BACKGROUND
1. Field of the Invention
[0001] The present disclosure generally relates to producing chlorine dioxide. More particularly,
the disclosure relates to a chlorine dioxide reactor and methods of producing chlorine
dioxide and treating aqueous systems.
2. Description of the Related Art
[0002] With the decline of gaseous chlorine as a microbiocide, various alternatives have
been explored; including bleach, bleach with bromide, bromo-chloro dimethylhydantoin,
ozone, and chlorine dioxide (ClO
2). Of these, chlorine dioxide has generated a great deal of interest for control of
microbiological growth in a number of different industries, including the dairy industry,
the beverage industry, the pulp and paper industry, the fruit and vegetable processing
industries, various canning plants, the poultry industry, the beef processing industry
and miscellaneous other food processing applications. Chlorine dioxide is also seeing
increased use in municipal potable water treatment facilities and in industrial waste
treatment facilities, because of its selectivity towards specific environmentally-objectionable
waste materials, including phenols, sulfides, cyanides, thiosulfates, and mercaptans.
In addition, chlorine dioxide is being used in the oil and gas industry for downhole
applications as a well stimulation enhancement additive.
[0003] Unlike chlorine, chlorine dioxide remains a gas when dissolved in aqueous solutions
and does not ionize to form weak acids. This property is at least partly responsible
for the biocidal effectiveness of chlorine dioxide over a wide pH range. Moreover,
chlorine dioxide is a highly effective microbiocide at concentrations as low as 0.1
parts per million (ppm) over a wide pH range.
[0004] The biocidal activity of chlorine dioxide is believed to be due to its ability to
penetrate bacterial cell walls and react with essential amino acids within the cell
cytoplasm to disrupt cell metabolism. This mechanism is more efficient than other
oxidizers that "burn" on contact and is highly effective against
legionella, algae and amoebal cysts, giardia cysts, coliforms,
salmonella, shigella, and
cryptosporidium.
[0005] Unfortunately, chlorine dioxide in solution is unstable with an extremely short shelf
life and thus, is not commercially available. Chlorine dioxide solutions must typically
be generated at its point of use such as, for example, by a reaction between a metal
chlorate or metal chlorite in aqueous solution and a liquid phase strong acid.
US 2005/244328 A1 and
US 2010/155341 A1 disclose such processes for the production of chlorine dioxide. However, the use
of liquid phase strong acids poses handling issues and safety concerns.
[0006] Production of chlorine dioxide using chlorate, hydrogen peroxide, and acid generates
heat and may result in inadvertent explosive decomposition of chlorine dioxide if
the temperature is not properly controlled.
BRIEF SUMMARY
[0007] A method of producing chlorine dioxide is disclosed. The method may include feeding
a first solution comprising an acid through a first feed line into a mixing device;
feeding a second solution comprising chlorite through a second feed line into the
mixing device; mixing the first solution and the second solution in the mixing device
to form a reaction mixture; feeding the reaction mixture into the reactor; reacting
the acid and the chlorite in the reactor, wherein the reactor comprises a proximal
portion in fluid communication with the mixing device and a distal portion in fluid
communication with a motive water line; and mixing chlorine dioxide with motive water
in the motive water line at the distal portion of the reactor. The mixing device is
in fluid communication with a reactor, and the mixing device, the reactor, a portion
of the first feed line, and a portion of the second feed line are positioned within
the motive water line The reactor comprises a coiled configuration having a coil plane
angle of 1 degree to 60 degrees.
[0008] In some embodiments, the acid is hydrochloric acid, phosphoric acid, sulfuric acid,
hypochlorous acid, or any combination thereof.
[0009] Another of producing chlorine dioxide is also disclosed. The method may include feeding
a first solution comprising an acid through a first feed line into a mixing device;
feeding a second solution comprising chlorate and hydrogen peroxide through a second
feed line into the mixing device; mixing the first solution and the second solution
in the mixing device to form a reaction mixture, wherein the mixing device is in fluid
communication with a reactor; feeding the reaction mixture into the reactor; reacting
the acid, the chlorate, and the hydrogen peroxide in the reactor, wherein the reactor
comprises a proximal portion in fluid communication with the mixing device and a distal
portion in fluid communication with a motive water line, wherein the mixing device,
the reactor, a portion of the first feed line, and a portion of the second feed line
are positioned within the motive water line; and mixing chlorine dioxide with motive
water in the motive water line at the distal portion of the reactor The reactor comprises
a coiled configuration having a coil plane angle of 1 degree to 60 degrees.
[0010] In some embodiments, the acid is sulfuric acid.
[0011] In other embodiments, a method of treating process water is disclosed. The method
may include producing chlorine dioxide as described herein and injecting the chlorine
dioxide and the motive water into the process water.
[0012] In some embodiments, the motive water line includes at least two longitudinal channels
through which motive water may flow.
[0013] In some embodiments, the reaction mixture has a residence time in the reactor of
at least about 0.1 minute, and a precursor velocity is at least about 25 cm/min, wherein
the precursor velocity is a velocity of the first and second solutions.
[0014] In some embodiments, the methods described herein may include cooling the mixing
device and the reactor with the motive water.
[0015] In some embodiments, the methods described herein may include producing the chlorine
dioxide at a rate ranging from 0.0005 kg.h
-1 (0.001 lb/ hour) to 9 kg.h
-1 (20 lb/hour).
[0016] In some embodiments, the methods described herein may include operating the reactor
at a temperature ranging from 2 °C to 80 °C.
[0017] In some embodiments, the method may include determining a chlorine dioxide demand
in the process water using measurements selected from a chlorine dioxide sensor, an
oxidation and reduction potential, a flow meter, a microbiological measurement, and
any combination thereof.
[0018] In some embodiments, a cooling tower comprises the process water.
[0019] In other embodiments, a reactor for producing chlorine dioxide is disclosed. The
reactor may include a mixing device; a first feed line in fluid communication with
the mixing device; a second feed line in fluid communication with the mixing device;
a reactor comprising a proximal portion in fluid communication with the mixing device
and a distal portion in fluid communication with a motive water line; wherein the
mixing device, the reactor, a portion of the first feed line, and a portion of the
second feed line are positioned within the motive water line.
[0020] The reactor includes a coiled configuration having a coil plane angle of 1 degree
to 60 degrees.
[0021] In some embodiments, the first feed line and the second feed line are opposite to
and directed against each other.
[0022] In some embodiments, the reactor is operated at a pressure about equal to or greater
than atmospheric pressure. Atmospheric pressure includes pressures ranging from about
101.3 kPa to about 33.7 kPa. In some embodiments, the reactor is operated at a pressure
of about 101.3 kPa.
[0023] The foregoing has outlined rather broadly the features and technical advantages of
the present disclosure in order that the detailed description that follows may be
better understood. Additional features and advantages of the disclosure will be described
hereinafter that form the subject of the claims of this application.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0024] A detailed description of the invention is hereafter described with specific reference
being made to the drawings in which:
FIG. 1 shows a conceptual diagram of an embodiment of a method of treating cooling
tower water by generating chlorine dioxide onsite;
FIG. 2 shows an embodiment of a chlorine dioxide mixer and reactor;
FIG. 3 shows an embodiment of a chlorine dioxide mixer and reactor;
FIG. 4 shows a cross-sectional view of an embodiment of a chlorine dioxide mixer and
reactor;
FIG. 5 shows an embodiment of a coiled reactor;
FIG. 6 shows a cross-sectional view of an embodiment of the motive water line and
the reactor; and
FIG. 7 shows a conceptual diagram of an embodiment of a method of treating cooling
tower water and other targets by generating chlorine dioxide onsite.
DETAILED DESCRIPTION
[0025] Various embodiments are described below with reference to the drawings in which like
elements generally are referred to by like numerals. The relationship and functioning
of the various elements of the embodiments may better be understood by reference to
the following detailed description. However, embodiments are not limited to those
illustrated in the drawings. It should be understood that the drawings are not necessarily
to scale, and in certain instances details may have been omitted that are not necessary
for an understanding of embodiments disclosed herein, such as - for example-conventional
fabrication and assembly.
[0026] Traditionally, an eductor withdraws the chlorine dioxide solution from the reactor
using reduced pressure. Reduced pressure is produced by feeding motive water through
the eductor; however, the quality and quantity of the motive water must be carefully
controlled to avoid producing varying pressures. Varying pressures can lead to inefficiencies
in chlorine dioxide production.
[0027] A method is disclosed for treating process water. The method may include feeding
a first solution comprising an acid through a first feed line into a mixing device
and feeding a second solution comprising chlorate and hydrogen peroxide through a
second feed line into the mixing device. The first and second solutions are then mixed
in the mixing device to form a reaction mixture. A reactor is in fluid communication
with the mixing device. After mixing, the reaction mixture is fed into the reactor.
The acid, chlorate, and hydrogen peroxide react in the reactor, thereby producing
chlorine dioxide. The reactor includes a proximal portion in fluid communication with
the mixing device and a distal portion in fluid communication with a motive water
line. The mixing device, the reactor, a portion of the first feed line, and a portion
of the second feed line are positioned within the motive water line. As the reaction
mixture exits the reactor, the reaction mixture mixes with motive water in the motive
water line at the distal portion of the reactor. The mixed chlorine dioxide and motive
water may be injected into the process water.
[0028] In some embodiments, the first solution may consist of or comprise sulfuric acid
and water, where the sulfuric acid concentration ranges from about 50% by weight to
about 98% by weight. The sulfuric acid concentration in the first solution may be
about 78%. In some embodiments, the second solution may comprise or consist of chlorate,
hydrogen peroxide, and water. The second solution may comprise a concentration of
chlorate that is in a range of about 25% by weight to about 60% by weight. The concentration
of chlorate in the second solution may be about 40% by weight. The concentration of
hydrogen peroxide in the second solution may be in the range of about 2% by weight
to about 30% by weight. The concentration of hydrogen peroxide in the second solution
may be about 8% by weight. In some embodiments, the acid may be sulfuric acid and
the chlorate may be sodium chlorate.
[0029] In some embodiments, the first solution may consist of or comprise hydrochloric acid
and water, where the hydrochloric acid concentration ranges from about 5% by weight
to about 38% by weight. The hydrochloric acid concentration in the first solution
may be about 37%. In some embodiments, the second solution may consist of or comprise
a chlorite and water. The second solution may have a chlorite concentration that ranges
from about 5% by weight to about 60% by weight. The chlorite concentration in the
second solution may be about 25% by weight. In some embodiments, the chlorite may
be sodium chlorite.
[0030] In certain embodiments, at least two feed lines carry precursor chemicals to the
mixing device. The precursors may include the first and second solutions. In other
embodiments, a third feed line may feed water or other chemicals to the mixing device.
In some embodiments, the feed lines to the mixing device may consist of a first feed
line and a second feed line.
[0031] In other embodiments, the method may further include the step of cooling the mixing
device and the reactor with the motive water. The motive water passing through the
motive water line may serve to control the temperature of the solutions in the feed
lines and the temperature of the reaction mixture.
[0032] The reactor comprises a coiled configuration, which may further increase mixing and
enhance mixing. The reactor having a coiled configuration includes a coil plane angle
in a range from 1 to 60 degrees. In some embodiments, the coil plane angle may be
from about 5 to about 30 degrees. The reactor having a coiled configuration may include
a coil diameter. The coil diameter may be in a range from about 0.1 to about 16.0
inches, about 1 inch to about 16 inches, about 2 inch to about 16 inches, about 2
inch to about 10 inches, or about 2 inches to about 4 inches
[0033] In some embodiments, the motive water line may comprise at least two channels. The
channels may be longitudinal. In some embodiments, the motive water line may be a
double containment pipe. The motive water line may have an inner channel and an outer
channel through which motive water may flow, and the reactor may be positioned within
the inner channel. The motive water flow rate in the outer channel may be different
than the flow rate of the motive water in the inner channel. The motive water flow
rate in the inner channel may be such that the temperature of the reaction mixture
is controlled within a certain range. The reaction mixture temperature may be 2 °C
to 80 °C, 2 °C to 70 °C, 35 °C to 70 °C, 40 °C to 70 °C, or 50 °C to 70 °C. The reaction
mixture temperature may be 60 °C. The temperature of the motive water in the outer
channel may be different from the temperature of the motive water in the inner channel.
The outer channel may contain motive water having a flow rate sufficient to dilute
the chlorine dioxide to a safe concentration such as less than about 3,000 ppm, less
than about 2,000 ppm, less than about 1,500 ppm, less than about 1,000, less than
about 750 ppm, less than about 500 ppm, less than about 250 ppm, less than about 100
ppm, or less than about 50 ppm.
[0034] In some embodiments, the first feed line and the second feed line may be opposite
to and directed against each other. In this configuration, the solutions fed through
the first and second feed lines may collide and mix.
[0035] In some embodiments, the reactor may include at least one contact zone. In some embodiments,
the reactor may include at least two, three, four, or more contact zones. In other
embodiments, the contact zone may comprise an inner diameter at least about two times
larger than an inner diameter of the reactor. In some embodiments, the contact zone
may comprise an inner diameter at least about three, four, or five times larger than
an inner diameter of the reactor.
[0036] In some embodiments, the acid, the chlorate, and the hydrogen peroxide may form a
reaction mixture in the mixing device. The first and second solutions combine to form
the reaction mixture. At least one advantage of using a solution of chlorate and hydrogen
peroxide to react with an acid solution is that no chlorine gas is produced. The absence
of chlorine gas provides a more safe and economical process.
[0037] In certain embodiments, the reaction mixture may have a residence time in the reactor
of at least 0.1 minute. In some embodiments, the reaction mixture may have a residence
time in the reactor of at least about 1 minute. In other embodiments, the reaction
mixture may reside in the reactor for at least about 3 minutes, at least about 4 minutes,
at least about 5 minutes, at least about 6 minutes, at least about 7 minutes, at least
about 8 minutes, at least about 9 minutes, or at least about 10 minutes. In some embodiments,
the reaction mixture may have a residence time in the reactor of about 3.8 minutes.
Residence time may be calculated by dividing total reactor volume by total precursor
flow rate.
[0038] In some embodiments, the precursors (acid and chlorate/hydrogen peroxide or chlorite)
may be fed into the mixing device at a flow velocity of 25 cm/minute. In some embodiments,
the precursors may be fed into the mixing device at a flow velocity in a range from
about 20 cm/minute to about 200 cm/minute, about 20 cm/minute to about 65 cm/minute,
or about 20 cm/minute to about 50 cm/minute. In some embodiments the precursor velocity
may be 25 cm/minute, 50 cm/minute, or 65 cm/min. Precursor velocity can be calculated
by dividing total precursor flow rate by the cross-sectional area of the reactor.
[0039] In other embodiments, the reactor may be operated at a pressure equal to or greater
than atmospheric pressure.
[0040] In some embodiments, the method may include withdrawing chlorine dioxide using an
eductor. In some embodiments, the methods disclosed do not use an eductor to withdraw
chlorine dioxide from the reactor. In some embodiments, the reactor does not comprise
an educator.
[0041] In some embodiments, the method may include operating the reactor at a temperature
in a range from 2 °C to 80 °C. In some embodiments, the method may include operating
the reactor at a temperature of 60 °C.
[0042] In some embodiments, the temperature of the motive water may be in a range from 2
°C to 80 °C. The motive water temperature may be in range from about 15 °C to about
70 °C, about 30 °C to about 70 °C, about 40 °C to about 70 °C, about 40 °C to about
60 °C, or about 50 °C to about 70 °C.
[0043] In some embodiments, the method may include determining a chlorine dioxide demand
in the process water using measurements from a sensor, such as a chlorine dioxide
sensor, an oxidation and reduction potential, a flow meter, a microbiological measurement,
or any combination thereof. In some embodiments, the chlorine dioxide may be added
to the process water in a cooling tower.
[0044] In some embodiments, the chlorine dioxide may be added to an aqueous system. The
present disclosure is not limited to adding chlorine dioxide to process water in cooling
towers.
[0045] In some embodiments, the method may include a process control system including a
Programmable Logic Controller (PLC), a chlorine dioxide analyzer, a pressure transmitter
(PT) and a flow transmitter (FT), controls the feed pumps for the chemicals to the
reactor and for the motive water.
[0046] In some embodiments, the method may include a distribution system. The distribution
system may include at least two independently controlled dosing points. The distribution
system may include, for example, 3, 4, 5, 6, 7, or 8 independently controlled dosing
points. When the different ClO
2 production set points are entered into the controller, the PLC automatically calculates
and adjusts the required production of the chlorine dioxide reactor. A distribution
system may allow chlorine dioxide solution to be distributed to multiple points directly
from the discharge chlorine dioxide reactor, thus avoiding a storage tank system.
The distribution system may incorporate a ClO
2 solution pump and flowmeters and control valves to manage the distribution among
various dosing points.
[0047] The flow meters that may be used with the disclosed methods may be any suitable flow
meter, such as but not limited to clamp-on or pulse flow meters. Pulse-based flow
meters detect the kinetic energy of flowing fluid using optical or magnetic sensors
and converting it into electrical energy in the form of digital pulses. The flow rate
can be determined by measuring the periods of the pulses.
[0048] The pumps used to feed the first and second solutions may be in communication with
the PLC. The PLC may also be in communication with any pumps placed on a product feed
line.
[0049] In some embodiments, the reactor may be in fluid communication with at least one
product feed line. Pumps may be placed on each one of the product feed lines, or in
some embodiments, multiple product feed lines may share a single pump.
[0050] In some embodiments, any of the methods disclosed herein may include determining
a flow rate of the first solution in the first feed line, a flow rate of the second
solution in the second feed line, a flow rate of a chlorine dioxide solution in a
product feed line, or a flow rate of the motive water in the motive water line.
[0051] In some embodiments, the flow rate of any solutions being fed into the reactor may
be determined using at least two flow meters that determine the flow rate based on
different principles to ensure that an accurate amount of precursor chemical is being
fed into the reactor.
[0052] In some embodiments, any of the methods disclosed herein may include sensing a reactor
pressure. In some embodiments, the product feed lines may be equipped with a check
valve, flow meter, and feed pump.
[0053] In certain embodiments, any of the methods disclosed herein may include calculating
a chlorine dioxide dose. The chlorine dioxide dose may be calculated using the flow
rates of the, first solution, second solution, motive water, chlorine dioxide solution
in the product feed lines, and the chlorine dioxide concentration. For example, the
chlorine dioxide concentration in the main line can be calculated using the formula:
Main Line Product Rate = (F
p + Fa + Fw - F
productline)*C
ClO2 where F
p is the flow rate of hydrogen peroxide and chlorate, F
a is the flow rate of the acid, F
w is the flow rate of the motive water, F
productline is the sum of flow rates in any product feed lines connected to the main line, and
C
ClO2 is the concentration of chlorine dioxide.
[0054] Multiple alarms and failsafe settings may be set using the PLC. For example, pump
issues may be detected by monitoring the differential between the flow meter readings
and the pump rate calculations. Some failsafes may include pressure relief valves
on the reactor or product feed lines. Any of the feed lines may have a pressure sensor
that communicates readings to the main control device. By way of example, the main
control device may include a PLC and an Adam AI/AO (analog input/analog output) module.
If the reactor is housed in a cabinet, then the cabinet may have leak detection sensors
and a cabinet door lock.
[0055] In other embodiments of the present disclosure, a method for producing chlorine dioxide
is provided. The method includes feeding a first solution comprising an acid through
a first feed line into a mixing device and feeding a second solution comprising chlorate
and hydrogen peroxide through a second feed line into the mixing device. The method
includes mixing the first solution and the second solution in the mixing device. The
mixing device is connected to a reactor. After mixing, the first solution and the
second solution are fed into the reactor where the acid, the chlorate, and the hydrogen
peroxide react to form chlorine dioxide. The reactor includes a proximal portion in
fluid communication with the mixing device and a distal portion in fluid communication
with a motive water line. The mixing device, the reactor, a portion of the first feed
line, and a portion of the second feed line are positioned within the motive water
line. The method includes mixing the chlorine dioxide with motive water in the motive
water line at the distal portion of the reactor The reactor comprises a coiled configuration
having a coil plane angle of 1 degree to 60 degrees.
[0056] In other embodiments, a method of producing chlorine dioxide is provided. The method
includes feeding a first solution, such as an acid, through a first feed line into
a mixing device. A second solution, such as chlorite, is fed through a second feed
line into the mixing device. The mixing device is in fluid communication with a reactor.
The method includes mixing the first solution and the second solution in the mixing
device to form a reaction mixture. The reaction mixture is fed into the reactor where
the acid and the chlorite react. The reactor includes a proximal portion in fluid
communication with the mixing device and a distal portion in fluid communication with
a motive water line. The mixing device, the reactor, a portion of the first feed line,
and a portion of the second feed line are positioned within the motive water line.
The method includes mixing chlorine dioxide with motive water in the motive water
line at the distal portion of the reactor. The reactor comprises a coiled configuration
having a coil plane angle of 1 degree to 60 degrees. In some embodiments, the acid
may be hydrochloric acid, phosphoric acid, sulfuric acid, hypochlorous acid, or any
combination thereof. In some embodiments, the acid may be hydrochloric acid.
[0057] A reactor for producing chlorine dioxide is provided. The reactor may include a mixing
device, a first feed line in fluid communication with the mixing device, and a second
feed line in fluid communication with the mixing device. The reactor may include a
proximal portion in fluid communication with the mixing device and a distal portion
in fluid communication with a motive water line. The mixing device, the reactor, a
portion of the first feed line, and a portion of the second feed line may be positioned
within the motive water line. The reactor comprises a coiled configuration having
a coil plane angle of 1 degree to 60 degrees.
[0058] In some embodiments, the diameter of the motive water line may be larger than the
diameter of the reactor and the first and second feed lines such that the reactor
and the feed lines may be positioned in the lumen of the motive water line.
[0059] in some embodiments, the first feed line and the second feed line may be opposite
to and directed against each other as in a "T" configuration, see, for example, the
orientation of components corresponding to reference numerals 11 and 12 in Fig. 4.
[0060] In certain embodiments, the reactor may include at least one contact zone. The contact
zone may include an inner diameter at least two times larger than an inner diameter
of the reactor. As the reaction mixture flows through the reactor it may reach a contact
zone where the reaction mixture may further mix. The outlet of the contact zone may
narrow to the diameter of the reactor.
[0061] In some embodiments, the reactor may have a length in a range from about 25 inches
to about 300 inches. In some embodiments, the reactor may have a length in a range
from about 30 inches to about 90 inches, about 30 inches to about 80 inches, about
30 inches to about 70 inches, about 30 inches to about 60 inches, about 30 inches
to about 50 inches, about 40 inches to about 90 inches, about 40 inches to about 80
inches, about 35 inches to about 45 inches, or about 35 inches to about 60 inches.
In other embodiments, the reactor may be about 40 inches in length.
[0062] The reactor may be positioned horizontally, vertically, or any angle in between.
In some embodiments, the reactor may be positioned vertically. In embodiments where
the reactor is a coiled reactor, the reactor may spiral upward.
[0063] In some embodiments, the reactor may have an inner diameter in a range from about
0.1 inches to about 4 inches. In some embodiments, the reactor may have an inner diameter
in a range from about 1 inch to about 1.25 inches, or about 0.25 inches to about 1.25
inches. In some embodiments, the reactor may have an inner diameter of about 0.25
inches, about 2 inches, about 3 inches, or about 4 inches. In other embodiments, the
reactor may have an inner diameter of about 1.25 inches, about 1 inch, about 0.75
inches, about 0.375 inches, or about 0.1875 inches.
[0064] In some embodiments, the chlorine dioxide may be produced at a rate in a range from
0.0005 kg.h
-1 (0.001 lb/hour) to 9 kg.h
-1 (20 lb/hour). In some embodiments, the chlorine dioxide may be produced at a rate
in a range from 0.0009 kg.h-1 (0.002 lb/hour) to 6.8 kg.h-1 (15 lb/hour). In some
embodiments, the chlorine dioxide may be produced at a rate in a range from 2.3 kg.h-1
(5 lb/hour) to 6.8 kg.h-1 (15 lb/hour). As chlorine dioxide is produced at a higher
rate, a larger diameter reactor may be used to ensure that the residence time in the
reactor is at least 3 minutes. In some embodiments, the residence time in the reactor
may be at least 2 minutes.
[0065] Referring to the figures, FIG. 1 shows a conceptual diagram of certain embodiments
for a method of treating cooling tower water onsite. Precursor chemicals may be stored
in a tank
10 onsite from which the chemicals may be fed through the first feed line
11 and the second feed line
12 into a chlorine dioxide mixer and reactor
15. Water may be fed into the mixer to dilute the precursor chemicals being fed into
the chlorine dioxide mixer and reactor
15. Water may be fed into the mixer and reactor
15 through a motive feed line
14. A water line
13 may supply water to the motive water line
14 and/or it may supply water to dilute acid before or after entering the mixer. Chlorine
dioxide may be injected into process water
16 that may be fed into a cooling tower
19. A pump
17 may feed the process water
16 through a heat exchanger
18.
[0066] FIG. 2 and FIG. 3 show a closer view of some embodiments of the chlorine dioxide
mixer and reactor
15. The first feed line
11 and the second feed line
12 may introduce precursor chemicals into the mixing device
20. In some embodiments, a water line
13 may feed water into the mixing device
20. A motive feed line
14 may supply water to the motive water line
24. In some embodiments, the water in the motive water line
24 may cool the reactor
21. In other embodiments, the water in the motive water line
24 dilutes and mixes with the chlorine dioxide at the distal portion of the reactor
23. The proximal portion of the reactor
22 may be connected to the mixing device
20. Fluid in the mixing device
20 may flow out of the mixing device
20 and into the reactor
21. In some embodiments, the reactor
21 may be in a coiled configuration. In some embodiments, a chlorine dioxide feed line
25 carries the chlorine dioxide mixed with motive water to the process water. Some embodiments
may include at least one contact zone
30 (see FIG. 3, for example). The contact zone
30 may allow increased mixing of the reaction mixture or increased residence time in
the reactor in order to increase reaction efficiency.
[0067] FIG. 4 shows an embodiment where the first feed line
11 and the second feed line
12 are opposite to and directed against each other. The solutions mix in the mixing
device
20 and then enter the proximal portion of the reactor
22. The reaction mixture may continue to flow through the reactor
21, exit the distal portion of the reactor
23, and mix with the motive water in the motive water line
24. Water may be fed into the motive water line
24 from the motive feed line
14. In some embodiments, the mixing device
20, the reactor
21, a portion of the first feed line
40, and a portion of the second feed line
41 are positioned within the motive water line
24.
[0068] FIG. 5 shows an embodiment where the reactor
21 may comprise a coiled configuration. The reactor having a coiled configuration may
include a coil plane angle
50 ranging from about 5 to about 30 degrees. The reactor having a coiled configuration
may include a coil diameter
51. The coil diameter may range from about 0.1 inch to about 4.0 inches. The inner diameter
of the coil reactor may be as described above for the reactor.
[0069] FIG. 6 show an embodiment where the motive water line comprises an outer channel
60 and an inner channel
61. The reactor
21 may be disposed within the lumen of the inner channel
61. In this configuration, the motive water may be fed into the motive water line via
two separate channels. The outer channel
60 and inner channel
61 may carry motive water at difference flow rates. The motive water in the outer channel
60 may have a different temperature than the motive water in the inner channel
61.
[0070] FIG. 7 shows a conceptual diagram of certain embodiments for a method of treating
cooling tower water and multiple targets. Precursor chemicals may be stored in a tank
10 onsite from which the chemicals may be fed through the first feed line
11 and the second feed line
12 into a chlorine dioxide mixer and reactor
15. Water may be fed into the mixer via line
13 to dilute the precursor chemicals being fed into the chlorine dioxide mixer and reactor
15. Water may be fed into the mixer and reactor
15 through a motive feed line
14. Chlorine dioxide may be injected into process water
16 that may be fed into a cooling tower
19. A pump
17 may feed the process water
16 through a heat exchanger
18. The chlorine dioxide generated in the reactor
15 can be added to process water
16 or diverted into a product feed line
70 for treating other targets. The product feed line
70 may include a valve
71, a flow meter
72, and a pump
73. All valves and pumps may be controlled using a PLC (not pictured).
Examples
Example 1
[0071] A solution containing about 40% sodium chlorate and about 8% hydrogen peroxide and
an aqueous solution of about 78% sulfuric acid were each fed at a rate of about 63
mL/h through 0.25 inch tubing into a 0.25 inch Kynar Union Tee that was inserted inside
a polyvinyl chloride cross tube with about a 2 inch inner diameter.
[0072] The precursors flowing through the Kynar Union Tee then flowed through about 40 inches
of 0.25 inch tubing (8 mL volume) that was inserted inside 0.5 inch tubing. Motive
water flowed into the polyvinyl chloride cross tube and out of the 0.5 inch tubing
(around the 0.25 inch tubing) to provide cooling and dilution. The reaction tube length
and precursor velocity of about 26.5 cm/min provided a residence time of about 3.81
minutes.
[0073] Each experiment ran for about 15 minutes, and the chlorine dioxide concentration
was measured about every 5 minutes. The motive water served two purposes: dilution
and cooling. Water to precursor ratio of about 30 or less was required to establish
the heat needed for the reaction. This generated chlorine dioxide concentrations of
greater than about 5,500 mg/L.
[0074] Flow velocity of the precursors was set at about 26.5 cm/min. Flow velocities may
be greater than about 25 cm/min to allow the gaseous oxygen to remain as nano- and
micro-bubbles and to accelerate the movement of nano- and micro-bubbles out of the
reactor tube.
[0075] The concentration of chlorine dioxide was determined using a spectrophotometer. Readings
from the spectrophotometer were used to calculate the chlorine dioxide concentration
using a calibration curve. The curve was prepared according to lodometric Method 4500-ClO
2 in Standard Methods for the Examinations of Water and Wastewater 20
th edition 1998.
[0076] The amount of solution consisting of about 40% sodium chlorate and about 7.99% hydrogen
peroxide required for 100% reaction efficiency was about 2.86 mL to produce about
1 gram of chlorine dioxide. The reaction or conversion efficiency was calculated from
the percentage ratio of the total chlorine dioxide generated to the theoretical chlorine
dioxide production based on the amount of Purate consumed:
ηcurrent = (C
ClO2 · Q
ClO2) / (Q
Purate / 2.86) where C
ClO2 is concentration of chlorine dioxide (g/L), Q
ClO2 flowrate of chlorine dioxide (L/hour), and Q
Purate flow rate of Purate (chlorate about 40% and hydrogen peroxide about 7.99% mixture)
(mL/hour).
Table 1. Reaction efficiency
| Motive Water |
|
|
|
|
|
|
|
|
|
| (L/h) |
7.50 |
7.50 |
7.50 |
3.76 |
3.76 |
3.76 |
3.14 |
3.14 |
3.14 |
| Purate Flow Rate |
|
|
|
|
|
|
|
|
|
| (mL/h) |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
| 78% Sulfuric Acid |
|
|
|
|
|
|
|
|
|
| Flow Rate (mL/h) |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
63.0 |
| Residence Time |
|
|
|
|
|
|
|
|
|
| (min) |
3.81 |
3.81 |
3.81 |
3.81 |
3.81 |
3.81 |
3.81 |
3.81 |
3.81 |
| Water:Prec. Ratio |
60 |
60 |
60 |
30 |
30 |
30 |
25 |
25 |
25 |
| Precursor Flow |
|
|
|
|
|
|
|
|
|
| Velocity (cm/m) |
26.5 |
26.5 |
26.5 |
26.5 |
26.5 |
26.5 |
26.5 |
26.5 |
26.5 |
| Chlorine Dioxide |
|
|
|
|
|
|
|
|
|
| Conc. (g/L) |
2.49 |
2.36 |
2.35 |
5.51 |
5.53 |
6.62 |
6.69 |
6.73 |
6.70 |
| Chlorine Dioxide |
|
|
|
|
|
|
|
|
|
| Flow Rate (L/h) |
7.63 |
7.63 |
7.63 |
3.89 |
3.89 |
3.89 |
3.27 |
3.27 |
3.27 |
| Actual Output |
|
|
|
|
|
|
|
|
|
| (g/h) |
18.7 |
17.7 |
17.6 |
21.4 |
21.5 |
21.8 |
21.8 |
22.0 |
21.9 |
| Theoretical |
|
|
|
|
|
|
|
|
|
| Output (g/h) |
22.0 |
22.0 |
22.0 |
22.0 |
22.0 |
22.0 |
22.0 |
22.0 |
22.0 |
| Reaction |
|
|
|
|
|
|
|
|
|
| Efficiency (%) |
84.9 |
80.3 |
79.9 |
97.2 |
97.6 |
99.1 |
99.1 |
99.8 |
99.3 |
Example 2
[0077] In this experiment, a 3/8" inch Tee connected to about 91.4 cm of 3/8" inch tubing
was used as a mixing device and reactor, respectively. Different residence times (calculated
by dividing reactor volume by total reactant flow rate) and motive water temperatures
were tested. The conversion rate was calculated as described above. Purate was a mixture
of chlorate and hydrogen peroxide as described above.
Table 2. Residence time and temperature effects on conversion.
| Residence Time |
Motive Water Temp |
Purate |
H2SO4 |
ClO2 |
H2SO4/Purate |
Conversion Rate |
| min |
°C |
mole/min |
mole/min |
Ib/hr |
mole/mole |
% |
| 15.6 |
34 |
0.0095 |
0.0250 |
0.085 |
2.64 |
88.4 |
| 15.6 |
37 |
0.0095 |
0.0250 |
0.085 |
2.64 |
93.4 |
| 8.6 |
36 |
0.0172 |
0.0455 |
0.154 |
2.64 |
87.1 |
| 8.6 |
43 |
0.0172 |
0.0455 |
0.154 |
2.64 |
88.1 |
| 8.6 |
53 |
0.0172 |
0.0455 |
0.154 |
2.64 |
99.7 |
| 8.6 |
51 |
0.0172 |
0.0366 |
0.154 |
2.13 |
86.2 |
| 15.6 |
50 |
0.0095 |
0.0250 |
0.085 |
2.64 |
95.9 |
| 7.8 |
51 |
0.0189 |
0.0500 |
0.169 |
2.64 |
99.9 |
| 3.9 |
50 |
0.0379 |
0.1001 |
0.338 |
2.64 |
89.0 |
| 5.2 |
48 |
0.0284 |
0.0751 |
0.254 |
2.64 |
96.0 |
Example 3
[0078] A 1/4" inch Tee connected to a 12 ml chamber by about 5.72 cm of 1/4" inch tubing
was used in this experiment. The chamber was also connected to about 26 cm of 1/4"
tubing. The configuration was similar to the reactor depicted in FIG. 3 where the
12 ml chamber may be a contact zone.
[0079] Table 3 shows the effects of motive water and the ratio of H
2SO
4/Purate on conversion rate. Table 4 shows the effects of reduced amount of acid at
a motive water temperature of about 62 °C and a residence time of about 14 min. The
residence time for these trials was fixed at about 14 min.
Table 3. Effects of motive water temperature and H
2SO
4/Purate on conversion
| Temp |
Purate |
H2SO4 |
ClO2 |
H2SO4/Purate |
Conversion Rate |
| °C |
mole/min |
mole/min |
Ib/hr |
mole/mole |
% |
| 16 |
0.0095 |
0.0250 |
0.085 |
2.64 |
64.8 |
| 30 |
0.0095 |
0.0250 |
0.085 |
2.64 |
92.6 |
| 41 |
0.0095 |
0.0250 |
0.085 |
2.64 |
95.1 |
| 53 |
0.0095 |
0.0250 |
0.085 |
2.64 |
94.4 |
| 62 |
0.0095 |
0.0250 |
0.085 |
2.64 |
97.7 |
| 41 |
0.0095 |
0.0205 |
0.085 |
2.16 |
87.8 |
| 47 |
0.0095 |
0.0208 |
0.085 |
2.20 |
95.4 |
| 62 |
0.0095 |
0.0208 |
0.085 |
2.20 |
97.4 |
Table 4. Effect of reduced acid at 62 °C.
| Temp |
Purate |
H2SO4 |
ClO2 |
H2SO4/Purate |
Conversion Rate |
| °C |
mole/min |
mole/min |
lb/hr |
mole/mole |
% |
| 62 |
0.0095 |
0.0254 |
0.085 |
2.68 |
97.1 |
| |
0.0095 |
0.0208 |
0.085 |
2.20 |
99.8 |
| |
0.0095 |
0.0162 |
0.085 |
1.71 |
92.7 |
| |
0.0095 |
0.0127 |
0.085 |
1.34 |
65.9 |
[0080] Table 5 shows the effects of residence time and motive water temperature on conversion
rate.
Table 5. Effect of residence time and temperature on conversion rate.
| Residence Time |
Temp |
Purate |
H2SO4 |
ClO2 |
H2SO4/Purate |
Conversion Rate |
| min |
°C |
mole/min |
mole/min |
lb/hr |
mole/mole |
% |
| 3 |
53 |
0.0095 |
0.0159 |
0.085 |
1.68 |
52.7 |
| 14 |
47 |
0.0095 |
0.0162 |
0.085 |
1.71 |
78.9 |
| 14 |
62 |
0.0095 |
0.0162 |
0.085 |
1.71 |
92.7 |
| 17 |
45 |
0.0095 |
0.0159 |
0.085 |
1.68 |
71.7 |
| 17 |
46 |
0.0095 |
0.0162 |
0.085 |
1.71 |
83.7 |
| 17 |
46 |
0.0189 |
0.0324 |
0.170 |
1.71 |
68.5 |
| 17 |
62 |
0.0095 |
0.0162 |
0.085 |
1.71 |
92.1 |
Example 4
[0081] In this experiment, a 1/4" inch Tee connected to a 12 ml chamber by about 2 feet
of 1/4" inch tubing was used. The chamber was also connected to about 10 feet of 1/4"
tubing. The configuration was similar to the reactor depicted in FIG. 3 where the
12 ml chamber may be a contact zone. The volume of the reactor was about 78.2 ml.
Table 6. Effect of residence time, motive water temperature, and acid on conversion
rate.
| Residence Time |
Temp |
Purate |
H2SO4 |
ClO2 |
H2SO4/Purate |
Conversion Rate |
| min |
°C |
mole/min |
mole/min |
Ib/hr |
mole/mole |
% |
| 21.1 |
31.2 |
0.0095 |
0.0250 |
0.085 |
2.64 |
95.0 |
| 21.1 |
29.3 |
0.0095 |
0.0205 |
0.085 |
2.16 |
90.0 |
| 21.1 |
35.6 |
0.0095 |
0.0205 |
0.085 |
2.16 |
88.5 |
| 21.1 |
37.5 |
0.0095 |
0.0205 |
0.085 |
2.16 |
93.0 |
| 21.1 |
44.1 |
0.0095 |
0.0205 |
0.085 |
2.16 |
99.1 |
| 10.6 |
43.9 |
0.0189 |
0.0409 |
0.169 |
2.16 |
87.6 |
| 10.6 |
43.5 |
0.0189 |
0.0455 |
0.169 |
2.40 |
89.3 |
| 11.6 |
43.3 |
0.0172 |
0.0455 |
0.154 |
2.64 |
97.1 |
| 11.6 |
33.8 |
0.0172 |
0.0455 |
0.154 |
2.64 |
85.7 |
Example 5
[0082] Chlorine dioxide production was tested using the reactor disclosed herein and chlorite
as a precursor instead of chlorate. A solution of about 25 wt% of chlorite and a solution
of about 29 wt% hydrochloric acid was fed to a reactor. The reactor included a 1/4"
inch Tee (mixing device) connected to a 12 ml chamber by about 5.72 cm of 1/4" inch
tubing. The chamber was also connected to about 26 cm of 1/4" tubing. Table 7 shows
the reaction efficiency as a function of time.
Table 7. Chlorine dioxide production using chlorite and hydrochloric acid.
| Time (min) |
ClO2 (mg/L) |
ClO2 Vol. (L/h) |
ClO2 Output (g/h) |
NaClO2 Rate (L/h) |
mL NaClO2/g ClO2 |
Rxn. Eff. (%) |
| 0 |
162 |
7.59 |
1.23 |
0.013 |
10.25 |
54.5 |
| 2 |
178 |
7.59 |
1.35 |
0.013 |
9.33 |
59.9 |
| 4 |
202 |
7.59 |
1.53 |
0.013 |
8.22 |
68.0 |
| 6 |
214 |
7.59 |
1.62 |
0.013 |
7.76 |
72.1 |
| 8 |
225 |
7.59 |
1.71 |
0.013 |
7.38 |
75.8 |
| 10 |
227 |
7.59 |
1.72 |
0.013 |
7.31 |
76.4 |
| 12 |
229 |
7.59 |
1.74 |
0.013 |
7.25 |
77.1 |
| 14 |
264 |
7.59 |
2.00 |
0.013 |
6.29 |
88.9 |
| 16 |
280 |
7.59 |
2.12 |
0.013 |
5.93 |
94.3 |
| 18 |
282 |
7.59 |
2.14 |
0.013 |
5.89 |
94.9 |
| 20 |
289 |
7.59 |
2.19 |
0.013 |
5.75 |
97.3 |
| 22 |
291 |
7.59 |
2.21 |
0.013 |
5.71 |
98.0 |
| 24 |
289 |
7.59 |
2.19 |
0.013 |
5.75 |
97.3 |
| 26 |
291 |
7.59 |
2.21 |
0.013 |
5.71 |
98.0 |
| 28 |
292 |
7.59 |
2.22 |
0.013 |
5.69 |
98.3 |
| 30 |
290 |
7.59 |
2.20 |
0.013 |
5.73 |
97.6 |
[0083] Chlorine dioxide production using chlorite and hydrochloric acid was tested in a
larger scale reactor. The reactor included a 3/8" inch Tee connected to about 91.4
cm of 3/8" inch tubing. Table 8 compares the theoretical production rate with the
actual production rate.
Table 8. Chlorine dioxide conversion efficiency in large scale reactor.
| Theoretical ClO2 Production Rate (Ib/h) |
Average Motive Water Flow Rate (gpm) |
Average ClO2 Concentration in Motive Water (ppm) |
Actual ClO2 Production Rate (Ib/hr) |
Average Conversion Efficiency (%) |
Standard Deviation (%) |
| 0.2 |
1.48 |
258.8 |
0.192 |
96.1 |
21.0 |
| 2.0 |
4.87 |
807.8 |
1.970 |
98.4 |
12.0 |
| 4.0 |
6.00 |
1336.8 |
4.019 |
100.4 |
5.1 |
1. A method of producing chlorine dioxide, comprising:
feeding a first solution comprising an acid through a first feed line (11) into a
mixing device (20);
feeding a second solution comprising chlorite through a second feed (12) line into
the mixing device (20);
mixing the first solution and the second solution in the mixing device (20) to form
a reaction mixture, wherein the mixing device is in fluid communication with a reactor
(21);
feeding the reaction mixture into the reactor (21);
reacting the acid and the chlorite in the reactor (21), wherein the reactor comprises
a proximal portion (22) in fluid communication with the mixing device (20) and a distal
portion (23) in fluid communication with a motive water line (24), wherein the mixing
device (20), the reactor (21), a portion of the first feed line (11), and a portion
of the second feed line (12) are positioned within the motive water line (24); and
mixing chlorine dioxide with motive water in the motive water line (24) at the distal
portion of the reactor (21),
wherein the reactor (21) comprises a coiled configuration having a coil plane angle
of 1 degree to 60 degrees.
2. The method of claim 1, wherein the acid is hydrochloric acid, phosphoric acid, sulfuric
acid, hypochlorous acid, or any combination thereof.
3. A method of producing chlorine dioxide, comprising:
feeding a first solution comprising an acid through a first feed line (11) into a
mixing device (20);
feeding a second solution comprising chlorate and hydrogen peroxide through a second
feed line (12) into the mixing device (20);
mixing the first solution and the second solution in the mixing device (20) to
form a reaction mixture, wherein the mixing device is in fluid communication with
a reactor (21);
feeding the reaction mixture into the reactor (21);
reacting the acid, the chlorate, and the hydrogen peroxide in the reactor (21),
wherein the reactor comprises a proximal portion (22) in fluid communication with
the mixing device and a distal portion (23) in fluid communication with a motive water
line (24), wherein the mixing device (20), the reactor (21), a portion of the first
feed line (11), and a portion of the second feed line (12) are positioned within the
motive water line (24), and
mixing chlorine dioxide with motive water in the motive water line (24) at the distal
portion (23) of the reactor,
wherein the reactor (21) comprises a coiled configuration having a coil plane angle
of 1 degree to 60 degrees.
4. The method of claim 3, wherein the acid is sulfuric acid.
5. A method of treating process water, comprising: producing chlorine dioxide according
to any one of claims 1-4; and injecting the chlorine dioxide and the motive water
into the process water.
6. The method of any one of claims 1-5, further comprising cooling the mixing device
and the reactor with the motive water.
7. The method of any one of claims 1-6, wherein the first feed line and the second feed
line are opposite to and directed against each other.
8. The method of any one of claims 1-7, wherein the motive water line comprises at least
two longitudinal channels through which motive water may flow, and/or wherein the
reactor is operated at a pressure equal to or greater than atmospheric pressure.
9. The method of any one of claims 1-8, wherein the reaction mixture has a residence
time in the reactor of at least 0.1 minute, and a precursor velocity is at least 25
cm/min, wherein the precursor velocity is a velocity of the first and second solutions.
10. The method of any one of claims 1-9, further comprising operating the reactor at a
temperature ranging from 2 °C to 80 °C.
11. The method of any of claims 5-10, wherein a cooling tower comprises the process water.
12. A reactor for producing chlorine dioxide, comprising:
a mixing device (20);
a motive water line (24);
a first feed line (11) in fluid communication with the mixing device;
a second feed line (12) in fluid communication with the mixing device; and
a reactor (21) comprising a proximal portion (22) in fluid communication with the
mixing device and a distal portion (23) in fluid communication with a motive water
line;
wherein the mixing device, the reactor, a portion of the first feed line, and a portion
of the second feed line are positioned within the motive water line and
wherein the reactor comprises a coiled configuration having a coil plane angle of
1 degree to 60 degrees.
13. The reactor of claim 12, wherein the first feed line and the second feed line are
opposite to and directed against each other.
1. Verfahren zum Erzeugen von Chlordioxid, das Folgendes umfasst:
Zuführen einer ersten Lösung, die eine Säure umfasst, durch eine erste Zuführungsleitung
(11) in eine Mischvorrichtung (20);
Zuführen einer zweiten Lösung, die Chlorit umfasst, durch eine zweite Zuführungsleitung
(12) in die Mischvorrichtung (20);
Mischen der ersten Lösung und der zweiten Lösung in der Mischvorrichtung (20), um
ein Reaktionsgemisch auszubilden, wobei die Mischvorrichtung in Fluidverbindung mit
einem Reaktor (21) steht;
Zuführen des Reaktionsgemisches in den Reaktor (21);
Umsetzen der Säure und des Chlorits in dem Reaktor (21), wobei der Reaktor einen proximalen
Abschnitt (22) in Fluidverbindung mit der Mischvorrichtung (20) und einen distalen
Abschnitt (23) in Fluidverbindung mit einer Treibwasserleitung (24) umfasst,
wobei die Mischvorrichtung (20), der Reaktor (21), ein Abschnitt der ersten Zuführungsleitung
(11) und ein Abschnitt der zweiten Zuführungsleitung (12) innerhalb der Treibwasserleitung
(24) positioniert sind; und
Mischen von Chlordioxid mit Treibwasser in der Treibwasserleitung (24) an dem distalen
Abschnitt des Reaktors (21), wobei der Reaktor (21) eine gespulte Konfiguration umfasst,
die einen Winkel einer Spulenebene von 1 Grad bis 60 Grad aufweist.
2. Verfahren nach Anspruch 1, wobei die Säure Chlorwasserstoffsäure, Phosphorsäure, Schwefelsäure,
Hypochlorsäure oder eine beliebige Kombination davon ist.
3. Verfahren zum Erzeugen von Chlordioxid, das Folgendes umfasst:
Zuführen einer ersten Lösung, die eine Säure umfasst, durch eine erste Zuführungsleitung
(11) in eine Mischvorrichtung (20);
Zuführen einer zweiten Lösung, die Chlorat und Wasserstoffperoxid umfasst, durch eine
zweite Zuführungsleitung (12) in die Mischvorrichtung (20);
Mischen der ersten Lösung und der zweiten Lösung in der Mischvorrichtung (20), um
ein Reaktionsgemisch auszubilden, wobei die Mischvorrichtung in Fluidverbindung mit
einem Reaktor (21) steht;
Zuführen des Reaktionsgemisches in den Reaktor (21);
Umsetzen der Säure, des Chlorats und des Wasserstoffperoxids in dem Reaktor (21),
wobei der Reaktor einen proximalen Abschnitt (22) in Fluidverbindung mit der Mischvorrichtung
und einen distalen Abschnitt (23) in Fluidverbindung mit einer Treibwasserleitung
(24) umfasst, wobei die Mischvorrichtung (20), der Reaktor (21), ein Abschnitt der
ersten Zuführungsleitung (11) und ein Abschnitt der zweiten Zuführungsleitung (12)
innerhalb der Treibwasserleitung (24) positioniert sind, und
Mischen von Chlordioxid mit Treibwasser in der Treibwasserleitung (24) an dem distalen
Abschnitt (23) des Reaktors, wobei der Reaktor (21) eine gespulte Konfiguration umfasst,
die einen Winkel der Spulenebene von 1 Grad bis 60 Grad aufweist.
4. Verfahren nach Anspruch 3, wobei die Säure Schwefelsäure ist.
5. Verfahren zum Behandeln von Betriebswasser, das Folgendes umfasst: Erzeugen von Chlordioxid
nach einem der Ansprüche 1-4; und Injizieren des Chlordioxids und des Treibwassers
in das Betriebswasser.
6. Verfahren nach einem der Ansprüche 1-5, das ferner ein Kühlen der Mischvorrichtung
und des Reaktors mit dem Treibwasser umfasst.
7. Verfahren nach einem der Ansprüche 1-6, wobei die erste Zuführungsleitung und die
zweite Zuführungsleitung sich gegenüber liegen und gegeneinander gerichtet sind.
8. Verfahren nach einem der Ansprüche 1-7, wobei die Treibwasserleitung wenigstens zwei
Längskanäle umfasst, durch die Treibwasser fließen kann, und/oder wobei der Reaktor
bei einem Druck betrieben wird, der gleich oder größer als Luftdruck ist.
9. Verfahren nach einem der Ansprüche 1-8, wobei das Reaktionsgemisch eine Verweilzeit
in dem Reaktor von wenigstens 0,1 Minuten aufweist und eine Vorläufergeschwindigkeit
wenigstens 25 cm/min beträgt, wobei die Vorläufergeschwindigkeit eine Geschwindigkeit
der ersten und der zweiten Lösung ist.
10. Verfahren nach einem der Ansprüche 1-9, das ferner das Betreiben des Reaktors bei
einer Temperatur umfasst, die von 2 °C bis 80 °C reicht.
11. Verfahren nach einem der Ansprüche 5-10, wobei ein Kühlturm das Betriebswasser umfasst.
12. Reaktor zum Erzeugen von Chlordioxid, der Folgendes umfasst:
eine Mischvorrichtung (20);
eine Treibwasserleitung (24);
eine erste Zuführungsleitung (11) in Fluidverbindung mit der Mischvorrichtung;
eine zweite Zuführungsleitung (12) in Fluidverbindung mit der Mischvorrichtung; und
einen Reaktor (21), der einen proximalen Abschnitt (22) in Fluidverbindung mit der
Mischvorrichtung und einen distalen Abschnitt (23) in Fluidverbindung mit einer Treibwasserleitung
umfasst;
wobei die Mischvorrichtung, der Reaktor, ein Abschnitt der ersten Zuführungsleitung
und ein Abschnitt der zweiten Zuführungsleitung innerhalb der Treibwasserleitung positioniert
sind und
wobei der Reaktor eine gespulte Konfiguration umfasst, die einen Winkel der Spulenebene
von 1 Grad bis 60 Grad aufweist.
13. Reaktor nach Anspruch 12, wobei die erste Zuführungsleitung und die zweite Zuführungsleitung
sich gegenüber liegen und gegeneinander gerichtet sind.
1. Procédé de production de dioxyde de chlore, comprenant :
l'introduction d'une première solution comprenant un acide à travers une première
conduite d'alimentation (11) dans un dispositif de mélange (20) ;
l'introduction d'une seconde solution comprenant du chlorite à travers une seconde
conduite d'alimentation (12) dans le dispositif de mélange (20) ;
le mélange de la première solution et de la seconde solution dans le dispositif de
mélange (20) pour former un mélange réactionnel, le dispositif de mélange étant en
communication fluidique avec un réacteur (21) ;
l'introduction du mélange réactionnel dans le réacteur (21) ;
la mise en réaction de l'acide et du chlorite dans le réacteur (21), le réacteur comprenant
une partie proximale (22) en communication fluidique avec le dispositif de mélange
(20) et une partie distale (23) en communication fluidique avec une conduite d'eau
motrice (24), le dispositif de mélange (20), le réacteur (21), une partie de la première
conduite d'alimentation (11) et une partie de la seconde conduite d'alimentation (12)
étant positionnés à l'intérieur de la conduite d'eau motrice (24) ; et
le mélange du dioxyde de chlore avec de l'eau motrice dans la conduite d'eau motrice
(24) au niveau de la partie distale du réacteur (21),
le réacteur (21) comprenant une configuration enroulée ayant un angle de plan de bobine
de 1 degré à 60 degrés.
2. Procédé selon la revendication 1, dans lequel l'acide est l'acide chlorhydrique, l'acide
phosphorique, l'acide sulfurique, l'acide hypochloreux ou toute combinaison de ceux-ci.
3. Procédé de production de dioxyde de chlore, comprenant :
l'introduction d'une première solution comprenant un acide à travers une première
conduite d'alimentation (11) dans un dispositif de mélange (20) ;
l'introduction d'une seconde solution comprenant du chlorate et du peroxyde d'hydrogène
à travers une seconde conduite d'alimentation (12) dans le dispositif de mélange (20)
;
le mélange de la première solution et de la seconde solution dans le dispositif de
mélange (20) pour former un mélange réactionnel, le dispositif de mélange étant en
communication fluidique avec un réacteur (21) ;
l'introduction du mélange réactionnel dans le réacteur (21) ;
la mise en réaction de l'acide, du chlorate et du peroxyde d'hydrogène dans le réacteur
(21), le réacteur comprenant une partie proximale (22) en communication fluidique
avec le dispositif de mélange et une partie distale (23) en communication fluidique
avec une conduite d'eau motrice (24), le dispositif de mélange (20), le réacteur (21),
une partie de la première conduite d'alimentation (11) et une partie de la seconde
conduite d'alimentation (12) étant positionnés dans la conduite d'eau motrice (24),
et le mélange du dioxyde de chlore avec de l'eau motrice dans la conduite d'eau motrice
(24) au niveau de la partie distale (23) du réacteur, le réacteur (21) comprenant
une configuration enroulée ayant un angle de plan de bobine de 1 degré à 60 degrés.
4. Procédé selon la revendication 3, dans lequel l'acide est l'acide sulfurique.
5. Procédé de traitement d'eau de process, comprenant : la production de dioxyde de chlore
selon l'une quelconque des revendications 1 à 4 ; et l'injection du dioxyde de chlore
et de l'eau motrice dans l'eau de process.
6. Procédé selon l'une quelconque des revendications 1 à 5, comprenant en outre le refroidissement
du dispositif de mélange et du réacteur avec l'eau motrice.
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel la première conduite
d'alimentation et la seconde conduite d'alimentation sont opposées et dirigées l'une
contre l'autre.
8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel la conduite d'eau
motrice comprend au moins deux canaux longitudinaux à travers lesquels l'eau motrice
peut s'écouler, et/ou dans lequel le réacteur fonctionne à une pression égale ou supérieure
à la pression atmosphérique.
9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel le mélange réactionnel
a un temps de séjour dans le réacteur d'au moins 0,1 minute et une vitesse de précurseur
est d'au moins 25 cm/min, la vitesse du précurseur étant une vitesse des première
et seconde solutions.
10. Procédé selon l'une quelconque des revendications 1 à 9, comprenant en outre le fonctionnement
du réacteur à une température comprise entre 2 °C et 80 °C.
11. Procédé selon l'une quelconque des revendications 5 à 10, dans lequel une tour de
refroidissement comprend l'eau de process.
12. Réacteur de production de dioxyde de chlore, comprenant :
un dispositif de mélange (20) ;
une conduite d'eau motrice (24) ;
une première conduite d'alimentation (11) en communication fluidique avec le dispositif
de mélange ;
une seconde conduite d'alimentation (12) en communication fluidique avec le dispositif
de mélange ; et
un réacteur (21) comprenant une partie proximale (22) en communication fluidique avec
le dispositif de mélange et une partie distale (23) en communication fluidique avec
une conduite d'eau motrice ;
dans lequel le dispositif de mélange, le réacteur, une partie de la première conduite
d'alimentation et une partie de la seconde conduite d'alimentation sont positionnés
dans la conduite d'eau motrice et
dans lequel le réacteur comprend une configuration enroulée ayant un angle de plan
de bobine de 1 degré à 60 degrés.
13. Réacteur selon la revendication 12, dans lequel la première conduite d'alimentation
et la seconde conduite d'alimentation sont opposées et dirigées l'une contre l'autre.