 1999-03-18
JP3124871B2 (ja) 2001-01-15
EP0581546B1 (de) 1999-02-03
JPH06154727A (ja) 1994-06-03
CA2108421A1 (en) 1995-04-15
DE69323359T2 (de) 1999-10-07
ES2127251T3 (es) 1999-04-16

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