U.S. patent number 3,716,485 [Application Number 05/105,163] was granted by the patent office on 1973-02-13 for process and apparatus for destroying hexavalent chromium in solution.
This patent grant is currently assigned to Ayteks International Corporation. Invention is credited to Richard G. Robertson.
United States Patent |
3,716,485 |
Robertson |
February 13, 1973 |
PROCESS AND APPARATUS FOR DESTROYING HEXAVALENT CHROMIUM IN
SOLUTION
Abstract
An apparatus and method for precipitating and/or destroying a
chemical material comprising a source of material connected in
series with an acidification unit, a reduction unit, and a pH
adjustment unit and with detention chambers between each unit and a
container to allow settling of the newly formed material. This
apparatus provides a circuit through which the reaction takes place
within engineered volumes of piping surrounding the unit.
Inventors: |
Robertson; Richard G. (Parma
Heights, OH) |
Assignee: |
Ayteks International
Corporation (Midina, OH)
|
Family
ID: |
22304392 |
Appl.
No.: |
05/105,163 |
Filed: |
January 11, 1971 |
Current U.S.
Class: |
210/709;
210/195.1; 210/256; 210/719; 210/96.2; 210/712; 210/913 |
Current CPC
Class: |
C02F
1/66 (20130101); Y10S 210/913 (20130101); C02F
2101/22 (20130101) |
Current International
Class: |
C02F
9/00 (20060101); C02c 005/02 () |
Field of
Search: |
;210/50,62,42,60,63,96,195,256,513,61 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Sweglar, C., Plating Solutions, Idustrial Wastes, May 1959, PP.
40-42 .
Pinkerton, H. L., Waste Disposal, Chapt. 11 of Electroplating
Engineering Handbook, pp. 285-287, 290, 294 and 301-305 relied
on.
|
Primary Examiner: Rogers; Michael
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. An apparatus for destroying hexavalent chrome comprising,
a series circuit including a first circuit element,
a chrome source,
a first pump,
an acid injection means,
a first detention and chemical reaction chamber,
a pH sensor means,
a pH correction means,
a means of diverting unacceptable material,
and a second detention chamber connected in series with said first
detention chamber,
said pH sensor being connected to control means on a diversion
valve actuated by said pH sensor whereby said material is
recirculated to said chrome source when the pH of said material is
above a predetermined value,
said pH sensor being connected to a proportional controller whereby
exactly the amount of acid required is injected to achieve desired
pH.
2. The apparatus recited in claim 1 wherein a reducing agent
additive unit is connected in series with said first detention
unit, a means of detecting oxidation, reduction potential, and a
means of correcting amount of reducing agent additive by means of a
proportionate controller in order to achieve exactly the correct
amount of reduction agent,
and said second detention unit is connected in series with said
reducing agent additive unit and said sensing and controlling
means.
3. The apparatus recited in claim 1 wherein a third series of
circuit elements is connected in series with said mentioned
elements,
said third circuit elements comprising a caustic additive unit,
a third detention chamber and a second pH sensing unit,
said second pH sensing unit having means thereon for selectively
directing material from said third detention chamber to said
settling chamber and to recirculate said material to said caustic
unit if the pH is below a predetermined level,
said second pH sensing unit being connected to a third proportional
controller whereby regulation is achieved to inject exactly the
correct amount of alkaline material to obtain desired pH.
4. The apparatus recited in claim 2 wherein a third series of
circuit elements is connected in series with said mentioned
elements,
said third circuit elements comprising a caustic additive unit,
a third detention chamber and a second pH sensing unit,
said second pH sensing unit having means thereon for selectively
directing material from said third detention chamber to said
settling chamber and to recirculate said material to said caustic
unit if the pH is below a predetermined level,
said second pH sensing unit being connected to a third proportional
controller whereby regulation is achieved to inject exactly the
correct amount of alkaline material to obtain desired pH.
5. The apparatus recited in claim 3 wherein a first sight-glass, a
second sight-glass, a third sight-glass, and a fourth sight-glass
are disposed in said circuit, said first sight-glass being disposed
prior to said acid injection point,
said second sight-glass being disposed following said first
detention chamber,
said third sight-glass being disposed in circuit adjacent said
second detention chamber,
and said fourth sight-glass being disposed adjacent said third
detention chamber.
6. The apparatus recited in claim 3 wherein a reducing agent
injection means is connected in series with said circuit between
said acid addition unit and said third circuit element,
and a second retention chamber is provided and an oxidation
reduction potential unit is connected to said circuit and means
connected to said oxidation reduction potential unit whereby said
material will be diverted when the oxidation reduction potential is
at a predetermined value.
7. An apparatus for removing a chemical ingredient from a solution
comprising,
a source of said solution,
a settling tank,
a plurality of large pipes and a plurality of small pipes connected
in series with each other and disposed around said tank,
said pipes each being disposed generally in the form of a helix
around said tank,
means for adding materials to said solution within said large
pipes,
each said large pipe having a diameter and length sufficient to
provide a predetermined detention time during which said solution
is in the particular said large pipe,
said large pipes having sufficient volume to provide said detention
time of a predetermined interval for said liquid flowing in said
circuit,
said material being adapted to precipitate solid material whereby
said solids will settle in said tank.
8. A chromate destruction module comprising a raw waste source,
a treated waste sump,
a circuit connecting said treated waste sump to said raw waste
source,
said circuit comprising a first detention means and a second
detention means, and a third detention means,
means connecting said detention means in series with each
other,
and said means connecting said detention means in series comprising
a first pH sensing device for selectively recirculating said liquid
to said raw waste source when said pH is above a predetermined
value and connecting said circuit to said second detention means
when said pH is below a predetermined value and continuously
adjusting volume of pH adjusting additive such that proper pH is
obtained,
said circuit further comprises means to inject caustic into said
circuit between said second detention means and said third
detention means and means for recirculating said liquid from said
circuit between said third detention means and said second
detention means when the pH of said liquid at said treated waste
sump has a pH below a predetermined value and transferring said
liquid from said circuit between said third detention means and
said treated waste sump when the pH of said liquid has a pH above a
predetermined value.
9. The circuit recited in claim 8 wherein said circuit comprises a
second detention means between said first detention means and said
third detention means,
and means to inject a reducing agent into said circuit at the end
of said first detention means adjacent said second detention
means.
10. The circuit recited in claim 9 wherein means is provided to
recirculate said material from said second detention means to said
chrome source when the ORP thereof is outside of a predetermined
range and a means of continuously adjusting the volume of ORP
adjustive additive such that stabilized proper oxidation reduction
potential is obtained and a means of circulating said material from
said second detention means to said third detention means when the
oxidation reduction potential thereof is within a predetermined
range.
11. The circuit recited in claim 8 wherein said circuit comprises
enlarged size pipes connected by reduced size pipes,
and said enlarged size pipes comprise a retention chamber.
12. The circuit recited in claim 11 wherein said pipes are
connected to a tank and said pipes are arranged generally in the
form of a helix around said tank.
13. A process of destroying hexavalent chromium in solution
comprising circulating said solution from a source through a series
of lines and detention chambers,
and adding acid and caustic to said solution in predetermined
amounts to said solution comprising,
sensing said solution in said lines at a point subsequent to a
first detention chamber and recirculating said solution when the pH
varies above a predetermined value,
passing said solution to an electrical signal means to
proportionally control an acid injection pump controlling the
acidity of said solution,
passing said solution through a reducing agent addition point and
adding a reducing agent to said solution,
passing said solution through a detention chamber to a pH detector
and recirculating said solution when the pH thereof downstream of
the point where said caustic is added is below a predetermined
amount and allowing said liquid to pass through said line when the
pH thereof is between predetermined limits.
14. The method recited in claim 13 wherein said liquid is passed
from said caustic addition unit through an electrical signal to a
proportional controller which transmits the signal to said caustic
injection means whereby the rate of addition of caustic to said
solution is controlled.
Description
GENERAL DESCRIPTION OF THE INVENTION
The apparatus disclosed herein operates on the principle of
acidification, reduction and then pH adjustment to allow settling
of the newly formed material. The chemical reactions take place
within engineered volumes of piping surrounding the module. The
final settling of sludge takes place within the main holding
vessel.
OBJECTS OF THE INVENTION
It is an object of the invention to provide a destruction unit
which is continuous and automatic in operation.
Another object of the invention is to provide a continuous chemical
reaction unit.
GENERAL DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of the machine according to the
invention.
FIG. 2 is a front view of the machine.
FIG. 3 is a right side view of the machine.
FIG. 4 is a left side view of the machine.
FIG. 5 is a top view of the machine.
FIG. 6 is a back view of the machine.
FIG. 7 is a schematic view of the apparatus.
FIG. 8 is a schematic view of the tank.
FIG. 9 is a schematic view of the proportioning pump circuit.
DETAILED DESCRIPTION OF THE DRAWINGS
The circuit shown in FIG. 7 is made up of the three detention
chambers 17, 25 and 32, which are connected in series with the
sight-glasses 14, 18, 26 and 33. These are, in turn, connected in
series with the sump 11 and the holding tank 38.
A pump 13 circulates liquid from the sump 11 through the line 12
and through the system.
Acid is added by means of a proportional acid injection pump 41
through line 16 and check valve V to the acid injection point 15 in
line 12. The detection chamber 17 is sufficiently large in cross
section and is internally baffled in such a manner to provide
approximately one minute of turbulent detention in a typical
example.
A pH cell 19 senses the pH of the liquid after it passes through
sight-glass 18 and controls a valve 20 so that when the pH is above
a predetermined value, the liquid is recirculated through line 21
back to the sump 11. If the pH is at or below the proper value, it
proceeds into line 22. pH cell 19 passes an electrical signal to
proportional controller 44 which, in turn, transmits a signal to
proportional acid injection pump 41. The controller 44 will balance
the pump 41 output rate such that said rate will stabilize at the
desired setpoint to obtain correct pH at pH sensing cell 19. The
liquid thence passes through line 22 to the reducing agent addition
point 23 where a reducing agent injection pump 42 feeds reducing
agent through check valve V and valve 24 and line 24'. The liquid
then continues through the detention chamber 25 where it is held
and mixed for a period of five minutes in a typical installation,
thence through sight-glass 26 to the oxidation reduction potential
detector 27. If the ORP reading is above or below the proper
oxidation reduction potential range, the fluid is diverted through
valve 28 into line 21 which recycles to sump 11. If the oxidation
reduction potential falls within the acceptable range, the fluid
will continue into line 29. ORP cell 27 passes an electrical signal
to proportional controller 45 which, in turn, transmits a signal to
reducing agent injection proportional pump 42. The controller 45
will balance the pump 42 output rate such that said rate will
stabilize at the desired setpoint to obtain correct ORP at sensing
cell 27. The liquid thence passes through line 29 to the caustic
addition point 30 where caustic is added by way of a proportional
caustic injection pump 43 through check valve V and through line 31
and valve 31'. The liquid then continues through the detention unit
32 where it is held and mixed for a period of one minute in a
typical installation, thence through sight-glass 33 and pH sensor
34 and into detention tank 38 primary chamber 35. If the pH is
below a predetermined level, the liquid is recirculated through
pump 36 and line 37 to a point of injection in line 29 prior to
caustic injection point 30. If the liquid is within the desired
limits of pH, the liquid passes undisturbed from primary chamber 35
into sump 38. pH cell 34 passes an electrical signal to
proportional controller 46 which, in turn, transmits a signal to
proportional caustic injection pump 43. The controller 46 will
balance the pump 43 output rate such that said rate will stabilize
at the desired setpoint to obtain correct pH at pH sensing cell 34.
The newly formed solids in the fluid are allowed to settle, for
example, for 2 hours thence clear water is discharged through a pH
cell and recorder 39 which will indicate the pH of the water
discharged from the unit.
EXAMPLE
A typical example of operation will be hexavalent chrome of 1,200
ppm Cr.sup.+.sup.6 at tank 11 which will be pumped by pump 13 at a
rate of 5 gallons per minute through sight-glass 14, chrome liquid
will be yellow in color, and will have 60 cc. per minute of
66.degree. Be.sup.- Sulfuric Acid injected at 15 and it will be
detained for a period of one minute at 17 where its color will
become a reddish-orange, which may be observed at sight-glass 18.
If the pH is below 2.5 at pH cell 19, the liquid will proceed past
point 23 where 12.6 pounds per hour of 98 percent purity sodium
bisulfite will be injected and shall be detained and mixed for a
period of five minutes at 25 thus changing the color of the fluid
to emerald green which can be observed at sight-glass 26. If the
oxidation reduction potential at ORP cell 27 is less than 210 mv
and greater than 190 mv, the liquid shall then proceed past point
30 where 6.8 pounds per hour of 98 percent sodium hydroxide will be
injected and shall be detained and mixed for a period of one minute
at 32 thus changing the color of the fluid to powder blue which can
be observed at sight-glass 33. If the pH of the liquid at pH cell
34 is greater than 8.0, it shall pass into tank 38 where it shall
be held for two hours to allow the chrome hydroxide to settle and
allow the clear supernate to pass through pH recorder 39. Periodic
removal of settled sludge will be accomplished through blowdown
port 40.
Typical chemical reactions that will occur within the above
circuitry are as follows:
Circuit 1:
2na.sub.2 Cr0.sub.4 + 2H.sub.2 SO.sub.4 .fwdarw.H.sub.2 Cr.sub.2
O.sub.7 + H.sub.2 O + 2Na.sub.2 SO.sub.4 .fwdarw.2H.sub.2 CrO.sub.4
+ 2Na.sub.2 SO.sub.4
Circuit 2:
6naHSO.sub.3 + 3H.sub.2 SO.sub.4 + 4H.sub.2 CrO.sub.4
.fwdarw.2Cr.sub.2 (SO.sub.4).sub.3 + 3Na.sub.2 SO.sub.4 + 10H.sub.2
O
Circuit 3:
cr.sub.2 (SO.sub.4).sub.3 + 6NaOH.fwdarw.2Cr(OH).sub.3 .uparw. +
3Na.sub.2 So.sub.4
* * * * *