U.S. patent application number 14/609738 was filed with the patent office on 2016-12-29 for apparatus and methods for treatment of radioactive organic waste.
The applicant listed for this patent is Studsvik, Inc.. Invention is credited to J. Bradley Mason.
Application Number | 20160379727 14/609738 |
Document ID | / |
Family ID | 56544163 |
Filed Date | 2016-12-29 |
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United States Patent
Application |
20160379727 |
Kind Code |
A1 |
Mason; J. Bradley |
December 29, 2016 |
APPARATUS AND METHODS FOR TREATMENT OF RADIOACTIVE ORGANIC
WASTE
Abstract
Treatment of radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds. An
apparatus comprises a reaction vessel comprising a filter for
carrying out thermal treatment of the waste and a thermal oxidizer.
Utilizing co-reactants to reduce gas phase sulfur and halogen from
treatment of wastes.
Inventors: |
Mason; J. Bradley; (McCall,
ID) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Studsvik, Inc. |
Atlanta |
GA |
US |
|
|
Family ID: |
56544163 |
Appl. No.: |
14/609738 |
Filed: |
January 30, 2015 |
Current U.S.
Class: |
588/19 |
Current CPC
Class: |
B01D 39/2075 20130101;
B01J 8/087 20130101; G21F 9/30 20130101; B01J 8/24 20130101; G21F
9/32 20130101; B01D 53/04 20130101; B01J 2208/00017 20130101; G21F
9/00 20130101; G21F 9/02 20130101; B01J 2208/00823 20130101; G21F
9/12 20130101; B01D 2257/20 20130101; B01D 2258/02 20130101; B01D
2259/40001 20130101; F23G 7/061 20130101; B01D 39/2034 20130101;
B01J 8/1836 20130101; B01D 2257/30 20130101 |
International
Class: |
G21F 9/00 20060101
G21F009/00; B01D 39/20 20060101 B01D039/20; F23G 7/06 20060101
F23G007/06; B01J 8/18 20060101 B01J008/18; B01J 8/08 20060101
B01J008/08; B01D 53/04 20060101 B01D053/04; B01J 8/24 20060101
B01J008/24 |
Claims
1. An apparatus for the treatment of radioactive waste comprising
organic compounds, and sulfur-containing compounds and/or
halogen-containing compounds, the apparatus comprising: (a) a
reaction vessel comprising a filter for carrying out thermal
treatment of the waste; and (b) a thermal oxidizer.
2. The apparatus of claim 1, wherein the apparatus further
comprises: (c) an adsorption vessel comprising one or more types of
adsorbent media for adsorbing sulfur-containing compounds and/or
halogen-containing compounds after treatment of the waste by the
reaction vessel.
3. The apparatus of claim 1, wherein the reaction vessel comprising
a filter further comprises a bed in the lower portion of the
reaction vessel comprising a filter.
4. The apparatus of claim 3, wherein the bed in the reaction vessel
comprising a filter comprises the waste, one or more co-reactants
and optionally, inert bed media.
5. The apparatus of claim 4, wherein the bed is partially fluidized
or jetted.
6. The apparatus of claim 1, wherein the apparatus further
comprises a process reaction vessel upstream of the reaction vessel
comprising a filter.
7. The apparatus of claim 6, wherein the process reaction vessel
further comprises a bed in the lower portion of the process
reaction vessel.
8. The apparatus of claim 7, wherein the bed in the process
reaction vessel comprises the waste, one or more co-reactants and
optionally, inert bed media.
9. The apparatus of claim 1, wherein the temperature of the
reaction vessel comprising a filter is below the temperature at
which the sulfur-containing compounds and/or halogen-containing
compounds volatilize.
10. The apparatus of claim 1, wherein the temperature of the
process reaction vessel is below the temperature at which the
sulfur-containing compounds and/or halogen-containing compounds
volatilize.
11. The apparatus of claim 2, wherein the adsorbent media comprises
one or more types of adsorbent media selected from the group
consisting of: compounds that adsorb sulfur-containing compounds
and produces a sulfate compound; compounds that adsorb
sulfur-containing compounds and produces a metal sulfide, alkaline
earth sulfide, or another sulfide; metal or alkaline earth
adsorbents; iron, nickel or zinc metals; metal oxides; and
Al(OH).sub.3.
12. A method for treating radioactive waste comprising organic
compounds, and sulfur-containing compounds and/or
halogen-containing compounds, the method comprising: (a) adding
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds;
and one or more co-reactants to a reaction vessel comprising a
filter to form a bed in the lower portion of the reaction vessel
comprising a filter; (b) heating the reaction vessel comprising a
filter to a temperature of in the range of about 250.degree. C. to
about 1050.degree. C. to form pyrolyzed radioactive waste residues
and waste gases; (c) agitating, partially fluidizing or jetting the
bed of the reaction vessel comprising a filter; (d) optionally,
adding a reactive gas to the reaction vessel to gasify carbon in
the pyrolyzed waste residues; (e) removing pyrolyzed radioactive
waste residues from the reaction vessel comprising a filter for
disposal; and (f) transferring the waste gases from the reaction
vessel comprising a filter to a thermal oxidizer for combustion;
wherein the reaction vessel comprising a filter may optionally be
heated to a temperature of in the range of about 250.degree. C. to
about 1050.degree. C. prior to step (a).
13. The method of claim 12, wherein step (b) may be carried out
prior to step (a).
14. The method of claim 12, wherein step (d) comprises adding a
reactive gas to the reaction vessel comprising a filter to gasify
carbon in the pyrolyzed waste residues.
15. The method of claim 14, wherein the step of adding a reactive
gas to gasify carbon in the pyrolyzed waste residues is carried out
at a temperature below that which the sulfur-containing compounds
and/or halogen-containing compounds volatilize.
16. The method of claim 12, wherein the one or more co-reactants is
for treatment of waste comprising sulfur-containing compounds under
reducing conditions and is selected from the group consisting of:
compounds of calcium; zinc; iron; nickel; tin; alkali metals, such
as sodium, potassium and lithium; alkaline earth metals, such as
magnesium and barium; aluminum; bismuth; manganese; molybdenum;
phosphorus; silicon; silver; strontium; tin; calcium silicates;
commercial H.sub.2S adsorbents; or other compounds which can be
reacted with sulfur-containing compounds to form stable sulfides
and/or H.sub.2S; and mixtures thereof.
17. The method of claim 12, wherein the one or more co-reactants is
for treatment of waste comprising sulfur-containing compounds under
oxidizing conditions and is selected from the group consisting of:
compounds of calcium, magnesium, barium, sodium, potassium,
lithium, aluminum, iron, nickel, manganese, clays, calcium
silicates, or other compounds which can be reacted with
sulfur-containing compounds to form stable sulfate and sulfite
compounds with sulfur oxides (SO.sub.4.sup.2- and SO.sub.3.sup.2-),
and mixtures thereof.
18. The method of claim 12, wherein the waste and the one or more
co-reactants are heated to a temperature of about 884.degree. C. or
less to prevent decomposition or melting of sodium sulfate.
19. The method of claim 12, wherein the waste and the one or more
co-reactants are heated to a temperature of about 602.degree. C. or
less to prevent decomposition of Fe.sub.2S.
20. The method of claim 12, wherein the waste and the one or more
co-reactants are heated to a temperature of about 1050.degree. C.
or less to prevent decomposition of calcium sulfide or zinc
sulfide.
21. The method of claim 12, wherein the one or more co-reactants is
for treatment of waste comprising halogen-containing compounds and
is selected from the group consisting of: compounds of calcium,
zinc, iron, nickel, sodium, potassium, lithium, aluminum,
magnesium, barium, bismuth, cerium, cobalt, manganese, molybdenum,
silver, tin, titanium, zirconium, clays, calcium silicates, or
other compounds which can be reacted with halogen-containing
compounds to form salts or stable, non-volatile halide compounds,
and mixtures thereof.
22. The method of claim 12, wherein the waste and the one or more
co-reactants are heated to a temperature of about 801.degree. C. or
less to prevent decomposition or melting of sodium chloride.
23. The method of claim 12, wherein the bed does not contain inert
bed media.
24. The method of claim 12, wherein the method further comprises
transferring the waste gases to an adsorption vessel comprising
adsorbent for adsorbing sulfur-containing compounds and/or
halogen-containing compounds prior to transferring the waste gases
to a thermal oxidizer for combustion.
25. The method of claim 24, wherein the method further comprises
transferring the waste gases to an adsorption vessel comprising
adsorbent for adsorbing sulfur-containing compounds and/or
halogen-containing compounds prior to transferring the waste gases
to a thermal oxidizer for combustion.
26. A method for treating radioactive waste comprising organic
compounds, and sulfur-containing compounds and/or
halogen-containing compounds, the method comprising: (a) adding
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds;
and one or more co-reactants to a process reaction vessel to form a
bed in the lower portion of the process reaction vessel; (b)
heating the process reaction vessel to a temperature in the range
of about 35.degree. C. to about 1050.degree. C.; (c) agitating,
partially fluidizing or jetting the bed while maintaining the
temperature of the process reaction vessel in the range of about
35.degree. C. to about 1050.degree. C. to form fully or partially
pyrolyzed radioactive waste residues and waste gases; (d)
transferring the fully or partially pyrolyzed radioactive waste
residues and waste gases from the process reaction vessel to a
reaction vessel comprising a filter to form a bed in the lower
portion of the reaction vessel comprising a filter; (e) heating the
reaction vessel comprising a filter to a temperature in the range
of about 250.degree. C. to about 1050.degree. C.; (f) agitating,
partially fluidizing or jetting the bed of the reaction vessel
comprising a filter while maintaining the temperature of the
reaction vessel comprising a filter in the range of about
250.degree. C. to about 1050.degree. C. to form fully or partially
pyrolyzed radioactive waste residues and waste gases; (g)
optionally, adding a reactive gas to the reaction vessel comprising
a filter to gasify carbon in the partially pyrolyzed waste
residues; (h) removing the fully pyrolyzed radioactive waste
residues from the reaction vessel comprising a filter for disposal;
and (i) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion; wherein
the process reaction vessel may optionally be heated to a
temperature in the range of about 35.degree. C. to about
1050.degree. C. prior to step (a); and wherein the reaction vessel
comprising a filter may optionally be to heated to a temperature in
the range of about 250.degree. C. to about 1050.degree. C. prior to
step (d).
27. The method of claim 26, wherein step (b) may be carried out
prior to step (a).
28. The method of claim 26, wherein step (e) may be carried out
prior to step (d).
29. The method of claim 26, wherein the process reaction vessel is
heated to a temperature in the range of about 250.degree. C. to
about 1050.degree. C.
30. The method of claim 26, further comprising adding a reactive
gas to the reaction vessel comprising a filter in step (g) to
gasify carbon in the pyrolyzed waste residues.
31. The method of claim 30, wherein the step of adding a reactive
gas to gasify carbon in the pyrolyzed waste residues is carried out
at a temperature below that which the sulfur-containing compounds
and/or halogen-containing compounds volatilize.
32. The method of claim 26, wherein the one or more co-reactants is
for treatment of waste comprising sulfur-containing compounds under
reducing conditions and is selected from the group consisting of:
compounds of calcium; zinc; iron; nickel; tin; alkali metals, such
as sodium, potassium and lithium; alkaline earth metals, such as
magnesium and barium; aluminum; bismuth; manganese; molybdenum;
phosphorus; silicon; silver; strontium; tin; calcium silicates;
commercial H.sub.2S adsorbents; or other compounds which can be
reacted with sulfur-containing compounds to form stable sulfides
and/or H.sub.2S; and mixtures thereof.
33. The method of claim 26, wherein the one or more co-reactants is
for treatment of waste comprising sulfur-containing compounds under
oxidizing conditions and is selected from the group consisting of:
compounds of calcium, magnesium, barium, sodium, potassium,
lithium, aluminum, iron, nickel, manganese, clays, calcium
silicates, or other compounds which can be reacted with
sulfur-containing compounds to form stable sulfate and sulfite
compounds with sulfur oxides (SO.sub.4.sup.2- and SO.sub.3.sup.2-),
and mixtures thereof.
34. The method of claim 26, wherein the waste and the one or more
co-reactants are heated to a temperature of about 884.degree. C. or
less to prevent decomposition or melting of sodium sulfate.
35. The method of claim 26, wherein the waste and the one or more
co-reactants are heated to a temperature of about 602.degree. C. or
less to prevent decomposition of Fe.sub.2S.
36. The method of claim 26, wherein the waste and the one or more
co-reactants are heated to a temperature of about 1050.degree. C.
or less to prevent decomposition of calcium sulfide or zinc
sulfide.
37. The method of claim 26, wherein the one or more co-reactants is
for treatment of waste comprising halogen-containing compounds and
is selected from the group consisting of: compounds of calcium,
zinc, iron, nickel, sodium, potassium, lithium, aluminum,
magnesium, barium, bismuth, cerium, cobalt, manganese, molybdenum,
silver, tin, titanium, zirconium, clays, calcium silicates, or
other compounds which can be reacted with halogen-containing
compounds to form salts or stable, non-volatile halide compounds,
and mixtures thereof.
38. The method of claim 26, wherein the waste and the one or more
co-reactants are heated to a temperature of about 801.degree. C. or
less to prevent decomposition or melting of sodium chloride.
39. The method of claim 26, wherein the bed does not contain inert
bed media.
Description
FIELD OF THE ART
[0001] The embodiments described herein relate to apparatus and
methods for treating radioactive waste.
BACKGROUND
[0002] There exist many hazardous waste materials that are
difficult to dispose because of the possibility that they may
contaminate the environment. Such hazardous materials include
compounds like radioactive elements, heavy metals, sulfur, and
halogens. These materials can be commonly found in many wastes,
products, and compounds.
[0003] Typically, such hazardous waste is either buried or burned,
both of which can be costly processes. Accordingly, it is desirable
to process such wastes into materials that are more easily disposed
of at lower costs. A large number of methods for treatment of such
materials are known.
[0004] In the past, waste materials containing sulfur and halogens
have typically been treated through processes like cementation,
pyrolysis and incineration. Incineration processes Incinerators and
related processes that utilize open-flame combustion fall under
stringent and comprehensive air pollution laws that typically
render the incinerators economically infeasible.
[0005] Pyrolysis methods are generally more flexible and can be
used for the treatment of most waste materials. However, secondary
waste streams that are generated from these processes, such as
particulate waste, large volumes of scrubber solutions or dried
salts that are difficult to solidify, and off gases, still present
process and disposal issues that must be addressed. For example,
the presence of sulfur-containing compounds in a vitrification
melter can cause a molten sulfur salt pool to accumulate on top of
the molten inorganic residue (glass). This pool causes high
corrosion rates for the melter equipment. The pool can also have a
high electrical conductivity, which causes short-circuiting of the
heating electrodes in the melter. Additionally, potentially
explosive conditions can result if large quantities of water
contact the molten sulfur salt pool.
[0006] There remains a need for a process that does not have the
limitations and shortcomings of the above described methods for
processing radioactive waste materials comprising sulfur-containing
compounds and/or halogen-containing compounds.
[0007] The description herein of certain advantages and
disadvantages of known methods is not intended to limit the scope
of the embodiments.
BRIEF SUMMARY
[0008] Disclosed herein are apparatus for the treatment of
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds,
the apparatus comprising: a reaction vessel comprising a filter for
carrying out thermal treatment of the waste; and a thermal
oxidizer. Optionally, the apparatus may further comprise a process
reaction vessel and/or an adsorption vessel comprising adsorbent
media for adsorbing sulfur-containing compounds and/or
halogen-containing compounds after treatment of the waste by the
reaction vessel. Also disclosed herein are methods for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds,
which utilize the apparatus in continuous, semi-continuous or batch
processes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a process diagram showing an exemplary embodiment
of the present invention.
[0010] FIG. 2 is a process diagram showing another exemplary
embodiment of the present invention.
[0011] Many aspects of the inventive technology can be better
understood with reference to the above drawings. The elements and
features shown in the drawings are not necessarily to scale,
emphasis being placed upon clearly illustrating the principles of
exemplary embodiments of the present technology. Moreover, certain
dimensions may be exaggerated to help visually convey such
principles.
DETAILED DESCRIPTION
[0012] The present invention relates generally to apparatus and
methods for treating, or decomposing, hazardous and radioactive
organic wastes which also comprise sulfur-containing compounds
and/or halogen-containing compounds. Generally, the apparatus and
methods facilitate the decomposing of the waste so that the volume
and mass of the waste to be disposed of is greatly reduced from the
initial volume and mass. Additionally, those components of the
process waste that are released to the environment, gases and water
vapor, are rendered harmless prior to release. The apparatus and
methods can be used advantageously to lower process and apparatus
complexity, reduce capital cost, lower final waste residue volumes,
increase final waste stability, reduce water solubility of the
final waste, and/or minimize secondary process wastes, compared to
prior art methods. The exemplary apparatus and methods effectively
reduce or eliminate the sulfur-containing compounds and
halogen-containing compounds in waste feed with greatly reduced or
minimal volatization of these compounds. Because the
sulfur-containing compounds and halogen-containing compounds are
substantially not volatilized, in certain embodiments, no wet
scrubber is needed or the production of the wet scrubber solution
secondary waste is greatly reduced or completely avoided. An
additional advantage of the exemplary apparatus and methods is that
the amount of salt waste, for example sulfate or halide salt waste,
is minimized or substantially reduced. Further, the exemplary
apparatus and methods facilitate the reduction of waste volumes by
converting the sulfur-containing compounds and halogen-containing
compounds to the lowest mass and highest density final treated
waste residue.
[0013] General Apparatus and Methods Description
[0014] FIGS. 1 and 2 are process diagrams that show processes and
components of alternative exemplary embodiments. In exemplary
embodiments, an apparatus comprises a reaction vessel comprising a
filter and a thermal oxidizer vessel. In exemplary embodiments, the
apparatus further comprises an adsorption vessel or a vessel
comprising adsorption media, which is downstream of the reaction
vessel and upstream of the thermal oxidizer vessel. In exemplary
embodiments, the apparatus further comprises a process reaction
vessel upstream of the filter reaction vessel. In certain
embodiments, the apparatus comprises a process vessel, a reaction
vessel comprising a filter, an adsorption vessel and a thermal
oxidizer vessel.
[0015] Referring now to FIG. 1, there is shown an exemplary
apparatus which includes a reaction vessel comprising a filter with
a reaction bed at the bottom of the vessel, an optional adsorption
vessel, and a thermal oxidizer (or thermal oxidizing vessel). In
the method for treating waste utilizing the exemplary apparatus,
waste feed 11 and co-reactants 23 pass into the reaction vessel
comprising a filter, simultaneously or sequentially, and form a bed
in the lower portion of the reaction vessel comprising a filter.
The co-reactant stream 23 may also contain inert bed media, if
desired. The reaction vessel comprising a filter includes a filter
in the upper portion of the vessel and a reaction bed in the bottom
of the vessel. The reaction bed comprises waste, co-reactants, and
optionally, inert bed media. In certain embodiments, the lower
portion of the reaction vessel comprising a filter is heated to a
temperature of, for example, at least about 250.degree. C.
Fluidizing or jet gas 20 passes into the bed or lower portion of
the reaction vessel comprising a filter to agitate the waste,
co-reactants and, if present, inert bed media. Filter pulse clean
gas 24 passes in the upper portion of the vessel. As, or after,
mineral products are formed in the lower portion of the reactor,
solid and liquid waste residues 21 are removed from the lower
portion of the reactor. Volatilized waste, or waste gases, are
treated at least in part by the filter in the upper part of the
reaction vessel comprising a filter. The waste gases and process
gas 22/32 are forwarded to a thermal oxidizer, optionally via an
adsorption vessel. If included, the adsorption vessel contains
adsorption media, or adsorbent, for adsorbing at least a portion of
the waste gases, for example volatized sulfur-containing compounds
and/or halogen-containing compounds. Adsorbent 30 passes into the
adsorption vessel and spent adsorbent 31 including adsorbed waste
passes out of the adsorption vessel. Remaining waste gases and
process gas 32 pass out of the adsorption vessel and into the
thermal oxidizer for further treatment. Combustion air and fuel 40
passes into the thermal oxidizer and after combustion of the waste
gases, for example carbon monoxide, hydrogen, and volatile organic
compounds, off-gas discharge 41 leaves the thermal oxidizer. The
off-gas discharge substantially comprises carbon dioxide and water
vapor.
[0016] Referring now to FIG. 2, there is shown an alternative
exemplary apparatus which includes a process reaction vessel,
reaction vessel comprising a filter, an optional adsorption vessel,
and a thermal oxidizer (or thermal oxidizing vessel). In the
process for treating waste utilizing the exemplary apparatus, waste
feed 11 and co-reactants 13 pass into the process reaction vessel,
simultaneously or sequentially, and form a bed in the lower portion
of the process reaction vessel. The co-reactant stream 13 may also
contain inert bed media, if desired. In certain embodiments, the
lower portion of the process reaction vessel is heated to a
temperature of, for example, at least about 150.degree. C.
Optionally, fluidizing or jet gas 10 passes into the bed or lower
portion of the process reaction vessel to agitate the waste,
co-reactants and, if present, inert bed media. After initial
treatment in the process reaction vessel, the waste, co-reactants,
and process gas 12 are transferred into the reaction vessel
comprising a filter. The reaction vessel comprising a filter
includes a filter in the upper portion of the vessel and,
optionally, inert bed media in the lower portion of the vessel.
Additional co-reactants 23 may be added to the reaction vessel
comprising a filter. The co-reactant stream 23 may also contain
inert bed media, if desired. The waste, co-reactants and inert bed
media, if present, form a bed in the lower portion of the reaction
vessel comprising a filter. The lower portion of the reaction
vessel comprising a filter is heated to a temperature of at least
about 250.degree. C. Fluidizing or jet gas 20 passes into the bed
or lower portion of the reaction vessel comprising a filter to
agitate the waste, co-reactants and, if present, inert bed media.
Filter pulse clean gas 24 passes in the upper portion of the
vessel. As, or after, mineral products are formed in the lower
portion of the reactor, solid waste residues 21 are removed from
the lower portion of the reactor. Volatilized waste residues, or
waste gases, are treated at least in part by the filter in the
upper part of the reaction vessel comprising a filter. The waste
gases and process gas 22/32 are forwarded to a thermal oxidizer,
optionally via an adsorption vessel. If included, the adsorption
vessel contains adsorbent for adsorbing at least a portion of the
waste gases, for example volatized sulfur-containing compounds
and/or halogen-containing compounds. Adsorbent 30 passes into the
adsorption vessel and spent adsorbent 31 including adsorbed waste
passes out of the adsorption vessel. Remaining waste gases and
process gas 32 pass out of the adsorption vessel and into the
thermal oxidizer for further treatment. Combustion air and fuel 40
passes into the thermal oxidizer and after combustion of the waste
gases, for example carbon monoxide, hydrogen, and volatile organic
compounds, off-gas discharge 41 leaves the thermal oxidizer. The
off-gas discharge substantially comprises carbon dioxide and water
vapor.
[0017] In exemplary embodiments, an apparatus for the treatment of
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the apparatus comprising: (a) a reaction vessel
comprising a filter for carrying out thermal treatment of the
waste; and (b) a thermal oxidizer. In exemplary embodiments, the
apparatus further comprises: (c) an adsorption vessel comprising
one or more types of adsorbent media for adsorbing
sulfur-containing compounds and/or halogen-containing compounds
after treatment of the waste by the reaction vessel comprising a
filter. In exemplary embodiments, the apparatus further comprises a
process reaction vessel upstream of the reaction vessel comprising
a filter.
[0018] In exemplary embodiments, an apparatus for the treatment of
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the apparatus comprising: (a) a process reaction vessel
comprising co-reactants for treating the waste; (b) a reaction
vessel comprising a filter for carrying out thermal treatment of
the waste after treatment of the waste in the process reaction
vessel; and (c) a thermal oxidizer. In exemplary embodiments, the
apparatus further comprises: (d) an adsorption vessel comprising
one or more types of adsorbent media for adsorbing
sulfur-containing compounds and/or halogen-containing compounds
after treatment of the waste by the reaction vessels.
[0019] In exemplary embodiments, the reaction vessel comprising a
filter comprises a bed in the lower portion of the reaction vessel
comprising a filter. In exemplary embodiments, the process reaction
vessel comprises a bed in the lower portion of the process reaction
vessel. In exemplary embodiments, the bed comprises waste, one or
more co-reactants and optionally, inert bed media. In exemplary
embodiments, the bed is partially fluidized or jetted.
[0020] In exemplary embodiments, the temperature of the reaction
vessel comprising a filter is below the temperature at which the
sulfur-containing compounds and/or halogen-containing compounds
volatilize. In exemplary embodiments, the temperature of the
process reaction vessel is below the temperature at which the
sulfur-containing compounds and/or halogen-containing compounds
volatilize.
[0021] Single Reaction Vessel Methods
[0022] In an exemplary embodiment, a method for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the method comprising:
[0023] (a) adding radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; and one or more co-reactants to a reaction vessel
comprising a filter to form a bed in the lower portion of the
reaction vessel comprising a filter;
[0024] (b) heating the reaction vessel comprising a filter to a
temperature in the range of about 250.degree. C. to about
1050.degree. C. to form pyrolyzed radioactive waste residues and
waste gases;
[0025] (c) agitating, partially fluidizing or jetting the bed of
the reaction vessel comprising a filter;
[0026] (d) optionally, adding a reactive gas to the reaction vessel
to gasify carbon in the pyrolyzed waste residues;
[0027] (e) removing pyrolyzed radioactive waste residues from the
reaction vessel comprising a filter for disposal; and
[0028] (f) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion;
[0029] wherein the reaction vessel comprising a filter may
optionally be heated to a temperature in the range of about
250.degree. C. to about 1050.degree. C. prior to step (a).
[0030] In an exemplary embodiment, step (b) may be carried out
prior to step (a).
[0031] In an exemplary embodiment, a method for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the method comprising:
[0032] (a) heating a reaction vessel comprising a filter to a
temperature in the range of about 250.degree. C. to about
1050.degree. C.;
[0033] (b) adding radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; and one or more co-reactants to the reaction vessel
comprising a filter to form a bed in the lower portion of the
reaction vessel comprising a filter;
[0034] (c) agitating, partially fluidizing or jetting the bed while
maintaining the temperature of the reaction vessel comprising a
filter in the range of about 250.degree. C. to about 1050.degree.
C. to form pyrolyzed radioactive waste residues and waste
gases;
[0035] (d) removing pyrolyzed radioactive waste residues from the
reaction vessel comprising a filter for disposal; and
[0036] (e) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion.
[0037] In exemplary embodiments, the method further comprises
adding a reactive gas to the reaction vessel comprising a filter in
step (c) to gasify carbon in the pyrolyzed waste residues. In
exemplary embodiments, the reactive gas may be an oxidizing or
reducing gas. In exemplary embodiments, the introduction of the
reactive gas can be used to reduce carbon content in the pyrolyzed
waste residues. In exemplary embodiments, the step of adding a
reactive gas to gasify carbon in the pyrolyzed waste residues is
carried out at a temperature below that which the sulfur-containing
compounds and/or halogen-containing compounds volatilize.
[0038] In an exemplary embodiment, a method for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the method comprising:
[0039] (a) adding radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; and one or more co-reactants to a reaction vessel
comprising a filter to form a bed in the lower portion of the
reaction vessel comprising a filter;
[0040] (b) heating the reaction vessel comprising a filter to a
temperature in the range of about 250.degree. C. to about
1050.degree. C. to form pyrolyzed radioactive waste residues and
waste gases;
[0041] (c) agitating, partially fluidizing or jetting the bed of
the reaction vessel comprising a filter;
[0042] (d) adding a reactive gas to the reaction vessel to gasify
carbon in the pyrolyzed waste residues;
[0043] (e) removing pyrolyzed radioactive waste residues from the
reaction vessel comprising a filter for disposal; and
[0044] (f) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion.
[0045] In an exemplary embodiment, step (b) may be carried out
prior to step (a).
[0046] In exemplary embodiments, the method further comprises
transferring the waste gases to an adsorption vessel comprising
adsorbent for adsorbing sulfur-containing compounds and/or
halogen-containing compounds prior to transferring the waste gases
to a thermal oxidizer for combustion.
[0047] In exemplary embodiments, the bed in the reaction vessel is
agitated, for example by a mechanical agitation method. In
exemplary embodiments, the bed in the reaction vessel is partially
fluidized such as by jetting. In exemplary embodiments, the bed in
the reaction vessel is not fluidized.
[0048] In exemplary embodiments, the radioactive waste comprising
organic compounds, and sulfur-containing compounds and/or
halogen-containing compounds; and the one or more co-reactants are
premixed prior to addition to the reaction vessel. In exemplary
embodiments, the radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing compounds
is added to the reaction vessel with the one or more co-reactants.
In exemplary embodiments, the radioactive waste comprising organic
compounds, and sulfur-containing compounds and/or
halogen-containing compounds is added to the reaction vessel before
the one or more co-reactants. In exemplary embodiments, the
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
added to the reaction vessel after the one or more
co-reactants.
[0049] In exemplary embodiments of any of the methods described
herein, the method comprises adding a reactive gas to the reaction
vessel comprising a filter to gasify carbon in the pyrolyzed waste
residues. In exemplary embodiments, the reactive gas may be an
oxidizing or reducing gas. In exemplary embodiments, the
introduction of the reactive gas can be used to reduce carbon
content in the pyrolyzed waste residues, for example partially
pyrolyzed waste residues. In exemplary embodiments, the step of
adding a reactive gas to gasify carbon in the pyrolyzed waste
residues is carried out at a temperature below that which the
sulfur-containing compounds and/or halogen-containing compounds
volatilize.
[0050] In exemplary embodiments, the reactive gas is an oxidizing
gas, for example nitrogen with a trace of oxygen, steam with a
trace of oxygen, or another slightly oxidizing gas or gas mixture.
In exemplary embodiments, the reactive gas comprises less than
about 10%, about 9%, about 8%, about 7%, about 6%, or about 5%
oxygen. In exemplary embodiments, the reactive gas comprises about
1% to about 10%, about 1% to about 8%, or about 2% to about 5%
oxygen. In exemplary embodiments, the amount of oxygen in the
reactive gas is any suitable amount such that the reaction of the
oxygen with the waste residues, for example carbon-containing waste
residues, does not produce an undesirable or detrimental amount of
heat. An excessive amount of oxygen in the reactive gas may produce
fires, deflagration mixtures and hot spots, which could melt or
agglomerate the bed. In exemplary embodiments, the reactive gas may
fluidize or partially fluidize the bed in the reaction vessel.
[0051] In exemplary embodiments, the bed comprises radioactive
waste comprising organic compounds, and sulfur-containing compounds
and/or halogen-containing compounds; one or more co-reactants,
pyrolyzed radioactive waste residues or a mixture thereof. In
exemplary embodiments, the bed further comprises inert media. In
exemplary embodiments, the bed does not contain inert media.
[0052] In exemplary embodiments, the method further comprises
injecting a pulse clean gas to clean the filter. In exemplary
embodiments, the pulse clean gas is an inert gas, for example
nitrogen gas. In exemplary embodiments, the pulse gas is used to
clean filter cake off the filter.
[0053] In exemplary embodiments, the method is a continuous
process. In exemplary embodiments, the method is a batch or
semi-continuous process.
[0054] Two Reaction Vessel Methods
[0055] In an exemplary embodiment, a method for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the method comprising:
[0056] (a) adding radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; and one or more co-reactants to a process reaction
vessel to form a bed in the lower portion of the process reaction
vessel;
[0057] (b) heating the process reaction vessel to a temperature in
the range of about 35.degree. C. to about 1050.degree. C.;
[0058] (c) agitating, partially fluidizing or jetting the bed while
maintaining the temperature of the process reaction vessel in the
range of about 35.degree. C. to about 1050.degree. C. to form fully
or partially pyrolyzed radioactive waste residues and waste
gases;
[0059] (d) transferring the fully or partially pyrolyzed
radioactive waste residues and waste gases from the process
reaction vessel to a reaction vessel comprising a filter to form a
bed in the lower portion of the reaction vessel comprising a
filter;
[0060] (e) heating the reaction vessel comprising a filter to a
temperature in the range of about 250.degree. C. to about
1050.degree. C.;
[0061] (f) agitating, partially fluidizing or jetting the bed of
the reaction vessel comprising a filter while maintaining the
temperature of the reaction vessel comprising a filter in the range
of about 250.degree. C. to about 1050.degree. C. to form fully or
partially pyrolyzed radioactive waste residues and waste gases;
[0062] (g) optionally, adding a reactive gas to the reaction vessel
comprising a filter to gasify carbon in the partially pyrolyzed
waste residues;
[0063] (h) removing the fully pyrolyzed radioactive waste residues
from the reaction vessel comprising a filter for disposal; and
[0064] (i) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion;
[0065] wherein the process reaction vessel may optionally be to
heated to a temperature in the range of about 35.degree. C. to
about 1050.degree. C. prior to step (a); and wherein the reaction
vessel comprising a filter may optionally be to heated to a
temperature in the range of about 250.degree. C. to about
1050.degree. C. prior to step (d).
[0066] In an exemplary embodiment, step (b) may be carried out
prior to step (a).
[0067] In an exemplary embodiment, step (e) may be carried out
prior to step (d).
[0068] In an exemplary embodiment, a method for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the method comprising:
[0069] (a) heating a process reaction vessel to a temperature in
the range of about 35.degree. C. to about 1050.degree. C.;
[0070] (b) adding radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; and one or more co-reactants to a process reaction
vessel to form a bed in the lower portion of the process reaction
vessel;
[0071] (c) agitating, partially fluidizing or jetting the bed while
maintaining the temperature of the process reaction vessel in the
range of about 35.degree. C. to about 1050.degree. C. to form fully
or partially pyrolyzed radioactive waste residues and waste
gases;
[0072] (d) transferring the fully or partially pyrolyzed
radioactive waste residues and waste gases from the process
reaction vessel to a reaction vessel comprising a filter at a
temperature in the range of about 250.degree. C. to about
1050.degree. C. to form a bed in the lower portion of the reaction
vessel comprising a filter;
[0073] (e) agitating, partially fluidizing or jetting the bed while
maintaining the temperature of the reaction vessel comprising a
filter in the range of about 250.degree. C. to about 1050.degree.
C. to form fully pyrolyzed radioactive waste residues and waste
gases;
[0074] (f) removing pyrolyzed radioactive waste residues from the
reaction vessel comprising a filter for disposal; and
[0075] (g) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion.
[0076] In an exemplary embodiment, a method for treating
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
provided, the method comprising:
[0077] (a) adding radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; and one or more co-reactants to a process reaction
vessel to form a bed in the lower portion of the process reaction
vessel;
[0078] (b) heating the process reaction vessel to a temperature in
the range of about 35.degree. C. to about 1050.degree. C.:
[0079] (c) agitating, partially fluidizing or jetting the bed while
maintaining the temperature of the process reaction vessel in the
range of about 35.degree. C. to about 1050.degree. C. to form fully
or partially pyrolyzed radioactive waste residues and waste
gases;
[0080] (d) transferring the fully or partially pyrolyzed
radioactive waste residues and waste gases from the process
reaction vessel to a reaction vessel comprising a filter to form a
bed in the lower portion of the reaction vessel comprising a
filter;
[0081] (e) heating the reaction vessel comprising a filter to a
temperature in the range of about 250.degree. C. to about
1050.degree. C.;
[0082] (f) agitating, partially fluidizing or jetting the bed of
the reaction vessel comprising a filter while maintaining the
temperature of the reaction vessel comprising a filter in the range
of about 250.degree. C. to about 1050.degree. C. to form fully or
partially pyrolyzed radioactive waste residues and waste gases;
[0083] (g) optionally, adding a reactive gas to the reaction vessel
comprising a filter to gasify carbon in the partially pyrolyzed
waste residues;
[0084] (h) removing the fully pyrolyzed radioactive waste residues
from the reaction vessel comprising a filter for disposal; and
[0085] (i) transferring the waste gases from the reaction vessel
comprising a filter to a thermal oxidizer for combustion.
[0086] In an exemplary embodiment, step (b) may be carried out
prior to step (a). In an exemplary embodiment, step (e) may be
carried out prior to step (d).
[0087] In exemplary embodiments, the method further comprises
transferring the waste gases to an adsorption vessel comprising
adsorbent for adsorbing sulfur-containing compounds and/or
halogen-containing compounds prior to transferring the waste gases
to a thermal oxidizer for combustion.
[0088] In exemplary embodiments, the bed in the process reaction
vessel is agitated, for example by a mechanical agitation method.
In exemplary embodiments, the bed in the process reaction vessel is
partially fluidized. In exemplary embodiments, the bed in the
process reaction vessel is jetted. In exemplary embodiments, the
bed in the process reaction vessel is not fluidized.
[0089] In exemplary embodiments, the bed in the reaction vessel
comprising a filter is agitated, for example by a mechanical
agitation method. In exemplary embodiments, the bed in the reaction
vessel comprising a filter is partially fluidized. In exemplary
embodiments, the bed in the reaction vessel comprising a filter is
jetted. In exemplary embodiments, the bed in the reaction vessel
comprising a filter is not fluidized.
[0090] In exemplary embodiments, the radioactive waste comprising
organic compounds, and sulfur-containing compounds and/or
halogen-containing compounds; and the one or more co-reactants are
premixed prior to addition to the process reaction vessel. In
exemplary embodiments, the radioactive waste comprising organic
compounds, and sulfur-containing compounds and/or
halogen-containing compounds is added to the process reaction
vessel with the one or more co-reactants. In exemplary embodiments,
the radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds is
added to the process reaction vessel before the one or more
co-reactants. In exemplary embodiments, the radioactive waste
comprising organic compounds, and sulfur-containing compounds
and/or halogen-containing compounds is added to the process
reaction vessel after the one or more co-reactants.
[0091] As referred to herein, fully pyrolyzed radioactive waste
residues do not substantially contain carbon, i.e., less than 1% by
weight. As referred to herein, partially pyrolyzed radioactive
waste residues contain carbon or organic compounds. In exemplary
embodiments of any of the foregoing methods, partially pyrolyzed
radioactive waste residues may be gasified to convert the carbon in
the residues to carbon dioxide, carbon monoxide or volatile organic
compounds. In exemplary embodiments, partially pyrolyzed
radioactive waste residues may be gasified, for example by adding a
reactive gas to the reaction vessel comprising the partially
pyrolyzed radioactive waste residues and allowing the reactive gas
to react with the partially pyrolyzed radioactive waste residues to
form fully pyrolyzed radioactive waste residues.
[0092] In exemplary embodiments, the fully or partially pyrolyzed
radioactive waste residues and waste gases are transferred to the
reaction vessel comprising a filter without the adding one or more
co-reactants. In exemplary embodiments, the fully or partially
pyrolyzed radioactive waste residues and waste gases and one or
more co-reactants are premixed prior to addition to the reaction
vessel comprising a filter. In exemplary embodiments, the fully or
partially pyrolyzed radioactive waste residues and waste gases are
added to the reaction vessel comprising a filter with one or more
co-reactants. In exemplary embodiments, the fully or partially
pyrolyzed radioactive waste residues and waste gases are added to
the reaction vessel comprising a filter before one or more
co-reactants. In exemplary embodiments, the fully or partially
pyrolyzed radioactive waste residues and waste gases are added to
the reaction vessel comprising a filter after one or more
co-reactants.
[0093] In exemplary embodiments, the reactive gas is an oxidizing
gas, including for example nitrogen with a trace of oxygen, steam,
and steam with a trace of oxygen. Alternatively, the reactive gases
may contain reducing gases, including for example nitrogen with
hydrogen; nitrogen with ammonia; steam with hydrogen; and steam
with hydrogen, ammonia, and/or volatile organic compound vapors. In
exemplary embodiments, the reactive gas, or a mixture of reactive
gases, may fluidize or partially fluidize the bed in the reaction
vessel. In exemplary embodiments, the reactive gas, or a mixture of
reactive gases, can be added to the process reaction vessel and/or
the reaction vessel comprising a filter. The reactive gas, or a
mixture of reactive gases, added to the process reaction vessel may
be the same or different from the reactive gas, or mixture of
reactive gases, that may be added to the reaction vessel comprising
the filter.
[0094] In exemplary embodiments, the bed in the process reaction
vessel comprises radioactive waste comprising organic compounds,
and sulfur-containing compounds and/or halogen-containing
compounds; one or more co-reactants, pyrolyzed radioactive waste
residues or a mixture thereof. In exemplary embodiments, the bed in
the process reaction vessel further comprises inert media. In
exemplary embodiments, the bed in the process reaction vessel does
not contain inert media.
[0095] In exemplary embodiments, the method further comprises
injecting a pulse clean gas to clean the filter in the reaction
vessel comprising a filter. In exemplary embodiments, the pulse
clean gas is an inert gas, for example nitrogen gas. In exemplary
embodiments, the pulse gas is used to clean filter cake off the
filter in the reaction vessel comprising a filter.
[0096] In exemplary embodiments, the temperature of the process
reactor is at a different temperature from that of the reaction
vessel comprising a filter. In exemplary embodiments, the
temperature of the process reactor is higher than that of the
reaction vessel comprising a filter. In exemplary embodiments, the
temperature of the process reactor is lower than that of the
reaction vessel comprising a filter.
[0097] In exemplary embodiments, the steam reformation does not
occur in the reaction vessel comprising the filter. In certain
embodiments, pyrolysis in reaction vessel comprising a filter
occurs under oxidizing conditions or in the presence of a small
amount of oxygen. In other embodiments the reaction vessel
comprising a filter occurs under reducing conditions or in the
presence of an amount of reducing gases such as, hydrogen, ammonia
and/or volatile organic vapors.
[0098] In exemplary embodiments, the method is a continuous
process. In exemplary embodiments, the method is a batch or
semi-continuous process.
[0099] Waste
[0100] Any waste or product stream containing organic compounds,
and sulfur-containing compounds and/or halogen-containing compounds
can be treated by the exemplary apparatus and methods. In exemplary
embodiments, the waste to be treated by the exemplary apparatus and
methods is radioactive waste, for example radioactive waste
comprising organic compounds, and sulfur-containing compounds
and/or halogen-containing compounds. Radioactive wastes are wastes
that comprise radioactive material or radionuclides. Common sources
of radioactive wastes include by-products of nuclear power
generation and other applications of nuclear fission or nuclear
technology, such as research and medicine. Radioactive waste is
hazardous to most forms of life and the environment, and is
regulated by government agencies in order to protect human health
and the environment.
[0101] In exemplary embodiments, the waste to be treated by the
exemplary apparatus and methods is generally from nuclear
facilities. In exemplary embodiments, the waste further comprises
alkali metals and/or heavy metals. In exemplary embodiments, the
waste comprises ion exchange resin, for example contaminated ion
exchange resin. In exemplary embodiments, the waste feed may be dry
or wet. The waste feed may comprise liquids, liquid slurries,
sludges, solids and gases. The waste feed can have any pH value and
need not be pre-processed before being introduced into the
exemplary methods for treatment. In exemplary embodiments, the
waste comprises about 5% to about 100% carbonaceous or organic
content by weight. In certain embodiments, the waste does not
contain more than 10% nitrate-containing compounds by weight.
[0102] Co-Reactants
[0103] In exemplary embodiments, one or more co-reactants are added
to reaction vessel comprising a filter, simultaneously or
sequentially, with the waste feed. In exemplary embodiments, one or
more co-reactants are added to reaction vessel comprising a filter
with the waste feed. In exemplary embodiments, one or more
co-reactants are added to reaction vessel comprising a filter
before the waste feed. In certain embodiments, co-reactants are
added to the process reaction vessel. In certain embodiments,
co-reactants are not added to the process reaction vessel.
[0104] In exemplary embodiments, one or more co-reactants may be
added to achieve mineralization of one or more compounds in the
waste. In exemplary embodiments, one or more co-reactants may be
added to react with sulfur-containing compounds and/or
halogen-containing compounds in the waste to form non-volatile
and/or water insoluble compounds. In exemplary embodiments, one or
more co-reactants may be added to react with alkali metals in the
waste to form high melting and/or water insoluble compounds. In
exemplary embodiments, one or more co-reactants may be added to
react with metals in the waste to form spinels or other water
insoluble compounds.
[0105] Co-reactant compounds will be known to those of ordinary
skill in the art and any suitable co-reactant compound may be used
in the exemplary apparatus and methods as necessary or desired.
Exemplary co-reactants such as lime, clay, kaolin clay, magnesium
compounds, calcium compounds, aluminum compounds, phosphate
compounds, iron compounds, zinc compounds, nickel compounds, tin
compounds, cerium compounds, and silica compounds may be used. In
certain embodiments, co-reactants may be mixed with the waste feed
before it is introduced into the reaction vessel comprising a
filter. This mixing step allows the co-reactants to, for example,
bind the sulfur-containing compounds, halogen-containing compounds,
alkali metals, certain radioactive elements, and heavy metals into
a stable mineral form. Alternatively, co-reactants may be added
separately into reaction vessel comprising a filter without first
mixing co-reactants with the waste feed. In exemplary embodiments,
the one or more co-reactants for treatment of waste comprising
sulfur-containing compounds under reducing conditions in the
process reaction vessel or the reaction vessel comprising a filter
are selected from the group consisting of: compounds of calcium,
zinc, iron, nickel, tin, alkali metals, such as sodium, potassium
and lithium; alkaline earth metals, such as magnesium and barium;
aluminum; bismuth; manganese; molybdenum; phosphorus; silicon;
silver; strontium; tin; calcium silicates; commercial H.sub.2S
adsorbents; or other compounds which can be reacted with
sulfur-containing compounds to form stable sulfides and/or
H.sub.2S; and mixtures thereof.
[0106] In exemplary embodiments, the one or more co-reactants for
treatment of waste comprising sulfur-containing compounds under
oxidizing conditions in the process reaction vessel or the reaction
vessel comprising a filter are selected from the group consisting
of: compounds of calcium, magnesium, barium, sodium, potassium,
lithium, aluminum, iron, nickel, manganese, clays, calcium
silicates, or other compounds which can be reacted with
sulfur-containing compounds to form stable sulfate and sulfite
compounds with sulfur oxides (SO.sub.4.sup.2- and SO.sub.3.sup.2-),
and mixtures thereof. In exemplary embodiments, the waste and one
or more co-reactants are heated to temperature sufficient to
accomplish the conversion of the sulfur-containing compounds into
the sulfate or sulfite compounds but less than the temperature at
which the sulfates and sulfites decompose or melt. In certain
embodiments, the waste and one or more co-reactants are heated to a
temperature of about 884.degree. C. or less, for example, to
prevent decomposition or melting of sodium sulfate.
[0107] In exemplary embodiments, the one or more co-reactants are
added to convert the sulfur-containing compounds into sulfide
compounds, for example iron sulfide (e.g. FeS or FeS.sub.2),
calcium sulfide, zinc sulfide and/or other high density sulfides.
In exemplary embodiments, the waste and one or more co-reactants
are heated to temperature sufficient to accomplish the conversion
of the sulfur-containing compounds into the sulfide compounds but
less than the temperature at which the sulfides are gasified, e.g.
through oxidation or thermal decomposition. In certain embodiments,
the waste and one or more co-reactants are heated to a temperature
of about 602.degree. C. or less, for example, to prevent
decomposition of Fe.sub.2S. In certain embodiments, the waste and
one or more co-reactants are heated to a temperature of about
1050.degree. C. or less, for example, to prevent decomposition of
calcium sulfide or zinc sulfide.
[0108] In exemplary embodiments, the one or more co-reactants for
treatment of waste comprising halogen-containing compounds in the
process reaction vessel or the reaction vessel comprising a filter
are selected from the group consisting of: compounds of calcium,
zinc, iron, nickel, sodium, potassium, lithium, aluminum,
magnesium, barium, bismuth, cerium, cobalt, manganese, molybdenum,
silver, tin, titanium, zirconium, clays, calcium silicates, or
other compounds which can be reacted with halogen-containing
compounds to form salts or stable, non-volatile halide compounds,
and mixtures thereof. In exemplary embodiments, the waste and one
or more co-reactants are heated to temperature sufficient to
accomplish the conversion of the halogen-containing compounds into
the salts or halide compounds but less than the temperature at
which the salts or halides decompose or melt. In certain
embodiments, the waste and one or more co-reactants are heated to a
temperature of about 801.degree. C. or less, for example, to
prevent decomposition or melting of sodium chloride.
[0109] Preferably less than 20% by weight of unbound co-reactants
are present in the reaction vessel comprising a filter at any given
time during the process to not unnecessarily add to the weight and
volume of the pyrolyzed solids residues. Accordingly, the amount of
co-reactants within the bed of the reaction vessel comprising a
filter can be controlled so the reactions occur with the least
amount of co-reactant. However, the presence of small amounts of
co-reactants can help prevent agglomeration to the point of
adversely impacting the treatment of the waste in the reaction
vessel comprising a filter.
[0110] A problem faced in disposing of some waste from nuclear
facilities is that products formed by typical treatment processes
are water-soluble. In the case that these water-soluble products
also contain radioactive isotopes, additional stabilization of the
products such as grouting, solidification, or vitrification, prior
to disposal will be required to prevent water dissolution of the
buried product into the ground water. Accordingly, the formation of
water-insoluble minerals is both advantageous and desirable,
because they are more easily disposed of and processed. It is also
desirable to select and produce a product that is non-hygroscopic.
The term non-hygroscopic refers to compounds that do not form
hydrates. Solids that form hydrates, such as sodium carbonate, can
swell over time and can rupture or damage the containers they are
stored in.
[0111] Co-reactants can bind heavy metals, sulfur-containing
compounds and halogen-containing compounds to form solid metal
sulfides, spinels or calcium product matrix, or other non-volatile
stable products. The resultant off-gas typically contains <5% of
incoming S, Cl, and F. This high retention of normal acid gases in
the solid product allows scrubber solutions to be recycled to the
reaction vessel thereby eliminating secondary scrubber solution
waste. A specific co-reactant that can be used is lime. The
sulfur-containing compounds and halogen-containing compounds can be
directly bonded by the addition of lime (CaO) to form CaSO.sub.4
(gypsum) or CaCl.sub.2 in the scrubber or the S as SO.sub.4 can be
bound into the crystalline structure of certain mineral forms such
as Nepheline or the Cl can be bound into the crystalline structure
of certain mineral forms thereby converting it to water insoluble
Sodalite.
[0112] Another advantage to the addition of co-reactants is the
formation of higher melting point compounds that will result in
less agglomeration in the reaction vessel comprising a filter.
Although the formation of higher melting point compounds helps to
prevent agglomeration in the reaction vessel, some agglomeration is
preferred in the present invention to increase the size of the
mineral products. However, it is not desirable to have
agglomeration to the point of ceasing the fluidization of the
reactor. Therefore, another feature of the present invention is to
add only the appropriate amounts of co-reactant to effectively
mineralize the sulfur-containing compounds, halogen-containing
compounds, alkali metals, phosphates, and/or boron compounds, and
to also prevent agglomeration to the point of adversely impacting
the treatment of the waste in the reaction vessel comprising a
filter.
[0113] In exemplary embodiments, the percentage of the one or more
co-reactants added to bind the sulfur-containing compounds,
halogen-containing compounds, alkali metals, phosphates, and/or
boron compounds is greater than 50% stoichiometric ratio, with a
preferred range of 100% to 125% stoichiometric ratio, to produce
the desired mineral product. For example, to produce Nepheline, the
preferred amounts of co-reactant to waste compound are as follows:
1 to 1.25 moles Kaolin clay (Al.sub.2O.sub.3-2-SiO.sub.2) with 2
moles of Na. In exemplary embodiments, the sulfur-containing
compounds in the treated or pyrolyzed waste solids are
substantially in the form of FeS.sub.2, FeS, ZnS, CaS or mixtures
thereof. In a preferred embodiment, the sulfur-containing compounds
in the treated or pyrolyzed waste solids are substantially in the
form of FeS.sub.2. FeS.sub.2 produces the lowest volume of
sulfur-containing compounds. In exemplary embodiments, when the
sulfur-containing compounds in the treated or pyrolyzed waste
solids are substantially in the form of FeS.sub.2 the waste need
not undergo further treatment with, for example, a scrubber, such
as a wet scrubber. However, if the waste type and operating
conditions are such that FeS.sub.2 is not readily formed or the
desired operating temperature of the reaction vessel is above the
decomposition temperature of FeS.sub.2, FeS may be formed or
alternative co-reactants can be added to produce other dense, high
temperature resistant sulfides, water insoluble sulfides such as:
CaS, ZnS.sub.2, SnS and/or SnS.sub.2. In exemplary embodiments, the
sulfur-containing compounds in the treated or pyrolyzed waste
solids undergo further treatment with a wet scrubber. In exemplary
embodiments, the sulfur-containing compounds in the treated or
pyrolyzed waste solids do not undergo further treatment with a wet
scrubber.
[0114] In exemplary embodiments, the one or more co-reactants
comprise calcium compounds, calcium silicate, and/or clay to
produce a calcium silicate rich composition. The calcium silicon
rich composition may be used as a high strength cement with the
addition of water.
[0115] In exemplary embodiments, co-reactants are added to the
process reaction vessel or the reaction vessel comprising a filter
to produce mineral compounds that are substantially water
insoluble. In certain embodiments, the one or more co-reactants
used do not change the valence state of the metal ions in the
waste.
[0116] Reaction Vessel Comprising a Filter
[0117] In exemplary embodiments, the reaction vessel comprising a
filter comprises a closed vessel or reactor with inlets for the
waste feed 11, fluidizing or jet gas 20, co-reactants and/or inert
bed media 23, and filter pulse clean gas 24, e.g. nitrogen; outlets
for the process gas 22/32 and waste residue 21; a filter in the
upper portion of the vessel; and a lower portion of the vessel
suitable for containing a partially fluidized or jetted bed
comprising co-reactants and waste. In exemplary embodiments, the
reaction vessel comprising a filter may be any suitable size for
carrying out treatment of waste. In exemplary embodiments, the
reaction vessel comprising a filter is where the waste is subjected
to pyrolysis and optional reactive gases. In exemplary embodiments,
the filter is included to remove solids from the process gas 22/32
before passage into the thermal oxidizer and optionally, the
adsorption vessel. In exemplary embodiments, the filter is made of
sintered metal or ceramic elements. In certain embodiments, a
reactive gas can be added to the reaction vessel comprising a
filter to gasify carbon in the radioactive waste. In certain
embodiments, the reaction vessel comprising a filter is the only
vessel used for pyrolysis in the apparatus for the treatment of
radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing compounds. In
certain embodiments, the reaction vessel comprising a filter is the
second of two vessels used for pyrolysis in the apparatus for the
treatment of radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing
compounds.
[0118] In exemplary embodiments, the minimum operating temperature
for the reaction vessel comprising a filter is about 150.degree.
C., or about 250.degree. C. In exemplary embodiments, the minimum
operating temperature for the reaction vessel comprising a filter
is the temperature at which the evaporation or pyrolysis of the
organic compounds in the waste occurs, for example about 35.degree.
C. when the waste comprises low-boiling organic solvents or greater
than 350.degree. C. for wastes with wood, cellulose, PVC plastic,
resins, and other long-chain organic polymers.
[0119] In exemplary embodiments, the maximum operating temperature
for the reaction vessel comprising a filter is about 1050.degree.
C., about 884.degree. C., about 801.degree. C., about 602.degree.
C., about 600.degree. C., about 420.degree. C., or about the
temperature at which the sulfides, sulfates, sulfites and/or halide
compounds formed from reaction with the one or more co-reactants
and the waste begin to decompose or melt.
[0120] In exemplary embodiments, the temperature of the reaction
vessel comprising a filter is in the range of about 150.degree. C.
to about 1050.degree. C., about 150.degree. C. to about 800.degree.
C., or about 200.degree. C. to about 550.degree. C.
[0121] In exemplary embodiments, the reaction vessel comprising a
filter is used to treat radioactive waste comprising ion exchange
resin. In exemplary embodiments, when the reaction vessel
comprising a filter is used to treat ion exchange resin, the
operating temperature for the reaction vessel comprising a filter
is in the range of about 250.degree. C. to about 800.degree. C., or
about 250.degree. C. to about 600.degree. C.
[0122] In exemplary embodiments, the reaction vessel comprising a
filter can operate at a slight negative pressure or at positive
pressures, for example a pressure of about 7 to about 115, about 10
to about 25, or about 12 to about 20 psia.
[0123] In exemplary embodiments, the fluidizing or jet gas for the
partially fluidized or jetted bed of the reaction vessel comprising
a filter comprising co-reactants and waste is, for example, steam,
hydrogen, oxygen, methane, ammonia, carbon dioxide, carbon
monoxide, inert gases, oxidizing gases, reducing gases, volatile
organic vapors and mixtures thereof. In certain embodiments, steam
is introduced into the reaction vessel comprising a filter. In
certain embodiments, steam is not introduced into the reaction
vessel comprising a filter. In certain embodiments, the fluidizing
or jet gas is not a reducing gas. In exemplary embodiments, the
fluidizing or jet gas is jetted into the bottom of the reaction
vessel comprising a filter sufficient to agitate and mix the solids
in the bed. In exemplary embodiments, the fluidizing or jet gas is,
for example, a mixture of nitrogen with as about 3 to about 8%
oxygen. In exemplary embodiments, the fluidizing or jet gas is any
gas that can oxidize the carbon in the waste or waste residues
while maintaining the bed of solids at less than 550.degree. C. to
ensure that any FeS2 is not decomposed.
[0124] In certain embodiments, the bed in the lower portion of the
reaction vessel comprising a filter is partially fluidized. In
exemplary embodiments, a partially fluidized bed is a bed of solids
that is agitated by mechanical means or by the localized
introduction of the jet gas where the jet gas flow is not
sufficient, or the flow is not sufficiently uniform, to fully
fluidize all the solids in the bed, e.g., maintain the solids above
their minimum fluidization velocity. For the partially fluidized or
jetted bed, the momentum of the gas jet will induce mixing in the
bed of solids without fluidizing the bulk of the solids. In certain
embodiments, the bed in the lower portion of the reaction vessel
comprising a filter is jetted. In certain embodiments, the bed in
the lower portion of the reaction vessel comprising a filter is not
fluidized. In certain embodiments, fluidizing or jet gas is not
added to the bed in the lower portion of the reaction vessel
comprising a filter. In certain embodiments, the bed in the lower
portion of the reaction vessel comprising a filter is agitated
mechanically. In certain embodiments, the bed in the lower portion
of the reaction vessel comprising a filter is agitated mechanically
and is not fluidized or jetted.
[0125] In exemplary embodiments, when the reaction vessel
comprising a filter is used for treatment of radioactive waste
after treatment by a process reaction vessel, the reaction vessel
comprising a filter is not uniformly fluidized. One of the primary
reasons the bed in the reaction vessel comprising a filter is not
fluidized is the solids from the process reaction vessel are
generally very fine and cannot be uniformly fluidized due to the
small particle size.
[0126] In exemplary embodiments, the partially fluidized or jetted
bed comprising co-reactants and waste further comprises inert bed
media, for example inert ceramic media such as silica, mullite,
corundum, corderite, or alumina; and other types of inert media,
such as bauxite, quartz or silica sand. In certain embodiments, the
inert bed media comprises bauxite. In certain embodiments, the
inert bed media comprises alumina beads. The size of the alumina
beads is in the range of about 100 to about 5000 microns, or about
200 to about 1000 microns, in diameter. Such size beads do not
easily elutriate out of the vessel and therefore minimize
carryover. In certain embodiments, the inert bed media does not
comprise alumina. In certain embodiments, the partially fluidized
or jetted bed comprising co-reactants and waste does not comprise
inert bed media.
[0127] In certain embodiments, the partially fluidized or jetted
bed of the reaction vessel comprising a filter comprises an
oxidizing zone or portion. In certain embodiments, the partially
fluidized or jetted bed of the reaction vessel comprising a filter
does not contain a reducing, or oxygen-starved, zone or portion. In
exemplary embodiments, the reaction vessel comprising a filter can
be operated under oxidizing conditions. In exemplary embodiments,
the reaction vessel comprising a filter can be operated under
reducing conditions. In exemplary embodiments, the reaction vessel
comprising a filter are not operated under reducing conditions.
[0128] In exemplary embodiments, the filter in the reaction vessel
comprising a filter comprises or consists essentially of a set of
sintered metal or ceramic media arranged as filter candles or
elements, and the filter candles or elements can be, for example,
sealed into a tubesheet near the top of the vessel. The filter
elements are pulse cleaned using an inert gas to remove accumulated
filter cake that will collect on the outside surface of the filter
elements. The size of the filter varies as needed to accommodate
the solids loading and gas flows in the vessel.
[0129] Thermal Oxidizer
[0130] A thermal oxidizer is a process unit for air pollution
control in many chemical plants that decomposes hazardous gases at
a high temperature and releases them into the atmosphere. In
exemplary embodiments, the thermal oxidizer heats the waste gases
up to combustion temperature and mixes the waste gases with air or
oxygen to facilitate complete oxidation of the hydrogen, ammonia,
carbon monoxide and volatile organic vapors from the reaction
vessel comprising a filter to carbon dioxide and water vapor. In
exemplary embodiments, the operating temperature of the thermal
oxidizer is about 800.degree. C. to about 1200.degree. C., or about
850.degree. C. to about 950.degree. C.
[0131] Adsorption Vessel
[0132] In exemplary embodiments, the apparatus and methods
optionally further comprise an adsorption vessel.
[0133] In exemplary embodiments, the apparatus and methods
optionally comprise an adsorption vessel, which is downstream of
the reaction vessel comprising a filter, and if present, the
process reaction vessel. The adsorption vessel comprises one or
more types of adsorbent media. In certain embodiments, the
adsorption vessel comprises one or more types of adsorbent media,
which can be used to adsorb sulfur-containing compounds and/or
halogen-containing compounds.
[0134] In exemplary embodiments, when the process reaction vessel
and/or the reaction vessel comprising a filter are operated at
oxidizing conditions or in the presence of a small amount of
oxygen, the methods further comprise transferring the waste gases
to an adsorption vessel comprises one or more types of adsorbent
media. In exemplary embodiments, the adsorbent media comprises one
or more types of adsorbent media that adsorb sulfur-containing
compounds and produces a sulfate compound, for example calcium
sulfate.
[0135] In exemplary embodiments, when the process reaction vessel
and/or the reaction vessel comprising a filter are operated at
reducing conditions or in the presence of reducing gases, the
methods further comprise transferring the waste gases to an
adsorption vessel comprising one or more types of adsorbent media.
In the exemplary embodiments, the one or more types of adsorbent
media comprise metal or alkaline earth adsorbents. In exemplary
embodiments, the one or more types of adsorbent media comprise
metals, for example iron, nickel or zinc. In exemplary embodiments,
the one or more types of adsorbent media comprise metal oxides, for
example Fe.sub.2O.sub.3, FeO, Fe.sub.3O.sub.4 or NiO. In exemplary
embodiments, the one or more types of adsorbent media comprise
Al(OH).sub.3. In exemplary embodiments, the adsorbent media
comprises one or more types of adsorbent media that adsorb
sulfur-containing compounds and produces a metal sulfide, for
example FeS and Fe.sub.2S; alkaline earth sulfide, for example CaS;
or another sulfide such as ZnS or SnS.
[0136] In exemplary embodiments, the process gas does not comprise
oxygen and the adsorbent media comprises one or more types of
adsorbent media that adsorb sulfur-containing compounds and
produces a metal sulfide, for example FeS and Fe.sub.2S; alkaline
earth sulfide, for example CaS; or another sulfide.
[0137] Process Reaction Vessel
[0138] In exemplary embodiments, the apparatus and methods
optionally further comprise a process reaction vessel. In exemplary
embodiments, the process reaction vessel comprises a closed vessel
or reactor with inlets for the waste feed 11, fluidizing or jet gas
10, co-reactants and/or inert bed media 13; outlets for the process
gas and waste residues 12; and a lower portion of the vessel
suitable for containing a bed comprising co-reactants and waste. In
exemplary embodiments, the process reaction vessel is where the
waste is subjected to initial pyrolysis. In exemplary embodiments,
the process gas and waste residues (or pyrolyzed waste solids and
waste gases) are transferred to a reaction vessel comprising a
filter after treatment in the process reaction vessel. In certain
embodiments, a reactive gas can be added to the process reaction
vessel to gasify carbon in the radioactive waste. In certain
embodiments, the process reaction vessel is the first of two
vessels used for pyrolysis in the apparatus or methods for the
treatment of radioactive waste comprising organic compounds, and
sulfur-containing compounds and/or halogen-containing
compounds.
[0139] In exemplary embodiments, the minimum operating temperature
for the process reaction vessel is about 35.degree. C., about
150.degree. C., about 250.degree. C., or about 350.degree. C. In
exemplary embodiments, the minimum operating temperature for the
process reaction vessel is the temperature at which the evaporation
or pyrolysis of the organic compounds in the waste occurs, for
example about 35.degree. C. when the waste comprises low-boiling
organic solvents, or at least about 350.degree. C. when the waste
comprises wood, resins, PVC plastics or other long-chain organic
polymers.
[0140] In exemplary embodiments, the maximum operating temperature
for the process reaction vessel is about 1050.degree. C., about
884.degree. C., about 801.degree. C., about 602.degree. C., about
600.degree. C., about 420.degree. C., or about the temperature at
which the sulfides, sulfates, sulfites and/or halide compounds
formed from reaction with the one or more co-reactants and the
waste begin to decompose or melt.
[0141] In exemplary embodiments, the temperature of the process
reaction vessel is in the range of about 150.degree. C. to about
1050.degree. C., or about 150.degree. C. to about 800.degree.
C.
[0142] In exemplary embodiments, the process reaction vessel is
used to treat radioactive waste comprising ion exchange resin. In
exemplary embodiments, when the process reaction vessel is used to
treat ion exchange resin, the operating temperature for the process
reaction vessel is in the range of about 250.degree. C. to about
800.degree. C., or about 350.degree. C. to about 600.degree. C.
[0143] In exemplary embodiments, the process reaction vessel can
operate at a slight negative pressure or at positive pressures, for
example a pressure of about 7 to about 115, about 10 to about 25,
or about 12 to about 20 psia.
[0144] In exemplary embodiments, the fluidizing or jet gas for the
partially fluidized or jetted bed of the process reaction vessel
comprising co-reactants and waste is, for example, steam, hydrogen,
oxygen, methane, ammonia, carbon dioxide, carbon monoxide, inert
gases, oxidizing gases, reducing gases, nitrogen, volatile organic
vapors, and mixtures thereof. In certain embodiments, steam is
introduced into the process reaction vessel. In certain
embodiments, steam is not introduced into the process reaction
vessel. In certain embodiments, the fluidizing or jet gas is not a
reducing gas.
[0145] In certain embodiments, the bed in the lower portion of the
process reaction vessel is partially fluidized. Partially fluidized
beds are described above. In certain embodiments, the bed in the
lower portion of the process reaction vessel is jetted. In certain
embodiments, the bed in the lower portion of the process reaction
vessel is not fluidized. In certain embodiments, fluidizing or jet
gas is not added to the bed in the lower portion of the process
reaction vessel. In certain embodiments, the bed in the lower
portion of the process reaction vessel is agitated mechanically. In
certain embodiments, the bed in the lower portion of the process
reaction vessel is agitated mechanically and is not fluidized or
jetted. In exemplary embodiments, the partially fluidized or jetted
bed comprising co-reactants and waste further comprises inert bed
media, for example inert ceramic media such as silica, mullite,
corundum, corderite, or alumina; and other types of inert media,
such as bauxite, quartz or silica sand. In certain embodiments, the
inert bed media comprises bauxite. In certain embodiments, the
inert bed media comprises alumina beads. The size of the inert bed
media beads is in the range of about 100 to about 5000 microns, or
about 200 to about 1000 microns, in diameter. Such size beads do
not easily elutriate out of the vessel and therefore minimize
carryover. In certain embodiments, the inert bed media does not
comprise alumina. In certain embodiments, the partially fluidized
or jetted bed comprising co-reactants and waste does not comprise
inert bed media.
[0146] In certain embodiments, the partially fluidized or jetted
bed of the process reaction vessel comprises an oxidizing zone or
portion. In certain embodiments, the partially fluidized or jetted
bed of the process reaction vessel does not contain a reducing, or
oxygen-starved, zone or portion. In exemplary embodiments, the
process reaction vessel can be operated under oxidizing conditions.
In exemplary embodiments, the process reaction vessel can be
operated under reducing conditions. In exemplary embodiments, the
process reaction vessel are not operated under reducing
conditions.
[0147] In exemplary embodiments, the process reaction vessel can be
used to substantially reduce the carbon content of the radioactive
waste. In exemplary embodiments, when the waste is first treated in
the process reaction vessel, the subsequent treatment of the waste
in the reaction vessel comprising a filter can be used to remove
sulfur-containing compounds and/or halogen-containing compounds and
to further reduce the carbon content of the waste.
[0148] From the description, it will be appreciated that
embodiments of the present technology overcome limitations of the
prior art. Those skilled in the art will appreciate that the
present technology is not limited to any specifically discussed
application or implementation and that the embodiments described
herein are illustrative and not restrictive. From the description
of the exemplary embodiments, equivalents of the elements shown
therein will suggest themselves to those skilled in the art, and
ways of constructing other embodiments of the present technology
will appear to practitioners of the art.
* * * * *