The invention relates generally to systems for controlling the presence
of contaminants in chemical reaction systems and, more particularly, the invention
relates to methods and apparatus for removing contaminants found in urea hydrolysis
reactors and others wherein contaminants are formed in the course of an ongoing
reaction.
Description of Background TechnologyThe Problem of Contaminant Formation
Solid urea is available in several commodity grades destined for uses
either in agricultural applications as fertilizers or in chemical process for production
of urea-formaldehyde resins and thermosetting polymers. Solid urea is available
in bags or bulk quantities, and is commonly transported in bulk truck or railcar
loads. Urea is a non-hazardous material, and affords a safe starting material in
certain process requiring gaseous ammonia as, for example, in processes for removal
of nitrogen oxides from the tail gas stream of combustion processes, such as in
fuel-fired boiler operations in public electric power generation plants. Such processes
use gaseous ammonia in Selective Catalytic Reduction (SCR) or Selective Non-Catalytic
Reduction (SNCR) methods for removal of nitrogen oxides. Another example is the
use of gaseous ammonia to treat fly ash in the tail gas system of a fuel-fired boiler
in a public electric power generation plant. Such treatment is beneficial for collection
of the fly ash. Common alternatives to use of urea include use of anhydrous ammonia
or of aqueous ammonia, both of which are hazardous chemicals presenting serious
risks in the transport, handling, storage, and use with attendant regulatory compliance
requirements.
Urea may be hydrolyzed to form gaseous ammonia for such uses. Such
processes typically employ solid urea supplied in bulk quantities, and of a composition
readily available as a commodity. Solid urea is a relatively soft solid that is
hygroscopic, which may cause problems in handling it in a highly pure form. Therefore,
it is a common practice in the industry to add certain chemical compounds to the
solid urea to improve its physical properties and to improve handling characteristics
of a granulated or prilled urea product. Such additives include but are not limited
to those disclosed in Belasco et al. U.S. Patent No. 3,248,255 (gaseous formaldehyde
to form urea-formaldehyde resin surface coating), Van Hijfte et al. U.S. Patent
No. 4,160,782 (dimethylolurea and/or trimethylolurea), Elstrom et al. U.S. Patent
No. 4,204,053 (formaldehyde), Blouin U.S. Patent No. 4,587,358 (lignosulfonates),
Gallant et al. U.S. Patent No. 5,102,440 (urea-formaldehyde compounds), and Kayaert
et al. U.S. Patent No. 5,653,781 (formaldehyde, methylolureum (methylolurea), urea-formaldehyde
pre-condensates, or hexamethylenetetramine), the disclosures of which are incorporated
herein by reference.
Such additives are typically present in the solid urea in concentrations
up to 2 wt. %. Therefore, during the continuous use of such solid urea in a hydrolysis
reactor designed to produce gaseous ammonia, the solid urea is first dissolved into
an aqueous solution, commonly in the concentration range 20 wt. % to 78 wt. %, preferably
in the range 40 wt. % to 60 wt. %, and while the urea is continuously decomposed
to ammonia and carbon dioxide and leaves the reactor in a gaseous form, the additives
present in the solid urea accumulate and may undergo various chemical reactions
that form, along with unreacted additives, a contaminant mass in the reaction mixture.
Several specific process systems have been described and patented
with the intent to generate a gaseous stream of ammonia, carbon dioxide, and water
vapor at a temperature and pressure useful for removal of nitrogen oxides or treatment
of fly ash as described, or for other process applications. Young (USP 5,252,308)
describes a process system that performs the hydrolysis reaction using aqueous solutions
of urea in the presence of catalyst systems, specifically mixtures of ammonium salts
of certain polyprotic mineral acids, such as phosphoric or sulfuric acid. Cooper
et al. (USP 6,077,491) describe a urea hydrolysis process that does not require
a catalyst and that may take a variety of forms in the apparatus. Lagana (USP 5,985,224)
describes a process that employs steam-stripping in the hydrolysis reactor to promote
the reaction. The disclosures of Young (USP 5,252,308), Cooper et al. (USP 6,077,491)
and Lagana (USP 5,985,224) are incorporated herein by reference.
These processes do not recognize the potential problems that may arise
from the accumulation of a contaminant mass in the reactor, nor do they describe
why such a contaminant may arise, nor do they provide means to address this contaminant.
It is the intent of the invention to describe some of the reasons why contaminants
arise in the reactor vessels of the various process systems, and to describe the
means to address these contaminants so that maintenance-free urea hydrolysis operation
can be achieved or at least the maintenance-free period of operation extended and
contaminants removed without the hazards and inconvenience of shutting the system
down and opening the reactor vessel for frequent cleaning.
SUMMARY OF THE INVENTION
It is an objective of the invention to provide technology for maintaining
the operation of reactors by incorporating means to remove soluble and/or insoluble
contaminant matter, either intermittently or continuously, from the reaction system.
According to the invention, a method of controlling the amount of
such contaminants in a liquid phase reaction mixture containing urea in a reaction
vessel includes the steps of withdrawing a portion of the reaction mixture containing
such soluble and/or insoluble contaminants from the liquid phase and the reaction
vessel, separating at least one contaminant from the remainder of the withdrawn
portion of the reaction mixture, and recycling at least a portion of the withdrawn
reaction mixture to the liquid phase in the reactor vessel.
The invention also provides apparatus for carrying out a chemical
reaction in a liquid phase containing such contaminants, including a reactor vessel,
means for withdrawing a portion of the reaction mixture from the reactor vessel,
means for separating contaminants from the remainder of the withdrawn portion of
the reaction mixture, and means for recycling any desired portion of the remainder
of the withdrawn portion of the reaction mixture to the reactor vessel.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates the molecular structure of methylene di-urea.
Figure 2 illustrates the molecular structure of a urea-formaldehyde resin.
Figure 3 illustrates the molecular structure of a potential polyamide contaminant
Figure 4 illustrates a urea hydrolysis process system with which the methods
and apparatus of the invention are useful.
Figure 5 illustrates an embodiment of a system for removing insoluble contaminant
material from a urea hydrolysis reactor according to the invention.
Figure 6 illustrates an embodiment of a system for removing insoluble contaminant
material from a urea hydrolysis reactor according to the invention.
Figure 7 illustrates an embodiment of a system for removing soluble and insoluble
contaminant materials from a urea hydrolysis reactor according to the invention.
Figure 8 illustrates an embodiment of a system for removing soluble and insoluble
contaminant materials from a urea hydrolysis reactor according to the invention.
Figure 9 illustrates an embodiment of a system for removing soluble and insoluble
contaminant materials from a urea hydrolysis reactor that contains a dissolved or
solid dispersed catalyst according to the invention.
Figure 10 illustrates an embodiment of a system for removing soluble and insoluble
contaminant materials from a urea hydrolysis reactor that contains a dissolved or
solid dispersed catalyst according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
Generally, a contaminant is any undesirable substance present in a
reactor. Put another way, a contaminant is any substance present in a reactor that
impairs the short-term or long-term operation of the reactor. A contaminant can
be defined as any substance present in a reactor that is not a reagent, reactant,
intermediate, product, solvent, indicator, or catalyst of a desired reaction in
the reactor, or a mechanical component of the reactor itself. A contaminant can
be introduced into the reactor directly (e.g., mixed with a reagent)
or indirectly (e.g., formed by reaction with another contaminant or
non-contaminant or formed by thermal decomposition).
The invention is useful in various methods for production of ammonia
by hydrolysis of urea, whether or not such hydrolysis is conducted with a catalyst
present in the urea hydrolysis reaction mixture. According to the invention, in
order to extend or indefinitely sustain the continuous operation of the urea hydrolysis
process, means to remove the by-product contaminants in the reaction mixture are
provided. Without such means, operation of a urea hydrolysis system would be interrupted
to enable physical cleaning of the reactor, which is complicated by the presence
of ammonia and its associated chemical hazards. Separation of the contaminant matter
may be performed intermittently or continuously in accordance with the invention.
Various means to enhance separation of contaminants are described.
Solid urea is commonly manufactured with certain urea-formaldehyde
additives present in concentrations up to 2 wt.%. These compounds are added to enhance
the handling characteristics of the urea. The additives reduce the tendency to form
fine dust and reduce the hygroscopic behavior, which causes particles to form into
clumps and cakes. Additives may be urea-formaldehyde oligomers or resins that have
been partially polymerized, such as that referred to by the manufacturer's trade
name UF-85. For example, in at least one process, a urea-formaldehyde compound is
added to the urea while the urea is in a molten state, and is believed to react
with the UF-85 additive to form methylene di-urea (MDU, Figure 1), which imparts
the desired physical properties to the final urea composition in the dry solid form.
Another additive is a type of saponate supplied under the trade designation
UREASOFT by Kao Corporation. UREASOFT additive is generally applied to the surface
of prilled urea just before storage as an aid in product storage and handling.
Preferred conditions in a urea hydrolysis reactor, according to various
patented processes, are limited to fairly narrow ranges of temperature and pressure.
Thus, in Cooper et al. the reactor preferably operates at about 150°C to about 155°C
and 75 psig to 90 psig, while in Lagana the reactor preferably operates at 195°C
and 200 psig to 275 psig.
Young describes a process that utilizes a catalyst in the aqueous
solution, and states that the reactor temperature must be at least 150°C, preferably
in the range 150°C to 200°C. The vapor pressure of pure water in this temperature
range is 70 psig to 225 psig and, thus, the generalized range of conditions described
in the Cooper et al. and Lagana patents overlaps the operating conditions first
described by Young.
Therefore, it can generally be said that such hydrolysis reactors
operate preferably in the range from about 150°C to 195°C and about 75 psig to 275
psig. All of these processes employ aqueous solutions of urea, which typically fall
in the concentration range 50 ± 15 wt %, commonly about
50 wt %.
Under these conditions the urea hydrolysis reaction occurs according
to the well-known mechanism:
These reactions taken together are endothermic, requiring a constant
supply of heat to the hydrolysis reactor to sustain the reaction. The ammonia and
carbon dioxide produced are formed as gases, which are released from the aqueous
solution of liquid reactants. Bubbles containing ammonia, carbon dioxide and water
vapor are released into the liquid by the chemical reaction, and rise in the liquid
to eventually coalesce into a bulk gas phase. The reactors therefore have a common
tendency to form a foamy cuff layer in which the bubbles of gas gradually break
and release trapped gases into a bulk gas phase. The urea is converted to ammonia
and carbon dioxide gases, which are discharged from the reactor.
However, the additives present in the urea composition must also be
considered. It is illustrative to consider the presence of methylene di-urea, a
compound known to be present in solid urea. This compound arises as a consequence
of adding UF-85, for example, to the urea as previously described.
Methylene di-urea has a chemical structure shown in Figure 1, and
in the urea hydrolysis reactor may combine with a water molecule to release urea
and formaldehyde, according to the following reaction:
Formaldehyde is a volatile compound and will tend to leave the liquid
phase governed by its vapor-liquid equilibrium at the conditions in the system.
Sufficient pressure may exist to sustain a significant concentration in the liquid
phase, enabling reaction of the dissolved formaldehyde and urea. A possible mechanism
for such reaction may follow the mechanism known to form the urea-formaldehyde resins,
thus:
Reactions 4, 5, and 6 illustrate the combination of urea and formaldehyde into
large polymeric structures by a familiar reaction mechanism (Morrison and Boyd,
Organic Chemistry, 2nd Ed., Allyn and Bacon, Inc., Boston 1966,
p. 923).
Oligomers of urea-formaldehyde reaction products may be applied to
solid urea by various means to impart desirable handling characteristics, and the
urea-formaldehyde oligomers may react to form dimethylolurea or may retain their
original structure to one degree or another. Use of such solid urea in the urea
hydrolysis process would result in continuous dosing of the reactor solution with
oligomers of urea-formaldehyde resin, which could continue to react and to grow
in mass according to the reactions 4, 5, and 6.
While such reactions as 4, 5, and 6 are normally carried out with
relatively pure reactants in processes intended to produce urea-formaldehyde resins
and molded plastics, the mechanism may also explain the appearance of a semi-solid
to solid contaminant matter in the urea hydrolysis reactor wherein the urea, formaldehyde
and intermediates are all present in the aqueous reactant solution. It is likely
that the concentration of the reactants, as well as the temperature, pressure, and
pH of the solution have an effect on the reaction rate. However, formation of large
oligomers of urea-formaldehyde polymer in the reactor with no means of removal will
eventually result in serious contamination and present an impediment to continued
operation.
Polymers, such as urea-formaldehyde reaction products, will vary in
molecular weight or polymer chain length, and will exhibit water solubility for
the smaller oligomers, and relative insolubility as the size of the oligomer molecule
increases. Large polymer molecules may therefore separate as a distinct phase in
the urea hydrolysis reaction mixture. When the polymer density is less than that
of the aqueous solution, the polymer will tend to collect on the surface in the
frothy layer where bubbles of gases are coalescing and breaking to release ammonia
and carbon dioxide. The compounds may affect the rate of foam-breaking in the reactor,
and cause problems in disengaging the product gases from the aqueous reaction mixture.
When the polymer density is greater than that of the aqueous solution, the polymer
will tend to sink and collect on the bottom of a reactor vessel.
Other additives have been reported, such as saponates (e.g., UREASOFT)
and lignosulfonates, which also would be retained in the urea hydrolysis reactor
if present in the feed urea. Lignosulfonates are mentioned with reference to urea
products destined for use as fertilizers, and may not be as prevalent in urea products
for chemical process applications. Nevertheless, both lignosulfonates and saponates
will exhibit affinity for the liquid-vapor interface, and may reduce the surface
tension of the liquid reaction mixture in this area. The effect would be to enhance
the foam stability in the reactor, and as more of the material is accumulated, a
contaminant mass may become isolated in a preferred location in the reactor just
as in the case described previously. Therefore, a similar means of removal will
be required.
Other potential contaminant masses include polyamides, such as polyacrylamides.
The following mechanism is proposed.
The proposed route starts with reaction of urea in the aqueous solution
to form ammonium carbamate, which in turn partially decomposes to ammonia and carbamic
acid. Carbamic acid can react with urea in a condensation polymerization reaction
to form the polyamide compounds.
The chemical reactions are as follows:
wherein x is a variable integer greater than zero.
The molecular structure of a potential polyamide contaminant is illustrated
in Figure 3.
This mechanism illustrates how certain species likely to be present
in the urea hydrolysis reactor may combine to form a polyamide compound. In the
reaction mixture, the polymerization process can continue to increase the molecular
weight of the polyamide compound until it is no longer soluble in the solution and
separates into a contaminant phase. An interesting aspect of this type of contaminant
is that it may arise even if purified urea were used in the hydrolysis reactor,
provided that conditions were favorable to the formation of carbamic acid. Amides
are formed by the reaction of carboxylic acids and amines, and therefore other carboxylic
acids, if present in the reaction mixture, could potentially undergo a reaction
analogous to the mechanism shown above and yield a similar polyamide compound.
Other contamination problems may arise from trace compounds present
in the process water or the solid urea, which would accumulate under continuous
operation over longer periods of time. For example, certain metals may be present
in urea in small amounts, such as Fe, Cd, Cr, Pb, As, and Hg, and ash may be present
at concentrations in the range 0.001 wt % to 0.01 wt %. The process water may contribute
calcium hardness and other minerals or solids. Furthermore, the means of transporting,
handling and dissolving the solid urea may introduce contaminants from the environment
or from contact with the equipment that is used.
A urea hydrolysis process is illustrated in Figure 4, which shows
the major elements of the process system and essential process controls. The system
in a generalized embodiment will include means for delivering solid urea, facilities
for storing and handling bulk solid urea, means for dissolving solid urea in process
water to produce a solution at a controlled concentration and temperature, means
for controlling the flow of aqueous urea to the hydrolysis reactor in response to
an external demand signal, a urea hydrolysis reaction means (e.g., a reactor vessel),
means for controlling the reactor pressure by controlled discharge of the produced
gases, and means for supplying warm dilution air to mix with the produced gases
and conveying the said second mixture to an injection manifold and injection probe
array. The produced ammonia, carbon dioxide, and water vapor mix into the warm air
and the conduit is heated to maintain the temperature at or above about 60 °C to
avoid the formation of ammonium carbonate salts. The hydrolysis reactor must be
heated to sustain the endothermic reaction, and at the temperature of the reaction
the vapor pressure of water requires a design able to sustain pressures in the range
50 psig to 300 psig. In some embodiments, the reactor vessel may have provision
for injection of steam to promote stripping of the ammonia from the aqueous solution.
In some embodiments a portion of the reactants may be removed from the reactor and
recycled back to the urea-dissolving step or just ahead of the aqueous urea flow
control means or elsewhere.
Contaminants may arise in the urea hydrolysis reaction mixture from
reactions of pure urea, such as the formation and/or accumulation of polymers such
as polyamides, or as a consequence of minor ingredients added to the solid urea,
which may give rise to formation and/or accumulation of contaminants including saponates,
ligno-sulfonates, urea-formaldehyde oligomers, urea-formaldehyde polymers, or other
compounds or reaction products derived from such additives in as-supplied solid
urea. As a consequence of the density of a contaminant component being different
from that of the aqueous solution of reactants, a layer of relatively high concentration
of contaminant tends to form on top of the liquid phase in the reactor or sink in
the bottom of the reactor vessel. The design of the means for removing this material
should take into consideration the design of the reactor vessel, and the capacity
of the reactor to restrict the location where the contaminant matter tends to accumulate.
In a fundamental description, the invention provides for the continuous
or intermittent removal of a portion of the reaction fluid mixture from the reactor
vessel and from a position within said reactor vessel where the solid and semi-solid
contaminants tend to form and/or accumulate, so that said contaminants may be efficiently
separated and removed from the reaction fluids. The fluids may then be pumped back
into the reactor vessel. An embodiment of the process is illustrated in Figure 5.
Various means for separating the insoluble matter may be employed in the invention,
including but not limited to such devices as strainers, filters, decanters, coalescing
filters, settlers, centrifuges, and other mechanical separators, and combinations
of such devices. The selection of the devices will depend upon the characteristics
of the contaminant(s) in relation to the aqueous reaction fluid mixture, the flow
rate of the side stream being treated, and the total quantity of contaminant(s)
present in the stream. It is desired to provide an improved process system capable
of continuous or extended maintenance-free operation of the urea hydrolysis system,
and requiring only occasional attention by the system operator.
In a preferred embodiment of a contaminant control means according
to the system of Figure 5, which focuses on separation of a contaminant material
with distinct physical properties from the aqueous reaction mixture, it may be assumed
that a urea hydrolysis reactor is designed to enable the collection of the contaminant
at a predictable location in the vessel. Such a design might be an upright cylindrical
vessel with volume for the liquid phase and volume for a contained gas phase. Since
one contaminant material is found to float upon the aqueous reaction mixture as
a distinct phase, effective removal may be effected by skimming off the contaminated
fluid layer in a desirable location, such as from the surface of the liquid phase
or in layers formed directly beneath the surface, for example. The skimmed fluids
containing the contaminant matter may be forced along a flow path by the pressure
of the reactor vessel under its normal operating pressure. The side-stream of skimmed
fluid is thus forced through a mechanical separation device, which may be a filtration
device which captures the contaminant, or which may separate the contaminant and
continuously discharge it as a distinct stream. Examples of the latter type of device
include a continuous centrifuge or a decanter. The cleaned reactant mixture is then
returned to the reactor by means of a suitable process pump and fluid conduit. The
fluid conduit may attach to the reactor vessel or the fluid conduit for the inlet
aqueous urea solution or at some other location upstream, so long as the material
is recovered and recycled to the reactor. The gaseous outlet from the physical separation
means can be in communication with the reactor vessel, as shown in Figure 5, or
with the gaseous product conduit downstream of pressure control means, as shown
in Figure 6.
The skimmed material can be diluted using water or, alternatively,
with an aqueous urea solution, such as a solution having the same or similar composition
as the inlet aqueous urea feed solution. The temperature of the skimmed material
may be adjusted upwardly or downwardly to enhance separation of contaminants. For
example, by lowering the temperature of the skimmed material, the contaminant mass
may solidify, enhancing the performance of solid filtration devices. Conversely,
by maintaining the material at a sufficiently high temperature to melt contaminant
components, separation of the contaminant liquid from the aqueous solution by decanting
is improved. In particular, it has been discovered that at least one component of
the contaminant mass melts at a temperature of about 100 °C. Furthermore, it has
been discovered that in a temperature range of about 100 °C and higher a contaminant
floats in a reaction mixture prepared with phosphoric acid catalyst, thus aiding
in separation of the contaminant liquid from the aqueous reaction mixture by decanting.
Allowing a tar-like contaminant to freeze when decanting is undesirable, since the
solid particles would adhere to surfaces in the decanter and would accumulate, leading
to problems sustaining the performance of the decanter. The aqueous urea or dilution
water stream can be heated or cooled to effectuate temperature control in the separation
operation.
Salts of ammonia increase in solubility as the temperature of a solution
increases. Salts of calcium decrease in solubility as the temperature of a solution
increases. This difference in solubility can be used to separate accumulating calcium
salts by filtering or decanting the skimmed material at higher temperatures, where
ammonia salts are soluble and calcium salts are not.
Similarly, if the reactor vessel is segmented or poorly agitated,
contaminants may tend to collect at several locations, requiring a plurality of
connection points where a side-stream can be drawn off and a skimming action effected
to remove the contaminant.
If the vessel is so thoroughly agitated that the insoluble material
is dispersed throughout the reaction mixture, then the location of one or more take-off
points for the side streams may be determined for convenience, and generally a low
point in the vessel is desirable.
In all cases the flow rate of the side stream will be sufficient to
turn over the entire contents of the reaction vessel within a certain time. The
rate of accumulation of the contaminant is directly proportional to the consumption
of the solid urea, which is known to the designer, and the quantity of fluid in
the reactor is also known. These parameters enable the designer to set a side stream
flow rate that will control the contaminant concentration in the system. Preferably,
the removal efficiency should be designed to exceed the contaminant formation and
accumulation rate.
In a second fundamental embodiment of the invention, a portion of
the stream removed from the reactor is deliberately discarded and the volume of
the discarded fluid is replaced by fresh reaction fluids, as shown in Figure 7,
enabling either continuous or intermittent removal of dissolved contaminants as
well as removal of the insoluble contaminants, thereby providing means to control
the maximum concentration all such contaminants may reach in the hydrolysis reactor.
In this instance, the quantity of material to be discarded and the frequency of
such discharge may be determined for the convenience of the operation. Generally,
intermittent discharge of small quantities would require a certain frequency of
such discharge to control the concentration in the reactor to a set maximum level.
Larger quantities would require less frequent discharge. In one example of the method,
a small portion of the side stream may be continuously discharged as a waste stream
to maintain the contaminants at an acceptable equilibrium concentration. As with
the embodiments depicted in Figures 5 and 6, the gaseous outlet from the physical
separation means can be in communication with the reactor vessel, as shown in Figure
7, or with the gaseous product conduit downstream of pressure control means, as
shown in Figure 8.
In an example of a preferred embodiment the process illustrated in
Figure 7, which provides means to remove insoluble contaminants and also dissolved
contaminants, the devices of the process embodiment of Figure 5 will include provision
to discharge a portion of the side stream and to replace this material with fresh
fluid reactants from a source of said make-up fluid. This accomplishes a "blow down"
or step reduction of the contaminants and is the most direct means to control the
build up of trace contaminants. The quantity of material removed and replaced is
set by the needs of the system and very much depends on the consequences of the
contaminant in the system.
Figure 9 illustrates an embodiment of a system for removing soluble
and insoluble contaminant materials from a urea hydrolysis reactor that contains
a dissolved or solid dispersed catalyst according to the invention. This method
has all of the features of that previously described in Figure 7, with the addition
of a process step in which process water is added to the side-stream as part of
the treatment step to remove the contaminants. When a dissolved or solid dispersed
catalyst is present in the process fluid reaction mixture the separation of contaminants
may benefit from dilution of the aqueous solution as part of the contaminant removal
step. Purified process water is used to make the aqueous urea feed solution, and
therefore a portion of said process water may be used as a diluent in the contaminant
removal step, provided this quantity of water is measured and accounted for in the
process control system. The concentration and the solubility of the dissolved catalyst
compounds will determine whether such dilution is beneficial. For example, dilution
may be beneficial when a dissolved catalyst might otherwise crystallize and form
a solid dispersed phase in the withdrawn liquid reaction mixture if the pressure
and/or temperature of the mixture is reduced relative to conditions in the reactor.
In addition, it may be beneficial to adjust the temperature of the side stream to
enhance removal of contaminants, and such temperature adjustment may also be conducted
as part of the processing method according to the invention. After such separation
of contaminants has been completed, the balance of the side-stream is recycled to
the liquid reaction mixture by means of a recycle pump and fluid conduit.
Figure 10 illustrates an embodiment of a system for removing soluble
and insoluble contaminant materials from a urea hydrolysis reactor that contains
a dissolved or solid dispersed catalyst according to the invention. This method
is a variation on that previously described in connection with Figure 9. The aqueous
urea feed is heated and combined with a side stream from a urea hydrolysis reactor
as part of the treatment step. The addition of aqueous urea feed at this point in
the process serves to dilute the process fluid reaction mixture with respect to
the concentration of a dissolved or solid dispersed catalyst. As with the method
described in connection with Figure 9, it may be beneficial to adjust the temperature
of the side stream to enhance removal of contaminants, and such temperature adjustment
may also be conducted as part of the processing method of the invention.
Uses for the discharged material should also be considered. The reaction
mixture from the hydrolysis reactor will likely contain water, urea, ammonia, polymers,
such as a polyamide and/or a urea-formaldehyde derivative, polymerization intermediates
and oligomers, both dissolved and suspended, and many minor contaminants introduced
with the reactants. The stream should be treated as a hazardous waste stream, and
may be chemically treated or combined in a safe manner with other solid wastes,
such as the ash from a fuel-fired boiler combustion process.
The removal of such trace contaminant material need only be considered
as a feature of the system when such contaminants are present in the feed materials
and a significant impact on the process performance is observed within an unacceptably
short period of operation. Provided that purified water is employed, the trace contaminants
in the urea and those that enter the system from the environment, if any, may not
present a serious problem, and may be dealt with effectively by regular cleaning
of the reactor, for example on an annual basis.
Fouling of the interior metal surfaces and particularly heat transfer
surfaces within the urea hydrolysis reactor by deposits of solids may present a
more difficult problem. Means to control such deposits may require more frequent
cleaning of the reaction fluid, agitation of the reaction fluid to increase the
shear forces at solid surfaces, and controlling the liquid level inside the reactor
to insure that heated surfaces are at least substantially submerged in the fluid
at all times. Agitation may be accomplished by any suitable means, including but
not limited to one or more mechanical agitators, gas injection, and steam injection.
The foregoing detailed description is given for clearness of understanding
only, and no unnecessary limitations should be understood therefrom, as modifications
within the scope of the invention may be apparent to those skilled in the art.
Anspruch[de]
Verfahren zum Steuern der Menge an löslichen und/oder unlöslichen Kontaminanten,
die in einer flüssigen Reaktionsmischung vorhanden sind, die in einem Reaktorgefäß
enthalten ist und eine Flüssigphase mit einer Oberfläche umfasst, wobei die Reaktionsmischung
in Wasser gelösten Harnstoff enthält, wobei die Kontaminanten im Verlauf einer Harnstoffhydrolysereaktion
gebildet werden und/oder akkumulieren, wobei das Verfahren die Schritte umfasst:
(a) Abnehmen eines Teils der die löslichen und/oder unlöslichen Kontaminanten
enthaltenden Reaktionsmischung aus der Flüssigphase und dem Reaktorgefäß;
und
(b) Abtrennen zumindest einer Kontaminante aus dem Rest des abgenommenen Teils
der Reaktionsmischung und Rückführen zumindest eines Teils des Rests der abgenommenen
Reaktionsmischung zur Flüssigphase in dem Reaktorgefäß.
Verfahren nach Anspruch 1, wobei eine unlösliche Kontaminante auf der Oberfläche
der Flüssigphase akkumuliert und die unlösliche Kontaminante in Schritt (b) abgetrennt
wird.
Verfahren nach Anspruch 1, wobei der gesamte Rest der abgenommenen Reaktionsmischung
zur Flüssigphase im Reaktorgefäß rückgeführt wird.
Verfahren nach Anspruch 1, wobei zumindest ein Teil des Rests der abgenommenen
Reaktionsmischung verworfen und durch eine äquivalente Menge an frischen flüssigen
und gelösten oder festen Reaktanten ersetzt wird, und zur Flüssigphase im Reaktorgefäß
rückgeführt wird, zusammen mit jeglichem nicht-verworfenen Teil der abgenommenen
Reaktionsmischung.
Verfahren nach Anspruch 1, wobei eine Kontaminante von der Oberfläche der Flüssigphase
entfernt wird.
Verfahren nach Anspruch 5, wobei die abgenommene Reaktionsmischung durch Abschöpfen
der Oberfläche der Flüssigphase gesammelt und aus dem Reaktorgefäß entfernt
wird.
Verfahren nach Anspruch 1, wobei eine Kontaminante von zumindest zwei Stellen
in der Flüssigphase entfernt wird.
Verfahren nach Anspruch 1, wobei eine Kontaminante von zumindest einem Punkt
unter der Oberfläche der Flüssigphase entfernt wird.
Verfahren nach Anspruch 8, wobei eine Kontaminante vom Boden des Reaktorgefäßes
entfernt wird.
Verfahren nach Anspruch 1, wobei der Teil der Reaktionsmischung während des
Verlaufs der Reaktion kontinuierlich aus dem Reaktorgefäß abgenommen wird.
Verfahren nach Anspruch 1, wobei der Teil der Reaktionsmischung während des
Verlaufs der Reaktion auf einer stoßweisen Basis abgenommen wird.
Verfahren nach Anspruch 1, wobei der abgenommene Teil der Reaktionsmischung,
der die löslichen und/oder unlöslichen Kontaminanten enthält, verdünnt wird.
Verfahren nach Anspruch 1, wobei die Reaktionsmischung ein gelöstes katalytisches
Agens oder ein gelöstes festes katalytisches Agens enthält.
Verfahren nach Anspruch 13, wobei die Kontaminante ausgewählt ist aus der Gruppe,
die aus im gelösten Harnstoff enthaltenen Harnstoff-Formaldehyd-Derivaten, Harnstoff-Formaldehyd-Oligomeren,
Harnstoff-Formaldehyd-Polymeren, Methylolharnstoff, Dimethylolharnstoff, Trimethylolharnstoff,
Harnstoff-Formaldehyd-Präkondensaten, Hexamethylentetramin, Saponaten, Lignosulfonaten
und Mischungen derselben besteht.
Verfahren nach Anspruch 13, wobei die Kontaminante ein Polyamid ist.
Anspruch[en]
A method of controlling the amount of soluble and/or insoluble contaminants
present in a liquid reaction mixture contained in a reactor vessel and comprising
a liquid phase having a surface, said reaction mixture containing urea dissolved
in water with said contaminants being formed and/or accumulated during the course
of a urea hydrolysis reaction, said method comprising the steps of:
(a) withdrawing a portion of the reaction mixture containing said soluble and/or
insoluble contaminants from the liquid phase and the reactor vessel; and,
(b) separating at least one contaminant from the remainder of the withdrawn
portion of the reaction mixture and recycling at least a portion of the remainder
of the withdrawn reaction mixture to the liquid phase in the reactor vessel.
The method of claim 1 wherein an insoluble contaminant accumulates on the surface
of the liquid phase and said insoluble contaminant is separated in step (b).
The method of claim 1 wherein all of the remainder of the withdrawn reaction
mixture is returned to the liquid phase in the reactor vessel.
The method of claim 1 wherein at least a portion of the remainder of the withdrawn
reaction mixture is discarded and replaced with an equivalent amount of fresh liquid
and dissolved or solid reactants and returned to the liquid phase in the reactor
vessel along with any non-discarded portion of the withdrawn reaction mixture.
The method of claim 1 wherein a contaminant is removed from the surface of the
liquid phase.
The method of claim 5 wherein the withdrawn reaction mixture is collected and
removed from the reactor vessel by skimming the surface of the liquid phase.
The method of claim 1 wherein a contaminant is removed from at least two locations
in the liquid phase.
The method of claim 1 wherein a contaminant is removed from at least one point
below the surface of the liquid phase.
The method of claim 8 wherein a contaminant is removed from the bottom of the
reactor vessel.
The method of claim 1 wherein said portion of the reaction mixture is withdrawn
from the reactor vessel continuously during the course of the reaction.
The method of claim 1 wherein said portion of the reaction mixture is withdrawn
on an intermittent basis during the course of the reaction.
The method of claim 1 wherein said withdrawn portion of the reaction mixture
containing said soluble and/or insoluble contaminants is diluted.
The method of claim 1 wherein said reaction mixture contains a dissolved catalytic
agent or a dispersed solid catalytic agent.
The method of claim 13 wherein said contaminant is selected from the group consisting
of urea-formaldehyde derivatives present in the dissolved urea, urea-formaldehyde
oligomers, urea-formaldehyde polymers, methylol urea, dimethylol urea, trimethylol
urea, urea-formaldehyde pre-condensates, hexamethylenetetramine, saponates, lignosulfonates,
and mixtures thereof.
The method of claim 13 wherein said contaminant is a polyamide.
Anspruch[fr]
Méthode pour contrôler la quantité de contaminants solubles et/ou insolubles
présents dans un mélange réactionnel liquide contenu dans une cuve de réacteur et
comprenant une phase liquide ayant une surface, ledit mélange réactionnel contenant
de l'urée dissoute dans de l'eau avec lesdits contaminants étant formés et/ou accumulés
durant le cours d'une réaction d'hydrolyse d'urée, ladite méthode comprenant les
étapes:
(a) retirer une portion du mélange réactionnel contenant lesdits contaminants
solubles et/ou insolubles de la phase liquide et de la cuve de réacteur; et,
(b) séparer au moins un contaminant du reste de la portion retirée du mélange
réactionnel et recycler au moins une portion du restant du mélange réactionnel retiré
dans la phase liquide de la cuve de réacteur.
La méthode de la revendication 1, dans laquelle un contaminant insoluble s'accumule
sur la surface de la phase liquide et ledit contaminant insoluble est séparé à l'étape
(b).
La méthode de la revendication 1, dans laquelle tout le restant du mélange réactionnel
retiré est retourné à la phase liquide dans la cuve de réacteur.
La méthode de la revendication 1, dans laquelle au moins une portion du restant
du mélange réactionnel retiré est jetée et remplacée par une quantité équivalente
de nouveau liquide et de réactifs dissous ou solides et retournée à la phase liquide
dans la cuve de réacteur avec quelconque portion gardée du mélange réactionnel retiré.
La méthode de la revendication 1, dans laquelle un contaminant est retiré de
la surface de la phase liquide.
La méthode de la revendication 5, dans laquelle le mélange réactionnel retiré
est recueilli et retiré de la cuve de réacteur en écumant la surface de la phase
liquide.
La méthode de la revendication 1, dans laquelle un contaminant est retiré d'au
moins deux emplacements dans la phase liquide.
La méthode de la revendication 1, dans laquelle un contaminant est retiré d'au
moins un endroit sous la surface de la phase liquide.
La méthode de la revendication 8, dans laquelle un contaminant est retiré du
fond de la cuve de réacteur.
La méthode de la revendication 1, dans laquelle ladite portion du mélange réactionnel
est retirée de la cuve de réacteur continuellement pendant le cours de la réaction.
La méthode de la revendication 1, dans laquelle ladite portion du mélange réactionnel
est retiré de façon intermittente pendant le cours de la réaction.
La méthode de la revendication 1, dans laquelle ladite portion retirée du mélange
réactionnel contenant lesdits contaminants solubles et/ou insolubles est diluée.
La méthode de la revendication 1, dans laquelle ledit mélange réactionnel contient
un agent catalytique dissout ou un agent catalytique solide dispersé.
La méthode de la revendication 13, dans laquelle ledit contaminant est sélectionné
parmi le groupe consistant de dérivés d' urée-formaldéhyde présents dans l'urée
dissoute, d'oligomères d'urée-formaldéhyde, de polymères d'urée-formaldéhyde, de
méthylolurée, de diméthylolurée, de triméthylolurée, de précondensats d'urée-formaldéhyde,
d'hexaméthylènetétramine, de saponats, de lignosulfonates, et de leurs mélanges.
La méthode de la revendication 13, dans laquelle ledit contaminant est un polyamide.